CA2565969A1 - Wax particles for protection of activators, and multifunctional autonomically healing composite materials - Google Patents
Wax particles for protection of activators, and multifunctional autonomically healing composite materials Download PDFInfo
- Publication number
- CA2565969A1 CA2565969A1 CA002565969A CA2565969A CA2565969A1 CA 2565969 A1 CA2565969 A1 CA 2565969A1 CA 002565969 A CA002565969 A CA 002565969A CA 2565969 A CA2565969 A CA 2565969A CA 2565969 A1 CA2565969 A1 CA 2565969A1
- Authority
- CA
- Canada
- Prior art keywords
- proceeding
- polymerizer
- catalyst
- polymer
- wax
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/22—Auto-repairing or self-sealing arrangements or agents the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/745—Polymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
A composite material comprises (i) a polymer, (ii) a polymerizer, (iii) a protected corresponding activator for the polymerizer, and (iv) a plurality of capsules. The polymerizer is in the capsules, and the corresponding activator is protected with a corresponding encapsulant for the polymer and the polymerizer.
Description
WAX PARTICLES FOR PROTECTION OF ACTIVATORS, AND
MULTIFUNCTIONAL AUTONOMICALLY HEALING COMPOSITE
MATERIALS
FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The subject matter of this application may in part have been funded by the Air Force (AFOSR Grant no. F49620-03-1-0179). The government may have certain rights in this invention.
BACKGROUND
Cracks that form within polymeric composites can be difficult to detect and almost impossible to repair. A successful method of autonomically repairing cracks which has the potential for significantly increasing the longevity of the material has been described in U.S. Patent No. 6,518,330, as well as in publications.1-5 This self-healing system includes a material containing, for example, solid particles of Grubbs' catalyst and capsules containing liquid dicyclopentadiene (DCPD) embedded in an epoxy matrix (Figure 1A). When a crack propagates through the material, it ruptures the microcapsules and releases DCPD into the crack plane. The DCPD then mixes with the Grubbs' catalyst, undergoes Ring Opening Metathesis Polymerization (ROMP), and cures to provide structural continuity where the crack had been.
This system performs well with a relatively large (2.5 wt %) loading of catalyst, but multiple factors have made lower catalyst loadings less effective.
First, the catalyst does not disperse well in the epoxy, so very few (but relatively large) catalyst particles are present on the crack plane when low catalyst loadings are used. Second, the epoxy's curing agent, diethylenetriamine (DETA), destructively attacks Grubbs' catalyst.2 A system where the catalyst is distributed better, and without exposing it to DETA, would allow more efficient use of the catalyst.
MULTIFUNCTIONAL AUTONOMICALLY HEALING COMPOSITE
MATERIALS
FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The subject matter of this application may in part have been funded by the Air Force (AFOSR Grant no. F49620-03-1-0179). The government may have certain rights in this invention.
BACKGROUND
Cracks that form within polymeric composites can be difficult to detect and almost impossible to repair. A successful method of autonomically repairing cracks which has the potential for significantly increasing the longevity of the material has been described in U.S. Patent No. 6,518,330, as well as in publications.1-5 This self-healing system includes a material containing, for example, solid particles of Grubbs' catalyst and capsules containing liquid dicyclopentadiene (DCPD) embedded in an epoxy matrix (Figure 1A). When a crack propagates through the material, it ruptures the microcapsules and releases DCPD into the crack plane. The DCPD then mixes with the Grubbs' catalyst, undergoes Ring Opening Metathesis Polymerization (ROMP), and cures to provide structural continuity where the crack had been.
This system performs well with a relatively large (2.5 wt %) loading of catalyst, but multiple factors have made lower catalyst loadings less effective.
First, the catalyst does not disperse well in the epoxy, so very few (but relatively large) catalyst particles are present on the crack plane when low catalyst loadings are used. Second, the epoxy's curing agent, diethylenetriamine (DETA), destructively attacks Grubbs' catalyst.2 A system where the catalyst is distributed better, and without exposing it to DETA, would allow more efficient use of the catalyst.
BRIEF SUMMARY
In a first aspect, the present invention is a composite material, comprising (i) a polymer, (ii) a polymerizer, (iii) a protected corresponding activator for the polymerizer, and (iv) a plurality of capsules. The polymerizer is in the capsules, and the corresponding activator is protected with a corresponding encapsulant for the polymer and the polymerizer.
In a second aspect, the present invention is a composite material, comprising (i) a polymer, (ii) a polymerizer, (iii) microparticels of a protected corresponding catalyst for the polymerizer, and (iv) a plurality of capsules.
The polymerizer is in the capsules, the corresponding catalyst is protected with a corresponding encapsulant for the polymer and the polymerizer, and the encapsulant comprises wax.
In a third aspect, the present invention is particles, comprising (a) a compound, and (b) a wax, surrounding the compound. The particles are microparticles.
Definitions A polymerizer is a composition that will form a polymer when it comes into contact with a corresponding activator for the polymerizer. Examples of polymerizers include monomers of polymers such as styrene, ethylene, (meth)acrylates, and dicyclopentadiene (DCPD); a monomer of a multi-monomer polymer system such as diols, diamines, and epoxide; and prepolymers such as partially polymerized monomers still capable of further polymerization.
An activator is anything that when contacted or mixed with a polymerizer will form a polymer. Examples of activators are catalysts, initiators, and native activating moieties. A corresponding activator for a polymerizer is an activator that when contacted or mixed with that specific polymerizer will form a polymer.
A catalyst is a compound or moiety that will cause a polymerizable composition to polymerize, and is not always consumed each time it causes polymerization. This is in contrast to initiators and native activating moieties.
In a first aspect, the present invention is a composite material, comprising (i) a polymer, (ii) a polymerizer, (iii) a protected corresponding activator for the polymerizer, and (iv) a plurality of capsules. The polymerizer is in the capsules, and the corresponding activator is protected with a corresponding encapsulant for the polymer and the polymerizer.
In a second aspect, the present invention is a composite material, comprising (i) a polymer, (ii) a polymerizer, (iii) microparticels of a protected corresponding catalyst for the polymerizer, and (iv) a plurality of capsules.
The polymerizer is in the capsules, the corresponding catalyst is protected with a corresponding encapsulant for the polymer and the polymerizer, and the encapsulant comprises wax.
In a third aspect, the present invention is particles, comprising (a) a compound, and (b) a wax, surrounding the compound. The particles are microparticles.
Definitions A polymerizer is a composition that will form a polymer when it comes into contact with a corresponding activator for the polymerizer. Examples of polymerizers include monomers of polymers such as styrene, ethylene, (meth)acrylates, and dicyclopentadiene (DCPD); a monomer of a multi-monomer polymer system such as diols, diamines, and epoxide; and prepolymers such as partially polymerized monomers still capable of further polymerization.
An activator is anything that when contacted or mixed with a polymerizer will form a polymer. Examples of activators are catalysts, initiators, and native activating moieties. A corresponding activator for a polymerizer is an activator that when contacted or mixed with that specific polymerizer will form a polymer.
A catalyst is a compound or moiety that will cause a polymerizable composition to polymerize, and is not always consumed each time it causes polymerization. This is in contrast to initiators and native activating moieties.
Examples of catalysts include ring opening polymerization (ROMP) catalysts such as Grubbs catalyst. A corresponding catalyst for a polymerizer is a catalyst that when contacted or mixed with that specific polymerizer will form a polymer.
An initiator is a compound that will cause a polymerizable composition to polymerize, and is always consumed at the time it causes polymerization.
Examples of initiators are peroxides (which will form a radical to cause polymerization of an unsaturated monomer); a monomer of a multi-monomer polymer system such as diols, diamines, and epoxide; and amines (which will form a polymer with an epoxide). A corresponding initiator for a polymerizer is an initiator that when contacted or mixed with that specific polymerizer will form a polymer.
A native activating moiety is a moiety of a polymer that when mixed or contacted with a polymerizer will form a polymer, and is always consumed at the time it causes polymerization. Examples of a native activating moiety include an amine moiety (which will form a polymer with an epoxide).
A water-deactivatible activator, water-deactivatible catalyst, water-deactivatible initiator, and water-deactivatible native activating moiety, are each a type of activator, catalyst, initiator and native activating moiety, respectively, that has a reduced ability to form a polymer from a polymerizer after exposure to moisture or water. Similarly, a water-deactivatible corresponding activator, water-deactivatible corresponding catalyst, water-deactivatible corresponding initiator, and water-deactivatible corresponding native activating moiety, are each a type of corresponding activator, corresponding catalyst, corresponding initiator and corresponding native activating moiety, respectively, that has a reduced ability to form a polymer from a polymerizer after exposure to moisture or water. Examples of water-deactivatible activators include WCI6, MoCI5 and Et2AICI.
A compound is a molecule that contains at most 100 repeating units.
This is in contrast to a polymer, which contains more than 100 repeating units.
A capsule is a hollow closed object having an aspect ratio of 1:1 to 1:10, that may contain a solid, liquid, gas, or combinations thereof. The aspect ratio of an object is the ratio of the shortest axis to the longest axis;
these axes need not be perpendicular. A capsule may have any shape that falls within this aspect ratio, such as a sphere, a toroid, or an irregular ameboid shape. The surface of a capsule may have any texture, for example rough or smooth.
An encapsulant is a material that will dissolve in a polymerizer and will protect an activator from reaction with materials used to form a polymer. A
corresponding encapsulant for a polymer and for a polymerizer will protect an activator from reaction with materials used to form that specific polymer and will dissolve in that specific polymerizer. Paraffin is an example of an encapsulant. When a compound or polymer is coated with an encasulant, it is referred to as "protected".
A microparticle is a particle with an average diameter of at most 500 micrometers.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1A illustrates a self-healing material using unprotected Grubbs' catalyst.
Figure 1 B illustrates a self-healing material with an activator embedded in a microparticle of an encapsulant.
Figure 2A is a photograph of a sections of epoxy samples cut to -300 m thick containing 2.5 wt % unprotected Grubbs' catalyst.
Figure 2A is a photograph of a sections of epoxy samples cut to -300 m thick containing 5 wt % wax microparticies that contain 5 wt % Grubbs' catalyst.
Figures 3A and 3B illustrate a virgin and a healed load-displacement curves for the cases of (A) low and (B) high non-linearity of the healed crack growth, 1 wt % of microparticles containing 25 wt % catalyst and 5 wt % of microparticles containing 5 wt % catalyst, respectively.
Figures 4A and 4B illustrate the dependence of healing efficiency on (A) the amount of catalyst in the microparticles (with 5 wt % microparticle loading in the epoxy) and (B) the way the catalyst loading in the wax and the microparticle loading in the epoxy are balanced to maintain an overall catalyst concentration of 0.25 wt %; each point is the average of three trials, and the error bars indicate one standard deviation.
DETAILED DESCRIPTION
Taber and coworkers have shown that Grubbs' catalyst can be incorporated into paraffin wax to protect the catalyst from air.6 Paraffin wax is insoluble in DETA and soluble in DCPD, so the wax would be expected to protect Grubbs' catalyst from the detrimental effects of DETA while still allowing the catalyst to be active when exposed to DCPD. However, an established method of dispersing the wax-protected catalyst as small particles in the epoxy matrix was not found in the literature. While the patent literature contains several techniques for producing wax spheres, there are no previously reported methods for producing small wax particles containing reagents.',$
The present invention makes use of the discovery that activators that are protected by an encapsulant allows for the used of activators that might not otherwise be possible, since with being protected they would de-activate while the polymer is being formed. Furthermore, when the activator is protected, significantly less is need to produce an otherwise similar self-healing material. These low loading levels may also improve the physical properties of the polymer before any self-healing takes place.
The present invention includes a composite material, containing capsules 4 and a protected activator 2 in a polymer 6, as shown in Figure 1 B.
The capsules contain a polymerizer. Preferably, the activator is not a corresponding native activating moiety for the polymerizer, and more preferably the activator is a corresponding initiator, or most preferably a corresponding catalyst, for the polymerizer. The activator is protected by a corresponding encapsulant for the polymer and the polymerizer, and more preferably the encapsulant is a wax.
The composite is the same, or similar, to the composite of U.S. Patent No. 6,518,330, (incorporated herein by reference), except that the activator is a protected activator. Furthermore, although less preferred, a native activating moiety may also be used as the activator.
The protected activator may be produced by a variety of methods. For example, a liquid containing the encapsulant may be formed, and powder or small particles of the activator may then be dispersed into the liquid. Then the encapsulant is solidified. Particles, preferably microparticles, of the protected activator are formed. It is these particles that are added to the polymer while it is being formed. In this way, the activator is protected from the substances used to form the polymer.
As an example, if the encapsulant can be melted, the activator may be added, and then the system cooled. The solid protected activator may then be ground up to form particles. Similarly, the encapsulant may be dissolved in a solvent to form a solution, mixed with the activator, the solvent removed, and again the solid mixture ground up to form particles. Alternatively, the molten mixture, or solution, may be formed into particles using the methods described in U.S. Patent No. 6,669,961, incorporated herein by reference.
In another system, the liquid mixture may be poured into a solvent in which both the encapsulant and the activator are insoluble, and then formed into a suspension by rapid stirring; cooling with rapid stirring solidifies the encapsulant, to form particles, more preferably microparticles, of the protected activator. Preferably a surfactant is included.
For example, a wax may be used as the encapsulant, and bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride (first generation Grubbs' catalyst)9 may be used as the activator. The wax-protected catalyst microparticles may be synthesized by pouring a mixture of the molten wax and into a hot, rapidly-stirred, aqueous solution of poly(ethylene-co-maleic anhydride) (EMA). The resulting suspension of molten wax droplets may then be rapidly cooled with the addition of cold water to solidify the wax. The wax microparticles can be filtered, dried, and sifted to give a coarse powder. When this was carried out, microscopy shows that catalyst particles are suspended in the colorless wax giving the microparticles a speckled appearance, but this heterogeneity was not apparent to the unaided eye.
A model system of wax without Grubbs' catalyst shows that the average size of the microparticles can be easily controlled by the rate of stirring. For example, with stirring rates of 450, 900, and 1500 RPM, the average diameters of collected wax microparticles were 150, 90, and 50 pm, respectively. The size distributions are large, but through the use of sieves, narrower size ranges can be isolated. The EMA is included as a surfactant to facilitate the formation of a suspension. In the absence of EMA, the average particle size is increased by more than a factor of three, and excessive non-spherical wax debris is formed.
If the encapsulant may be formed by the reaction of two or more compounds, such as a polymer, then a solution or liquid containing compounds may be formed, the activator mixed in, and then the reaction of the compounds forms the protected activator. Again, the solid may be ground up to form particles.
The encapsulant is soluble in the polymerizer, and solid at room temperature. Examples of encapsulants are polymers and waxes. Waxes include waxy polymers. Waxes are water insoluble, organic materials that are solid or semi-solid at room temperature and usually of lower density than water, and typically can be melted above room temperature to form a liquid.
Preferred waxes include any naturally occurring and synthetic waxes, wax esters, and greases that generally have a melting temperature of 30 C or more with a melting range of less than 10 C and are usually non-reactive with the reagents or solvents to which they are exposed. Examples of waxes are esters of various long-chain (fatty) alcohols and long-chain acids, preferably where at least one member of the ester has 10 or more carbon atoms, including various unsaturated and branched chain types and also those esters of glycerols and sterols. Also, certain free alcohols or acids have wax-like properties of melting temperature and inertness. Examples of saturated fatty acids that can be used are capric, lauric, myristic, palmitic, margaric, stearic, arachidic, behenic, tetracosanic, lignoceric, cerotic, and melissic. Some examples of unsaturated fatty acids that can be used are tiglic, hypogaeic, gaidic, physetoleic, elaidic, oleic, isooleic, erudic, brassidic, and isoerudic.
Some examples of fatty alcohols that can be used are octadecyl, carnaubyl, ceryl, melissyl, and phytol. Also included are various esters of these and other fatty acids with any suitable fatty alcohols, or sterols such as cholesterol, or glycerols. Other examples are natural or suitably modified or derivatized waxes such as various plant derived waxes, greases and oils including carnauba wax, cranberry wax, ouricuri wax, candelilla wax, raphia wax, apple, cotton and cactus waxes; waxes (including greases) produced by bacteria (e.g. cetyl stearate); fungi, protozoa and algae; various invertebrate waxes and greases including insect waxes such as beeswaxes (e.g. triacontyl palmitate, palmatyl palmitate), and Coccus sp. derived waxes (e.g. lac, cochineal and Chinese insect); other animal fats (e.g. triglycerides) and waxes including spermaceti (e.g. cetyl paimitate), lanolin and wool grease.
Also included are various derivatives, extracts, and combinations of these materials. Other suitable waxes are many natural or synthetic hydrocarbons such as white waxes, paraffins, ceresins, vaselines, silicon greases and waxes, polychlorinated or polyfluorinated hydrocarbons, aromatic hydrocarbons (such as naphthalene and durene (1,2,4,5-tetramethylbenzene)), polyether waxes and polyester waxes. Waxy polymers are polymers that have wax-like chemical or physical properties alone or when combined with other waxes. Examples of wax-like polymers are polyethylenes and polypropylenes. Examples of polymers that may be combined with waxes to produce waxy polymers are certain gums and rubbers, various kinds of latex, gutta-percha, balata, chicle and various derivatives. Also included are synthetic rubbers such as isoprene polymers, hydrogenated rubber, butadiene polymers, chloroprene polymers and butyl polymers.
An initiator is a compound that will cause a polymerizable composition to polymerize, and is always consumed at the time it causes polymerization.
Examples of initiators are peroxides (which will form a radical to cause polymerization of an unsaturated monomer); a monomer of a multi-monomer polymer system such as diols, diamines, and epoxide; and amines (which will form a polymer with an epoxide). A corresponding initiator for a polymerizer is an initiator that when contacted or mixed with that specific polymerizer will form a polymer.
A native activating moiety is a moiety of a polymer that when mixed or contacted with a polymerizer will form a polymer, and is always consumed at the time it causes polymerization. Examples of a native activating moiety include an amine moiety (which will form a polymer with an epoxide).
A water-deactivatible activator, water-deactivatible catalyst, water-deactivatible initiator, and water-deactivatible native activating moiety, are each a type of activator, catalyst, initiator and native activating moiety, respectively, that has a reduced ability to form a polymer from a polymerizer after exposure to moisture or water. Similarly, a water-deactivatible corresponding activator, water-deactivatible corresponding catalyst, water-deactivatible corresponding initiator, and water-deactivatible corresponding native activating moiety, are each a type of corresponding activator, corresponding catalyst, corresponding initiator and corresponding native activating moiety, respectively, that has a reduced ability to form a polymer from a polymerizer after exposure to moisture or water. Examples of water-deactivatible activators include WCI6, MoCI5 and Et2AICI.
A compound is a molecule that contains at most 100 repeating units.
This is in contrast to a polymer, which contains more than 100 repeating units.
A capsule is a hollow closed object having an aspect ratio of 1:1 to 1:10, that may contain a solid, liquid, gas, or combinations thereof. The aspect ratio of an object is the ratio of the shortest axis to the longest axis;
these axes need not be perpendicular. A capsule may have any shape that falls within this aspect ratio, such as a sphere, a toroid, or an irregular ameboid shape. The surface of a capsule may have any texture, for example rough or smooth.
An encapsulant is a material that will dissolve in a polymerizer and will protect an activator from reaction with materials used to form a polymer. A
corresponding encapsulant for a polymer and for a polymerizer will protect an activator from reaction with materials used to form that specific polymer and will dissolve in that specific polymerizer. Paraffin is an example of an encapsulant. When a compound or polymer is coated with an encasulant, it is referred to as "protected".
A microparticle is a particle with an average diameter of at most 500 micrometers.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1A illustrates a self-healing material using unprotected Grubbs' catalyst.
Figure 1 B illustrates a self-healing material with an activator embedded in a microparticle of an encapsulant.
Figure 2A is a photograph of a sections of epoxy samples cut to -300 m thick containing 2.5 wt % unprotected Grubbs' catalyst.
Figure 2A is a photograph of a sections of epoxy samples cut to -300 m thick containing 5 wt % wax microparticies that contain 5 wt % Grubbs' catalyst.
Figures 3A and 3B illustrate a virgin and a healed load-displacement curves for the cases of (A) low and (B) high non-linearity of the healed crack growth, 1 wt % of microparticles containing 25 wt % catalyst and 5 wt % of microparticles containing 5 wt % catalyst, respectively.
Figures 4A and 4B illustrate the dependence of healing efficiency on (A) the amount of catalyst in the microparticles (with 5 wt % microparticle loading in the epoxy) and (B) the way the catalyst loading in the wax and the microparticle loading in the epoxy are balanced to maintain an overall catalyst concentration of 0.25 wt %; each point is the average of three trials, and the error bars indicate one standard deviation.
DETAILED DESCRIPTION
Taber and coworkers have shown that Grubbs' catalyst can be incorporated into paraffin wax to protect the catalyst from air.6 Paraffin wax is insoluble in DETA and soluble in DCPD, so the wax would be expected to protect Grubbs' catalyst from the detrimental effects of DETA while still allowing the catalyst to be active when exposed to DCPD. However, an established method of dispersing the wax-protected catalyst as small particles in the epoxy matrix was not found in the literature. While the patent literature contains several techniques for producing wax spheres, there are no previously reported methods for producing small wax particles containing reagents.',$
The present invention makes use of the discovery that activators that are protected by an encapsulant allows for the used of activators that might not otherwise be possible, since with being protected they would de-activate while the polymer is being formed. Furthermore, when the activator is protected, significantly less is need to produce an otherwise similar self-healing material. These low loading levels may also improve the physical properties of the polymer before any self-healing takes place.
The present invention includes a composite material, containing capsules 4 and a protected activator 2 in a polymer 6, as shown in Figure 1 B.
The capsules contain a polymerizer. Preferably, the activator is not a corresponding native activating moiety for the polymerizer, and more preferably the activator is a corresponding initiator, or most preferably a corresponding catalyst, for the polymerizer. The activator is protected by a corresponding encapsulant for the polymer and the polymerizer, and more preferably the encapsulant is a wax.
The composite is the same, or similar, to the composite of U.S. Patent No. 6,518,330, (incorporated herein by reference), except that the activator is a protected activator. Furthermore, although less preferred, a native activating moiety may also be used as the activator.
The protected activator may be produced by a variety of methods. For example, a liquid containing the encapsulant may be formed, and powder or small particles of the activator may then be dispersed into the liquid. Then the encapsulant is solidified. Particles, preferably microparticles, of the protected activator are formed. It is these particles that are added to the polymer while it is being formed. In this way, the activator is protected from the substances used to form the polymer.
As an example, if the encapsulant can be melted, the activator may be added, and then the system cooled. The solid protected activator may then be ground up to form particles. Similarly, the encapsulant may be dissolved in a solvent to form a solution, mixed with the activator, the solvent removed, and again the solid mixture ground up to form particles. Alternatively, the molten mixture, or solution, may be formed into particles using the methods described in U.S. Patent No. 6,669,961, incorporated herein by reference.
In another system, the liquid mixture may be poured into a solvent in which both the encapsulant and the activator are insoluble, and then formed into a suspension by rapid stirring; cooling with rapid stirring solidifies the encapsulant, to form particles, more preferably microparticles, of the protected activator. Preferably a surfactant is included.
For example, a wax may be used as the encapsulant, and bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride (first generation Grubbs' catalyst)9 may be used as the activator. The wax-protected catalyst microparticles may be synthesized by pouring a mixture of the molten wax and into a hot, rapidly-stirred, aqueous solution of poly(ethylene-co-maleic anhydride) (EMA). The resulting suspension of molten wax droplets may then be rapidly cooled with the addition of cold water to solidify the wax. The wax microparticles can be filtered, dried, and sifted to give a coarse powder. When this was carried out, microscopy shows that catalyst particles are suspended in the colorless wax giving the microparticles a speckled appearance, but this heterogeneity was not apparent to the unaided eye.
A model system of wax without Grubbs' catalyst shows that the average size of the microparticles can be easily controlled by the rate of stirring. For example, with stirring rates of 450, 900, and 1500 RPM, the average diameters of collected wax microparticles were 150, 90, and 50 pm, respectively. The size distributions are large, but through the use of sieves, narrower size ranges can be isolated. The EMA is included as a surfactant to facilitate the formation of a suspension. In the absence of EMA, the average particle size is increased by more than a factor of three, and excessive non-spherical wax debris is formed.
If the encapsulant may be formed by the reaction of two or more compounds, such as a polymer, then a solution or liquid containing compounds may be formed, the activator mixed in, and then the reaction of the compounds forms the protected activator. Again, the solid may be ground up to form particles.
The encapsulant is soluble in the polymerizer, and solid at room temperature. Examples of encapsulants are polymers and waxes. Waxes include waxy polymers. Waxes are water insoluble, organic materials that are solid or semi-solid at room temperature and usually of lower density than water, and typically can be melted above room temperature to form a liquid.
Preferred waxes include any naturally occurring and synthetic waxes, wax esters, and greases that generally have a melting temperature of 30 C or more with a melting range of less than 10 C and are usually non-reactive with the reagents or solvents to which they are exposed. Examples of waxes are esters of various long-chain (fatty) alcohols and long-chain acids, preferably where at least one member of the ester has 10 or more carbon atoms, including various unsaturated and branched chain types and also those esters of glycerols and sterols. Also, certain free alcohols or acids have wax-like properties of melting temperature and inertness. Examples of saturated fatty acids that can be used are capric, lauric, myristic, palmitic, margaric, stearic, arachidic, behenic, tetracosanic, lignoceric, cerotic, and melissic. Some examples of unsaturated fatty acids that can be used are tiglic, hypogaeic, gaidic, physetoleic, elaidic, oleic, isooleic, erudic, brassidic, and isoerudic.
Some examples of fatty alcohols that can be used are octadecyl, carnaubyl, ceryl, melissyl, and phytol. Also included are various esters of these and other fatty acids with any suitable fatty alcohols, or sterols such as cholesterol, or glycerols. Other examples are natural or suitably modified or derivatized waxes such as various plant derived waxes, greases and oils including carnauba wax, cranberry wax, ouricuri wax, candelilla wax, raphia wax, apple, cotton and cactus waxes; waxes (including greases) produced by bacteria (e.g. cetyl stearate); fungi, protozoa and algae; various invertebrate waxes and greases including insect waxes such as beeswaxes (e.g. triacontyl palmitate, palmatyl palmitate), and Coccus sp. derived waxes (e.g. lac, cochineal and Chinese insect); other animal fats (e.g. triglycerides) and waxes including spermaceti (e.g. cetyl paimitate), lanolin and wool grease.
Also included are various derivatives, extracts, and combinations of these materials. Other suitable waxes are many natural or synthetic hydrocarbons such as white waxes, paraffins, ceresins, vaselines, silicon greases and waxes, polychlorinated or polyfluorinated hydrocarbons, aromatic hydrocarbons (such as naphthalene and durene (1,2,4,5-tetramethylbenzene)), polyether waxes and polyester waxes. Waxy polymers are polymers that have wax-like chemical or physical properties alone or when combined with other waxes. Examples of wax-like polymers are polyethylenes and polypropylenes. Examples of polymers that may be combined with waxes to produce waxy polymers are certain gums and rubbers, various kinds of latex, gutta-percha, balata, chicle and various derivatives. Also included are synthetic rubbers such as isoprene polymers, hydrogenated rubber, butadiene polymers, chloroprene polymers and butyl polymers.
The table below lists examples of encapsulants.
Paraffin wax Gelatin Carboxymethyl cellulose Ceresine wax Guar gum Ethyl cellulose Beeswax Acacia (gum arabic) Methyl cellulose Microcrystalline wax Carob bean gum Cellulose acetate Petroleum wax Carrageenan Cellulose nitrate Xanthan gum Food starch Silcone rubber Polyurethane Polyethylene glycol Butyl rubber Epoxy Polystyrene Butadiene-styrene rubber Polyvinyl alcohol Polymethyl methacrylate Polyvinyl acetate Polypropylene Polydimethyl siloxane Polyvinyl chloride Urea formaldehyde Polyvinyl alcohol Polyethylene Polycarbonate Polyamide The term "soluble" as used herein, particularly in the case of waxy polymers, also includes swellable; i.e. the polymerizer need not actually dissolve the wax, as long as it can penetrate the encapsulant sufficiently to allow polymerization of the polymerizer when it contacts the activator.
The capsules contain a polymerizer. The polymerizer contains a polymerizable compound such as a monomer or prepolymer, and may optionally contain other ingredients, such as other monomers and/or prepolymers, stabilizers, solvents, viscosity modifiers such as polymers, odorants, colorant and dyes, blowing agents, antioxidants, and co-catalysts.
Preferably, the polymerizer is a liquid at room temperatue.
Preferably, the activator is a catalyst or an initiator. Examples of polymerizable compounds are cyclic olefins, preferably containing 4-50 carbon atoms and optionally containing heteratoms, such as DCPD, substituted DCPDs, norbornene, substituted norbornene, cyclooctadiene, and substituted cyclooctadiene. Corresponding catalysts for these are ring opening metathesis polymerization (ROMP) catalysts such as Schrock catalysts'a,15 Another example of polymerizable compounds are lactones such as caprolactone, and lactams, that when polymerized will form polyesters and nylons, respectively. Corresponding catalysts for these are cyclic ester polymerization catalysts and cyclic amide polymerization catalysts, such as scandium triflate.
Furthermore, a polymerizer may contain a polymerizable compound and one part of a two-part catalyst, with a corresponding initiator being the other part of the two-part catalyst. For example, the polymerizable compound may be a cyclic olefin; one part of a two-part catalyst may be a tungsten compound, such as an organoammonium tungstate, an organoarsonium tungstate, or an organophosphonium tungstate; or a molybdenum compound, such as organoammonium molybdate, an organoarsonium molybdate, or an organophosphonium molybdate. The second part of the two-part catalyst may be an alkyl aluminum compound, such as an alkoxyalkylaluminum halide, an aryloxyalkylaluminum halide, or a metaloxyalkylaluminum halide in which the metal in the compound is tin, lead, or aluminum; or an organic tin compound, such as a tetraalkyltin, a trialkyltin hydride, or a triaryltin hydride.
In another such system, the polymerizable compound may be unsaturated compounds such as acrylates; acrylic acids; alkyl acrylates; alkyl acrylic acids; styrenes; isoprene; and butadiene. In this case, atom transfer radical polymerization (ATRP) may be used, with one of the two components being mixed with the polymerizable compound and the other acting as the initiator: one component being an organohalide such as 1-chloro-l-phenylethane, and the other component could be a copper(l) source such as copper(l) bipyridyl complex. Alternatively, one component could be a peroxide such as benzoyl peroxide, and the other component could be a nitroxo precursor such as 2,2,6,6-tetramethylpiperidinyl-l-oxy (TEMPO).
These systems are described in Malcolm P. Stevens; Polymer Chemistry: An Introduction, 3rd Edition; New York: Oxford University Press, 1999, p. 184 -186.
In another such system, the polymerizable compound may contain isocyanate functional groups (-N=C=O) with hydroxyl functional groups (-OH).
Paraffin wax Gelatin Carboxymethyl cellulose Ceresine wax Guar gum Ethyl cellulose Beeswax Acacia (gum arabic) Methyl cellulose Microcrystalline wax Carob bean gum Cellulose acetate Petroleum wax Carrageenan Cellulose nitrate Xanthan gum Food starch Silcone rubber Polyurethane Polyethylene glycol Butyl rubber Epoxy Polystyrene Butadiene-styrene rubber Polyvinyl alcohol Polymethyl methacrylate Polyvinyl acetate Polypropylene Polydimethyl siloxane Polyvinyl chloride Urea formaldehyde Polyvinyl alcohol Polyethylene Polycarbonate Polyamide The term "soluble" as used herein, particularly in the case of waxy polymers, also includes swellable; i.e. the polymerizer need not actually dissolve the wax, as long as it can penetrate the encapsulant sufficiently to allow polymerization of the polymerizer when it contacts the activator.
The capsules contain a polymerizer. The polymerizer contains a polymerizable compound such as a monomer or prepolymer, and may optionally contain other ingredients, such as other monomers and/or prepolymers, stabilizers, solvents, viscosity modifiers such as polymers, odorants, colorant and dyes, blowing agents, antioxidants, and co-catalysts.
Preferably, the polymerizer is a liquid at room temperatue.
Preferably, the activator is a catalyst or an initiator. Examples of polymerizable compounds are cyclic olefins, preferably containing 4-50 carbon atoms and optionally containing heteratoms, such as DCPD, substituted DCPDs, norbornene, substituted norbornene, cyclooctadiene, and substituted cyclooctadiene. Corresponding catalysts for these are ring opening metathesis polymerization (ROMP) catalysts such as Schrock catalysts'a,15 Another example of polymerizable compounds are lactones such as caprolactone, and lactams, that when polymerized will form polyesters and nylons, respectively. Corresponding catalysts for these are cyclic ester polymerization catalysts and cyclic amide polymerization catalysts, such as scandium triflate.
Furthermore, a polymerizer may contain a polymerizable compound and one part of a two-part catalyst, with a corresponding initiator being the other part of the two-part catalyst. For example, the polymerizable compound may be a cyclic olefin; one part of a two-part catalyst may be a tungsten compound, such as an organoammonium tungstate, an organoarsonium tungstate, or an organophosphonium tungstate; or a molybdenum compound, such as organoammonium molybdate, an organoarsonium molybdate, or an organophosphonium molybdate. The second part of the two-part catalyst may be an alkyl aluminum compound, such as an alkoxyalkylaluminum halide, an aryloxyalkylaluminum halide, or a metaloxyalkylaluminum halide in which the metal in the compound is tin, lead, or aluminum; or an organic tin compound, such as a tetraalkyltin, a trialkyltin hydride, or a triaryltin hydride.
In another such system, the polymerizable compound may be unsaturated compounds such as acrylates; acrylic acids; alkyl acrylates; alkyl acrylic acids; styrenes; isoprene; and butadiene. In this case, atom transfer radical polymerization (ATRP) may be used, with one of the two components being mixed with the polymerizable compound and the other acting as the initiator: one component being an organohalide such as 1-chloro-l-phenylethane, and the other component could be a copper(l) source such as copper(l) bipyridyl complex. Alternatively, one component could be a peroxide such as benzoyl peroxide, and the other component could be a nitroxo precursor such as 2,2,6,6-tetramethylpiperidinyl-l-oxy (TEMPO).
These systems are described in Malcolm P. Stevens; Polymer Chemistry: An Introduction, 3rd Edition; New York: Oxford University Press, 1999, p. 184 -186.
In another such system, the polymerizable compound may contain isocyanate functional groups (-N=C=O) with hydroxyl functional groups (-OH).
For this system, the polymerizable material may for example be a compound containing both an isocyanate group and a hydroxyl group, or two different compounds, one compound containing at least two isocyanate groups and the other compound containing at least two hydroxyl groups. The reaction between an isocyanate group and a hydroxyl group can form a urethane linkage (-N-C(=O)-O-) between the compounds, possibly releasing carbon dioxide. This carbon dioxide can provide for the creation of expanded polyurethane foam; optionally the polymerizer may contain a blowing agent, for example a volatile liquid such as dichloromethane. In this case, condensation polymerization may be used, with one of the two components being mixed with the polymerizable compound and the other acting as the initiator: for example, one component could be an alkyltin compound such as stannous 2-ethylhexanoate, and the other component could be a tertiary amine such as diazabicyclo[2.2.2]octane (DABCO). These systems are described in Malcolm P. Stevens; Polymer Chemistry: An Introduction, 3rd Edition'; New York: Oxford University Press, 1999, p. 378 - 381.
By using a protected activator, a larger variety of polymerizers and corresponding activators, particularly catalysts, may be used. The table below includes additional polymerizers and corresponding activatiors.
Ring Opening Metathesis Polymerization Monomers Catalysts endo-DCPD Grubbs' catalysts (particularly exo-DCPD bis(tricyclohexylphosphine) norbornene benzylidine ruthenium(IV) chloride and cyclooctene benzylidene[1,3-bis(2,4,6-cyclooctadiene trimethylphenyl)-2-imidazolidinylidene]
dichloro(tricyclohexylphosphine) ruthenium) RuC13-3H2O
transition metal compounds (particularly WCI6, WCIOa, MoCI5,and ReC15) and either an acetylene cocatalyst (particularly phenylacetylene and 1-alkynes) or an organometallic co-catalyst (particularly Bu'3AI, Et3AI, Et2AICI, EtAICIz, Me4Sn, Et4Sn,BuaSn, Ph4Sn, Me2(aIIyI)2Si, or aluminoxanes) Schrock catalysts (particularly 2,6-diisopropylphenylimidoneophylidene molybdenum (VI) bis(t-butoxide) and 2,6-Diisopropylphenylimidoneophylidene molybdenum (VI) bis(hexafluoro-t-butoxide)) Ziegler-Natta Polymerization Monomer Catalysts dicylopentadiene metallocene catalyst (particularly based ethylidenenorbornene on Zr, Ti, or Hf) with methylaluminoxane hexadiene 1-decene vinyl ethers Cationic Polymerization Monomers Catalysts alpha-methylstyrene cation-forming initiator (particularly H20, vinyl ethers Ph3CCI, tropylium halides, or 12) with a coumarone Lewis acid coinitiator (particularly indene AICI3,AIBr3, BF3, TiCI4, and SnCI4) mineral acid (Particularly H2SO4 and H3P04) The polymer contains both capsules and a corresponding activator for the polymerizer. Optionally, a set of capsules may be present that contain one or more additional ingredients, such as stabilizers, solvents, viscosity modifiers such as polymers, odorants, colorant and dyes, blowing agents, antioxidants, and co-catalysts.
Preferably, the capsules have an average diameter of 10 nm to 1 mm, more preferably 30-500 pm, most preferably to 50-300 pm. The capsules have an aspect ratio of 1:1 to 1:10, preferably 1:1 to 1:5, more preferably 1:1 to 1:3, and even more preferably 1:1 to 1:2, and most preferably 1:1 to 1:1.5.
The wall thickness of the capsules is preferably 100 nm to 3 pm. The selection of capsule walls thickness depends on the polymer in the composite.
For example, capsule walls that are too thick will not rupture when a crack approaches, while capsules with very thin walls will break during processing.
The adhesion between the capsules and the polymer of the composite influences whether the capsules will rupture or debond in the presence of an approaching crack. To promote the adhesion between the polymer and capsule wall, various silane coupling agents may be used. Typically, these are compounds of the formula R-SiX3 Where R is preferably a reactive group R' separated by a propylene group from silicon, and X is an alkoxy group (preferably methoxy), such as R'CH2CHZCH2Si(OCH3)3. Examples include silane coupling agents available from DOW CORNING (with reactive group following the name in parentheses): Z6020 (Diamino); Z6030 (Methacrylate);
Z6032 (Styrylamine Cationic); Z6040 (Epoxy); and Z6075 (Vinyl).
To increase the adhesion between the capsules and a polymer in the composite, the capsules may be treated by washing them in a solution of the coupling agent. For example, urea-formaldehyde capsules may be washed in a solution of Silane Z6020 or Z6040 and hexane (1:20 wt.) followed by adding Silane Z6032 to the polymer (1 % wt.).
Capsules may be made by a variety of techniques, and from a variety of materials, such as those described in Microencapsulation: Methods and Industrial Applications Ed. Benita, Simon Marcel Dekker, New York, 1996;
Microencapsulation: Processes and Applications Ed. Vandegaer, J. Plenum Press, New York, 1974; and Microcapsule Processing and Technology Kondo, A. Marcel Dekker, New York, 1979. Examples of materials from which the capsules may be made, and the techniques for making them include:
By using a protected activator, a larger variety of polymerizers and corresponding activators, particularly catalysts, may be used. The table below includes additional polymerizers and corresponding activatiors.
Ring Opening Metathesis Polymerization Monomers Catalysts endo-DCPD Grubbs' catalysts (particularly exo-DCPD bis(tricyclohexylphosphine) norbornene benzylidine ruthenium(IV) chloride and cyclooctene benzylidene[1,3-bis(2,4,6-cyclooctadiene trimethylphenyl)-2-imidazolidinylidene]
dichloro(tricyclohexylphosphine) ruthenium) RuC13-3H2O
transition metal compounds (particularly WCI6, WCIOa, MoCI5,and ReC15) and either an acetylene cocatalyst (particularly phenylacetylene and 1-alkynes) or an organometallic co-catalyst (particularly Bu'3AI, Et3AI, Et2AICI, EtAICIz, Me4Sn, Et4Sn,BuaSn, Ph4Sn, Me2(aIIyI)2Si, or aluminoxanes) Schrock catalysts (particularly 2,6-diisopropylphenylimidoneophylidene molybdenum (VI) bis(t-butoxide) and 2,6-Diisopropylphenylimidoneophylidene molybdenum (VI) bis(hexafluoro-t-butoxide)) Ziegler-Natta Polymerization Monomer Catalysts dicylopentadiene metallocene catalyst (particularly based ethylidenenorbornene on Zr, Ti, or Hf) with methylaluminoxane hexadiene 1-decene vinyl ethers Cationic Polymerization Monomers Catalysts alpha-methylstyrene cation-forming initiator (particularly H20, vinyl ethers Ph3CCI, tropylium halides, or 12) with a coumarone Lewis acid coinitiator (particularly indene AICI3,AIBr3, BF3, TiCI4, and SnCI4) mineral acid (Particularly H2SO4 and H3P04) The polymer contains both capsules and a corresponding activator for the polymerizer. Optionally, a set of capsules may be present that contain one or more additional ingredients, such as stabilizers, solvents, viscosity modifiers such as polymers, odorants, colorant and dyes, blowing agents, antioxidants, and co-catalysts.
Preferably, the capsules have an average diameter of 10 nm to 1 mm, more preferably 30-500 pm, most preferably to 50-300 pm. The capsules have an aspect ratio of 1:1 to 1:10, preferably 1:1 to 1:5, more preferably 1:1 to 1:3, and even more preferably 1:1 to 1:2, and most preferably 1:1 to 1:1.5.
The wall thickness of the capsules is preferably 100 nm to 3 pm. The selection of capsule walls thickness depends on the polymer in the composite.
For example, capsule walls that are too thick will not rupture when a crack approaches, while capsules with very thin walls will break during processing.
The adhesion between the capsules and the polymer of the composite influences whether the capsules will rupture or debond in the presence of an approaching crack. To promote the adhesion between the polymer and capsule wall, various silane coupling agents may be used. Typically, these are compounds of the formula R-SiX3 Where R is preferably a reactive group R' separated by a propylene group from silicon, and X is an alkoxy group (preferably methoxy), such as R'CH2CHZCH2Si(OCH3)3. Examples include silane coupling agents available from DOW CORNING (with reactive group following the name in parentheses): Z6020 (Diamino); Z6030 (Methacrylate);
Z6032 (Styrylamine Cationic); Z6040 (Epoxy); and Z6075 (Vinyl).
To increase the adhesion between the capsules and a polymer in the composite, the capsules may be treated by washing them in a solution of the coupling agent. For example, urea-formaldehyde capsules may be washed in a solution of Silane Z6020 or Z6040 and hexane (1:20 wt.) followed by adding Silane Z6032 to the polymer (1 % wt.).
Capsules may be made by a variety of techniques, and from a variety of materials, such as those described in Microencapsulation: Methods and Industrial Applications Ed. Benita, Simon Marcel Dekker, New York, 1996;
Microencapsulation: Processes and Applications Ed. Vandegaer, J. Plenum Press, New York, 1974; and Microcapsule Processing and Technology Kondo, A. Marcel Dekker, New York, 1979. Examples of materials from which the capsules may be made, and the techniques for making them include:
urea-formaldehyde, formed by in situ polymerization; gelatin, formed by complex coacervation; polyurea, formed by the reaction of isocyanates with a diamine or a triamine, depending on the degree of crosslinking desired (the extent of crosslinking also determines the brittleness of the capsule);and polyamide, formed by the use of a suitable acid chloride and a water soluble triamine.
The polymer may be any polymeric material into which the capsules may be dispersed. Examples include polyamides such as nylons; polyesters such as poly(ethylene terephthalate) and polycaprolactone; polycarbonates;
polyethers such as epoxides; polyimides such as polypyromellitimide (for example KAPTAN); phenol-formaldehyde resins (for example BAKELITE);
amine-formaldehyde resins such as a melamine resin; polysulfones;
poly(acrylonitrile-butadiene-styrene) (ABS); polyurethanes; polyolefins such as polyethylene, polystyrene, polyacrylonitrile, polyvinyls, polyvinyl chloride, poly(DCPD) and poly(methyl methacrylate); polysilanes such as poly(carborane-siloxane); and polyphosphazenes.
The capsules and protected activator (such as the catalyst or initiator) may be dispersed into the polymer by forming the polymer around the capsules and activator, such as by polymerizing monomer to form the polymer with the capsules and activator mixed into the monomer. Alternatively, the polymer may be first formed, and then the capsules and protected activator mixed in. For example, the polymer may be dissolved in a solvent and the capsules and protected activator mixed into the solution, followed by removal of the solvent. Furthermore, other components may be added to the polymer, such as fibers, fillers, adhesion modifiers, blowing agents, anti-oxidants, colorants and dyes, and fragrances.
EXAMPLES
Synthesis of Wax Microparticles Containing Grubbs' Catalyst.
In an N2-filled glovebox, paraffin wax (Aldrich, 10.0 g, mp = 58-62 C) and Grubbs' Catalyst (Strem, 525 mg) were sealed in a vial. The vial was removed from the glovebox. A solution of water (225 mL), poly(ethylene-co-maleic anhydride) (0.63 g, 0.28 wt %) and octanol (1 drop) was placed in a 1000 mL beaker in an 82 C water bath and stirred with a mechanical stirrer at 900 RPM. The vial containing the wax and the catalyst was submerged in the same 82 C water bath. After 10 min, the wax had melted and the aqueous solution had reached 65-70 C. The vial with the molten wax was shaken to disperse the catalyst. The vial was then opened (in air), and the wax was poured into the aqueous solution. After 2 min, cold water (600 mL, 0 C) was quickly added, and the stirring was stopped. The microparticles were collected by filtration and dried under vacuum.
Kinetics of ROMP Catalyzed by Wax-Protected Grubbs' Catalyst In an N2-filled glovebox, a stock solution of PCy3 (4.1 mM) in d-8 toluene was prepared. This stock solution was then added to an NMR tube with wax microparticles (140 mg) containing 5 wt % Grubbs' catalyst (0.0085 mmol). A control sample with unprotected Grubbs' catalyst (7.0 mg, 0.0085 mmol) and wax microparticles without included catalyst (133 mg) was prepared using the same stock solution of PCy3 in d-8 toluene. The total weight of each solution was 0.70 g. The samples were capped with septa and removed from the glovebox. Mesitylene (10 L) was added via syringe as an internal standard. The ROMP kinetics with endo-DCPD were obtained by in situ'H NMR as described previously.10 Fracture Tests Using the established method,',2," fracture samples with a tapered double-cantilever beam (TDCB) geometry were prepared containing 10 wt %
of 180 m diameter DCPD-filled microcapsules.1 2," The TDCB geometry, developed by Mostovoy et al.,12 provided a crack-length-independent measure of strain energy:
,6 30 Jc = ~ ~c ~ (1) Thus, the geometric term a, the critical fracture load Pc, and the term Q
were the only required measurements. As discussed by Brown et al., it can be experimentally determined that a= 11.2x103 m"312 for the TDCB sample geometry .2 4 The nonlinearity term ,6 was introduced to account for nonlinear elastic behavior of the healed interface prior to crack growth. For fracture of the virgin (linear elastic) material, ,6 is uniquely unity (1); for fracture of the healed materials, 8 is calculated by dividing the area under the measured load-displacement curve up to the point of crack growth by the area under a linear elastic load displacement curve of the same initial compliance and peak load. Virgin fracture was brittle in all cases and was statistically independent of microparticle size, concentration, or catalyst concentration (Jc = Gc _ 250 50 J/m2, Kic = 0.84 0.07 MPa m1/2).
Healing efficiency was assessed by modifying the protocol established by White et al.' TDCB fracture specimens were pin loaded and tested under displacement control, at 5 m/s displacement rate. Samples were tested to failure, measuring initial compliance and peak load to establish the initial (virgin) strain energy release rate. Load was then removed, and the crack faces were allowed to come in contact. Samples were retested after 24 hours to determine the healed, non-linear strain energy release rate. Crack healing efficiency, 77, was defined as the ability to recover strain energy:13 77 _ ~Cheuled = ~ PCheuled (2) J p CvirEin C virgin The reactivity of the wax-embedded catalyst was quantified by using in situ'H NMR to measure the ROMP kinetics of endo-DCPD in the presence of the microparticles.10 The rate constant for ROMP of DCPD measured for a sample prepared with Grubbs' catalyst obtained from the wax microparticles was 0.0162 s-'. An analogous control sample prepared with unprotected Grubbs' catalyst had a rate constant of 0.0179 s-', which shows that the process of embedding the catalyst in wax microparticies only reduces the reactivity by 9%. This small reduction in rate shows that the brief exposure of the catalyst to heat and air only mildly affects its reactivity. Furthermore, when the wax-protected catalyst is melted and cast into new microparticles, the measured rate constant does not change significantly from that of the original microparticles. Because this recycling process can be done without loss of reactivity, microparticles that fall outside the desired size range can be reformed with useful diameters, thus avoiding the costly waste of catalyst.
The wax greatly increases the resistance of the catalyst to ethylenediamine (EDA). As a control, a sample of unprotected Grubbs' catalyst was exposed to neat EDA and immediately placed under vacuum.
Within 10 min, the EDA had completely evaporated. The same procedure was performed with wax-protected catalyst microparticles. NMR samples were prepared using the non-volatile catalyst and wax residues, and the kinetics of ROMP of DCPD using the exposed catalyst were measured. The wax preserved 69% of the catalyst's reactivity while the unprotected catalyst showed no reactivity. Because of its low volatility, DETA could not be used in a similar experiment, but the wax appears to similarly protect the catalyst from DETA. Because the wax can protect the catalyst from the DETA used to prepare self-healing samples, less catalyst will be destroyed during sample preparation and healing should be possible with reduced catalyst loadings.
The wax microparticles also appear to be useful for dispersing Grubbs' catalyst uniformly throughout the epoxy matrix. Figure 2A shows a sample of epoxy containing unprotected catalyst (2.5 wt %), and the micrograph shows that the catalyst tends to form rather large particles with relatively large separations. Figure 2B shows a similar sample with 5 wt % wax microparticles. However, because the microparticles contain only 5 wt %
Grubbs' catalyst, the sample has only 0.25 wt % overall loading of Grubbs' catalyst, which is an order of magnitiude lower than the sample in Figure 2A.
As Figure 2B shows, the wax microparticles are well distributed throughout the sample giving a much higher sectional density of catalyst particles even with a much lower overall catalyst loading. Thus, the catalyst will also be more evenly distributed across the crack plane of a fractured sample, and this uniformity facilitates healing by delivering catalyst to the DCPD on the entire crack plane rather than only to localized areas near scarce catalyst particles.
The polymer may be any polymeric material into which the capsules may be dispersed. Examples include polyamides such as nylons; polyesters such as poly(ethylene terephthalate) and polycaprolactone; polycarbonates;
polyethers such as epoxides; polyimides such as polypyromellitimide (for example KAPTAN); phenol-formaldehyde resins (for example BAKELITE);
amine-formaldehyde resins such as a melamine resin; polysulfones;
poly(acrylonitrile-butadiene-styrene) (ABS); polyurethanes; polyolefins such as polyethylene, polystyrene, polyacrylonitrile, polyvinyls, polyvinyl chloride, poly(DCPD) and poly(methyl methacrylate); polysilanes such as poly(carborane-siloxane); and polyphosphazenes.
The capsules and protected activator (such as the catalyst or initiator) may be dispersed into the polymer by forming the polymer around the capsules and activator, such as by polymerizing monomer to form the polymer with the capsules and activator mixed into the monomer. Alternatively, the polymer may be first formed, and then the capsules and protected activator mixed in. For example, the polymer may be dissolved in a solvent and the capsules and protected activator mixed into the solution, followed by removal of the solvent. Furthermore, other components may be added to the polymer, such as fibers, fillers, adhesion modifiers, blowing agents, anti-oxidants, colorants and dyes, and fragrances.
EXAMPLES
Synthesis of Wax Microparticles Containing Grubbs' Catalyst.
In an N2-filled glovebox, paraffin wax (Aldrich, 10.0 g, mp = 58-62 C) and Grubbs' Catalyst (Strem, 525 mg) were sealed in a vial. The vial was removed from the glovebox. A solution of water (225 mL), poly(ethylene-co-maleic anhydride) (0.63 g, 0.28 wt %) and octanol (1 drop) was placed in a 1000 mL beaker in an 82 C water bath and stirred with a mechanical stirrer at 900 RPM. The vial containing the wax and the catalyst was submerged in the same 82 C water bath. After 10 min, the wax had melted and the aqueous solution had reached 65-70 C. The vial with the molten wax was shaken to disperse the catalyst. The vial was then opened (in air), and the wax was poured into the aqueous solution. After 2 min, cold water (600 mL, 0 C) was quickly added, and the stirring was stopped. The microparticles were collected by filtration and dried under vacuum.
Kinetics of ROMP Catalyzed by Wax-Protected Grubbs' Catalyst In an N2-filled glovebox, a stock solution of PCy3 (4.1 mM) in d-8 toluene was prepared. This stock solution was then added to an NMR tube with wax microparticles (140 mg) containing 5 wt % Grubbs' catalyst (0.0085 mmol). A control sample with unprotected Grubbs' catalyst (7.0 mg, 0.0085 mmol) and wax microparticles without included catalyst (133 mg) was prepared using the same stock solution of PCy3 in d-8 toluene. The total weight of each solution was 0.70 g. The samples were capped with septa and removed from the glovebox. Mesitylene (10 L) was added via syringe as an internal standard. The ROMP kinetics with endo-DCPD were obtained by in situ'H NMR as described previously.10 Fracture Tests Using the established method,',2," fracture samples with a tapered double-cantilever beam (TDCB) geometry were prepared containing 10 wt %
of 180 m diameter DCPD-filled microcapsules.1 2," The TDCB geometry, developed by Mostovoy et al.,12 provided a crack-length-independent measure of strain energy:
,6 30 Jc = ~ ~c ~ (1) Thus, the geometric term a, the critical fracture load Pc, and the term Q
were the only required measurements. As discussed by Brown et al., it can be experimentally determined that a= 11.2x103 m"312 for the TDCB sample geometry .2 4 The nonlinearity term ,6 was introduced to account for nonlinear elastic behavior of the healed interface prior to crack growth. For fracture of the virgin (linear elastic) material, ,6 is uniquely unity (1); for fracture of the healed materials, 8 is calculated by dividing the area under the measured load-displacement curve up to the point of crack growth by the area under a linear elastic load displacement curve of the same initial compliance and peak load. Virgin fracture was brittle in all cases and was statistically independent of microparticle size, concentration, or catalyst concentration (Jc = Gc _ 250 50 J/m2, Kic = 0.84 0.07 MPa m1/2).
Healing efficiency was assessed by modifying the protocol established by White et al.' TDCB fracture specimens were pin loaded and tested under displacement control, at 5 m/s displacement rate. Samples were tested to failure, measuring initial compliance and peak load to establish the initial (virgin) strain energy release rate. Load was then removed, and the crack faces were allowed to come in contact. Samples were retested after 24 hours to determine the healed, non-linear strain energy release rate. Crack healing efficiency, 77, was defined as the ability to recover strain energy:13 77 _ ~Cheuled = ~ PCheuled (2) J p CvirEin C virgin The reactivity of the wax-embedded catalyst was quantified by using in situ'H NMR to measure the ROMP kinetics of endo-DCPD in the presence of the microparticles.10 The rate constant for ROMP of DCPD measured for a sample prepared with Grubbs' catalyst obtained from the wax microparticles was 0.0162 s-'. An analogous control sample prepared with unprotected Grubbs' catalyst had a rate constant of 0.0179 s-', which shows that the process of embedding the catalyst in wax microparticies only reduces the reactivity by 9%. This small reduction in rate shows that the brief exposure of the catalyst to heat and air only mildly affects its reactivity. Furthermore, when the wax-protected catalyst is melted and cast into new microparticles, the measured rate constant does not change significantly from that of the original microparticles. Because this recycling process can be done without loss of reactivity, microparticles that fall outside the desired size range can be reformed with useful diameters, thus avoiding the costly waste of catalyst.
The wax greatly increases the resistance of the catalyst to ethylenediamine (EDA). As a control, a sample of unprotected Grubbs' catalyst was exposed to neat EDA and immediately placed under vacuum.
Within 10 min, the EDA had completely evaporated. The same procedure was performed with wax-protected catalyst microparticles. NMR samples were prepared using the non-volatile catalyst and wax residues, and the kinetics of ROMP of DCPD using the exposed catalyst were measured. The wax preserved 69% of the catalyst's reactivity while the unprotected catalyst showed no reactivity. Because of its low volatility, DETA could not be used in a similar experiment, but the wax appears to similarly protect the catalyst from DETA. Because the wax can protect the catalyst from the DETA used to prepare self-healing samples, less catalyst will be destroyed during sample preparation and healing should be possible with reduced catalyst loadings.
The wax microparticles also appear to be useful for dispersing Grubbs' catalyst uniformly throughout the epoxy matrix. Figure 2A shows a sample of epoxy containing unprotected catalyst (2.5 wt %), and the micrograph shows that the catalyst tends to form rather large particles with relatively large separations. Figure 2B shows a similar sample with 5 wt % wax microparticles. However, because the microparticles contain only 5 wt %
Grubbs' catalyst, the sample has only 0.25 wt % overall loading of Grubbs' catalyst, which is an order of magnitiude lower than the sample in Figure 2A.
As Figure 2B shows, the wax microparticles are well distributed throughout the sample giving a much higher sectional density of catalyst particles even with a much lower overall catalyst loading. Thus, the catalyst will also be more evenly distributed across the crack plane of a fractured sample, and this uniformity facilitates healing by delivering catalyst to the DCPD on the entire crack plane rather than only to localized areas near scarce catalyst particles.
Using the techniques reported previously,1,2,4 fracture samples were prepared and tested with 10 wt % DCPD microcapsules and various loadings of catalyst microparticles. Representative load-displacement curves for virgin and healed specimens are shown in Figures 3A and 3B. Unlike the behavior previously reported for self-healing samples prepared with unprotected catalyst, the self-healing achieved with catalyst microparticles exhibits non-linear behavior prior to the onset of crack propagation. The non-linearity appears to result from the polydicyclopentadiene being softened by the wax that is dissolved in the DCPD prior to curing, and this softening effect is being examined in more detail in a separate study. Due to this non-linearity, strain energy (Jc) at crack propagation is a better measure of healing ability than stress,intensity (Kic) at fracture (which was used in our previous reports), and the healed critical strain energy is dependent on both the critical load for the crack to propagate (Pc) and the extent of non-linearity captured by the parameter /3; increasing either of these terms increases healing. Moreover, while healing efficiency is a measure of recovery of the strain energy prior to crack propagation, the greater resistance to crack growth in the healed material after the start of propagation yields a total energy to sample failure that is greater than the brittle failure of the virgin material. Therefore, the healing efficiencies calculated using critical strain energy may underestimate the full recovery effect of self-healing.
Figure 4A shows how healing efficiencies vary with the amount of catalyst included in the wax microparticies. As expected, the samples with the largest amounts of catalyst gave the best healing efficiencies (93%), but even with the lowest attempted catalyst loading good healing (59%) was observed. In this series, the loading of microparticles in the epoxy is held constant at 5 wt %. If it is assumed that the non-linearity in this system results from wax being incorporated into the polyDCPD, the relatively constant values for R in this series are likely due to the nearly constant amount of wax in each sample.
The data in Figure 4A show that an overall catalyst loading of 0.25 wt % (i.e. 5 wt % catalyst in the microparticles multiplied by 5 wt %
microparticles in the epoxy) is sufficient for good healing. Based on this result, an additional series of samples was tested to optimize the healing that can be achieved using this concentration of catalyst. In this series, the loading of catalyst in the wax was varied inversely with the loading of microparticles in the epoxy in order to maintain an overall catalyst level of 0.25 wt % (Figure 4B). The highest healing efficiency resulted from a 5 wt % catalyst loading in the microparticles and a 5 wt % microparticle loading in the epoxy, and this optimal efficiency is primarily due to the large value for the non-linearity term P. The cause for the high value of R probably stems from the fact that the amount of wax in the sample is at its highest level with 5 wt % microparticles in the epoxy, and high wax loadings appear to enhance non-linearity.
As Figures 4A and 4B show, an average healing efficiency of 59% is obtained with a 0.25 wt % catalyst in the sample. As previously reported,4 the self-healing system using unprotected catalyst gave an optimized average healing efficiency of 62% (based on strain energy Jc) and only 24% for the comparable case of 10 wt % 180 m diameter microcapsules with 2.5 wt %
catalyst. Thus, by using the wax protected catalyst microparticles, comparable or, in some cases, superior healing efficiency is achieved while reducing the overali catalyst loading by an order of magnitude.
Suspending Grubbs' catalyst in wax microparticles retains its reactivity while it is protected from the conditions required for the preparation and curing of epoxy materials. This method of delivery produces comparable healing efficiencies to those previously achieved while requiring only one tenth as much catalyst. Additionally, healing efficiencies of 93% (which surpass any previously reported healing efficiencies when expressed in terms of strain energy) can be achieved with this system while using lower catalyst loadings than the previous systems. This increased efficiency may result from more uniform dispersion of the wax-protected catalyst in the epoxy matrix along with the ability of the wax to protect the catalyst from detrimental interaction with DETA. These results may be extended to other polymers, and other protected activators.
Figure 4A shows how healing efficiencies vary with the amount of catalyst included in the wax microparticies. As expected, the samples with the largest amounts of catalyst gave the best healing efficiencies (93%), but even with the lowest attempted catalyst loading good healing (59%) was observed. In this series, the loading of microparticles in the epoxy is held constant at 5 wt %. If it is assumed that the non-linearity in this system results from wax being incorporated into the polyDCPD, the relatively constant values for R in this series are likely due to the nearly constant amount of wax in each sample.
The data in Figure 4A show that an overall catalyst loading of 0.25 wt % (i.e. 5 wt % catalyst in the microparticles multiplied by 5 wt %
microparticles in the epoxy) is sufficient for good healing. Based on this result, an additional series of samples was tested to optimize the healing that can be achieved using this concentration of catalyst. In this series, the loading of catalyst in the wax was varied inversely with the loading of microparticles in the epoxy in order to maintain an overall catalyst level of 0.25 wt % (Figure 4B). The highest healing efficiency resulted from a 5 wt % catalyst loading in the microparticles and a 5 wt % microparticle loading in the epoxy, and this optimal efficiency is primarily due to the large value for the non-linearity term P. The cause for the high value of R probably stems from the fact that the amount of wax in the sample is at its highest level with 5 wt % microparticles in the epoxy, and high wax loadings appear to enhance non-linearity.
As Figures 4A and 4B show, an average healing efficiency of 59% is obtained with a 0.25 wt % catalyst in the sample. As previously reported,4 the self-healing system using unprotected catalyst gave an optimized average healing efficiency of 62% (based on strain energy Jc) and only 24% for the comparable case of 10 wt % 180 m diameter microcapsules with 2.5 wt %
catalyst. Thus, by using the wax protected catalyst microparticles, comparable or, in some cases, superior healing efficiency is achieved while reducing the overali catalyst loading by an order of magnitude.
Suspending Grubbs' catalyst in wax microparticles retains its reactivity while it is protected from the conditions required for the preparation and curing of epoxy materials. This method of delivery produces comparable healing efficiencies to those previously achieved while requiring only one tenth as much catalyst. Additionally, healing efficiencies of 93% (which surpass any previously reported healing efficiencies when expressed in terms of strain energy) can be achieved with this system while using lower catalyst loadings than the previous systems. This increased efficiency may result from more uniform dispersion of the wax-protected catalyst in the epoxy matrix along with the ability of the wax to protect the catalyst from detrimental interaction with DETA. These results may be extended to other polymers, and other protected activators.
REFERENCES:
11] White, S. R.; Sottos, N. R.; Geubelle, P. H.; Moore, J. S.; Kessler, M.
R.; Sriram, S. R.; Brown, E. N.; Viswanathan, S. Nature 2001, 409, 794-797.
[2] Brown, E. N.; Sottos, N. R.; White, S. R. Exp. Mech. 2002, 42, 372-379.
[3] Kessler, M. R.; White, S. R. J. Polym. Sci. Pol. Chem. 2002, 40, 2373-2383.
[4] Brown, E. N.; White, S. R.; Sottos, N. R. J. Mater. Sci. 2004, 39, 1703-1710.
[5] Kessler, M. R.; Sottos, N. R.; White, S. R. Compos. Part A-Appl. S.
2003, 34, 743-753.
[6] Taber, D. F.; Frankowski, K. J. J. Org. Chem. 2003, 68, 6047-6048.
[7] Kosak, et al., U. S. Patent Nos. 5,413,924; 5,550,044; and 5,643,764.
[8] Shimandle, D. J.: U. S. Patent No. 5,185,108.
[9] Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
[10] Rule, J. D.; Moore, J. S. Macromolecules 2002, 35, 7878-7882.
[11] Brown, E. N.; Kessler, M. R.; Sottos, N. R.; White, S. R. J.
Microencapsul. 2003, 20, 719-730.
[12] Mostovoy, S.; Crosley, P. B.; Ripling, E. J. J. Mater. Sci. 1967, 2, 661-681.
[13] Wool, R. P.; O'Conner, K. M. J. Appl. Phys. 1981, 52, 5953-5963.
[14] Bazan, G.C.; Schrock, R.R.; Cho, H.-N.; Gibson, V.C. Macromolecules 1991, 24, 4495-4502.) [15] Grubbs, R.H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
11] White, S. R.; Sottos, N. R.; Geubelle, P. H.; Moore, J. S.; Kessler, M.
R.; Sriram, S. R.; Brown, E. N.; Viswanathan, S. Nature 2001, 409, 794-797.
[2] Brown, E. N.; Sottos, N. R.; White, S. R. Exp. Mech. 2002, 42, 372-379.
[3] Kessler, M. R.; White, S. R. J. Polym. Sci. Pol. Chem. 2002, 40, 2373-2383.
[4] Brown, E. N.; White, S. R.; Sottos, N. R. J. Mater. Sci. 2004, 39, 1703-1710.
[5] Kessler, M. R.; Sottos, N. R.; White, S. R. Compos. Part A-Appl. S.
2003, 34, 743-753.
[6] Taber, D. F.; Frankowski, K. J. J. Org. Chem. 2003, 68, 6047-6048.
[7] Kosak, et al., U. S. Patent Nos. 5,413,924; 5,550,044; and 5,643,764.
[8] Shimandle, D. J.: U. S. Patent No. 5,185,108.
[9] Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
[10] Rule, J. D.; Moore, J. S. Macromolecules 2002, 35, 7878-7882.
[11] Brown, E. N.; Kessler, M. R.; Sottos, N. R.; White, S. R. J.
Microencapsul. 2003, 20, 719-730.
[12] Mostovoy, S.; Crosley, P. B.; Ripling, E. J. J. Mater. Sci. 1967, 2, 661-681.
[13] Wool, R. P.; O'Conner, K. M. J. Appl. Phys. 1981, 52, 5953-5963.
[14] Bazan, G.C.; Schrock, R.R.; Cho, H.-N.; Gibson, V.C. Macromolecules 1991, 24, 4495-4502.) [15] Grubbs, R.H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
Claims (23)
1. A composite material, comprising:
(i) a polymer, (ii) a polymerizer, (iii) a protected corresponding activator for the polymerizer, and (iv) a plurality of capsules, wherein the polymerizer is in the capsules, and the corresponding activator is protected with a corresponding encapsulant for the polymer and the polymerizer.
(i) a polymer, (ii) a polymerizer, (iii) a protected corresponding activator for the polymerizer, and (iv) a plurality of capsules, wherein the polymerizer is in the capsules, and the corresponding activator is protected with a corresponding encapsulant for the polymer and the polymerizer.
2. The composite material of claim 1, wherein the polymerizer comprises at least one monomer selected from the group consisting of cyclic olefins, lactones, lactams, acrylates, acrylic acids, alkyl acrylates, alkyl acrylic acids, styrenes, isoprene and butadiene.
3. The composite material of any of the proceeding claims, wherein the polymerizer comprises cyclic olefins.
4. The composite material of any of the proceeding claims, wherein the polymer comprises at least one member selected from the group consisting of polyamides, polyesters, polycarbonates, polyethers, polyimides, phenol-formaldehyde resins, amine-formaldehyde resins, polysulfones, poly(acrylonitrile-butadiene-styrene), polyurethanes, polyolefins, and polysilanes.
5. The composite material of any of the proceeding claims, wherein the polymer comprises at least one member selected from the group consisting of polyesters and polyethers.
6. The composite material of any of the proceeding claims, wherein the corresponding activator for the polymerizer comprises at least one monomer selected from the group consisting of ROMP catalysts and cyclic ester polymerization catalysts.
7. The composite material of any of the proceeding claims, wherein the corresponding activator for the polymerizer comprises a ROMP catalyst.
8. The composite material of any of the proceeding claims, wherein the encapsulant is a wax.
9. The composite material of any of the proceeding claims, wherein the capsules comprise a polymer of urea and formaldehyde, gelatin, polyurea, and polyamide.
10. The composite material of any of the proceeding claims, wherein the polymerizer comprises DCPD, the polymer comprises epoxy, the protected corresponding activator for the polymerizer comprises a ROMP catalyst protected by a wax, and is present as microparticless, the capsules have an aspect ratio of 1:1 to 1:1.5, and an average diameter of 30-300 µm, and the capsules comprise a polymer of urea and formaldehyde.
11. A composite material, comprising:
(i) a polymer, (ii) a polymerizer, (iii) microparticels of a protected corresponding catalyst for the polymerizer, and (iv) a plurality of capsules, wherein the polymerizer is in the capsules, the corresponding catalyst is protected with a corresponding encapsulant for the polymer and the polymerizer, and the encapsulant comprises wax.
(i) a polymer, (ii) a polymerizer, (iii) microparticels of a protected corresponding catalyst for the polymerizer, and (iv) a plurality of capsules, wherein the polymerizer is in the capsules, the corresponding catalyst is protected with a corresponding encapsulant for the polymer and the polymerizer, and the encapsulant comprises wax.
12. The composite material of any of the proceeding claims, wherein
13. The composite material of any of the proceeding claims, wherein the polymer comprises at least one member selected from the group consisting of polyamides, polyesters, polycarbonates, polyethers, polyimides, phenol-formaldehyde resins, amine-formaldehyde resins, polysulfones, poly(acrylonitrile-butadiene-styrene), polyurethanes, polyolefins, and polysilanes.
14. The composite material of any of the proceeding claims, wherein the capsules comprise a polymer of urea and formaldehyde, gelatin, polyurea, and polyamide.
15. A method for making the composite of any of the proceeding claims, comprising:
dispersing the capsules and the protected corresponding activator into the polymer.
dispersing the capsules and the protected corresponding activator into the polymer.
16. A method for making the composite of any of the proceeding claims, comprising:
dispersing the capsules and the protected corresponding activator into the polymer.
dispersing the capsules and the protected corresponding activator into the polymer.
17. Particles, comprising:
(a) a compound, and (b) a wax, surrounding the compound, wherein the particles are microparticles.
(a) a compound, and (b) a wax, surrounding the compound, wherein the particles are microparticles.
18. The particles of any of the proceeding claims, wherein the compound is an activator.
19. The particles of any of the proceeding claims, wherein the compound is a catalyst.
20. The particles of any of the proceeding claims, wherein the compound is a ROMP catalyst.
21. The particles of any of the proceeding claims, wherein the ROMP catalyst is a metal halide.
22. The particles of any of the proceeding claims, wherein the compound is an WCI6.
23. The particles of any of the proceeding claims, wherein the wax is paraffin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/840,937 US7566747B2 (en) | 2004-05-07 | 2004-05-07 | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
| US10/840,937 | 2004-05-07 | ||
| PCT/US2005/015783 WO2005118703A1 (en) | 2004-05-07 | 2005-05-06 | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2565969A1 true CA2565969A1 (en) | 2005-12-15 |
Family
ID=35149253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002565969A Abandoned CA2565969A1 (en) | 2004-05-07 | 2005-05-06 | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US7566747B2 (en) |
| EP (1) | EP1751224A1 (en) |
| JP (1) | JP2007536410A (en) |
| KR (1) | KR20070011575A (en) |
| CN (1) | CN1950441A (en) |
| CA (1) | CA2565969A1 (en) |
| WO (1) | WO2005118703A1 (en) |
Families Citing this family (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518330B2 (en) * | 2001-02-13 | 2003-02-11 | Board Of Trustees Of University Of Illinois | Multifunctional autonomically healing composite material |
| US7566747B2 (en) | 2004-05-07 | 2009-07-28 | The Board Of Trustees Of The University Of Illinois | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
| US8114517B2 (en) * | 2004-07-30 | 2012-02-14 | Battelle Memorial Institute | Micronetworks, microchannels/cylinders and the process for making the same |
| DE102004062225A1 (en) * | 2004-12-23 | 2006-07-06 | Hilti Ag | Multi-component foam system for the production of interpenetrating polymeric networks and its use |
| US7749934B2 (en) * | 2005-02-22 | 2010-07-06 | Rohm And Haas Company | Protected catalytic composition and its preparation and use for preparing polymers from ethylenically unsaturated monomers |
| US7612152B2 (en) * | 2005-05-06 | 2009-11-03 | The Board Of Trustees Of The University Of Illinois | Self-healing polymers |
| US7811666B2 (en) * | 2005-07-01 | 2010-10-12 | Carolyn Dry | Multiple function, self-repairing composites with special adhesives |
| US7723405B2 (en) | 2006-01-05 | 2010-05-25 | The Board Of Trustees Of The University Of Illinois | Self-healing coating system |
| AU2007206684B2 (en) * | 2006-01-17 | 2012-03-22 | Philip Morris Products S.A. | Cigarette components having encapsulated catalyst particles and methods of making and use thereof |
| US7569625B2 (en) * | 2006-06-02 | 2009-08-04 | The Board Of Trustees Of The University Of Illinois | Self-healing elastomer system |
| US8168298B2 (en) * | 2006-12-01 | 2012-05-01 | Basf Corporation | Article and method of producing same |
| US20080299391A1 (en) * | 2007-05-31 | 2008-12-04 | White Scott R | Capsules, methods for making capsules, and self-healing composites including the same |
| US8735463B2 (en) | 2007-05-31 | 2014-05-27 | Creighton University | Self-healing dental composites and related methods |
| US8920879B2 (en) * | 2007-06-08 | 2014-12-30 | Board Of Trustees Of The University Of Illinois | Self-healing materials with microfluidic networks |
| WO2009018111A1 (en) * | 2007-07-27 | 2009-02-05 | The Board Of Trustees Of The University Of Illinois | Self-assessing mechanochromic materials |
| WO2009055772A1 (en) * | 2007-10-26 | 2009-04-30 | The Board Of Trustees Of The University Of Illinois | Solvent-promoted self-healing materials |
| US8088015B2 (en) | 2007-11-01 | 2012-01-03 | Gkn Driveline North America, Inc. | Self-repairing boot for a constant velocity joint |
| US20090181254A1 (en) * | 2008-01-15 | 2009-07-16 | The Board Of Trustees Of The University Of Illinois | Multi-capsule system and its use for encapsulating active agents |
| US9415575B2 (en) * | 2008-01-25 | 2016-08-16 | The Board Of Trustees Of The University Of Illinois | Self-healing laminate system |
| WO2009115671A1 (en) * | 2008-02-15 | 2009-09-24 | Catalyse | Self-repairing composition, self-repairing materials, self-repairing methods and applications |
| US8703285B2 (en) * | 2008-08-19 | 2014-04-22 | The Board Of Trustees Of The University Of Illinois | Interfacial functionalization for self-healing composites |
| US9533469B2 (en) * | 2008-12-23 | 2017-01-03 | Syracuse University | Self-healing product |
| US8383697B2 (en) * | 2009-04-30 | 2013-02-26 | Board Of Trustees Of The University Of Illinois | Systems for self-healing composite materials |
| US9119774B2 (en) * | 2009-09-18 | 2015-09-01 | Premier Dental Products Company | Self-healing dental restorative formulations and related methods |
| US8683798B2 (en) * | 2010-01-15 | 2014-04-01 | Syracuse University | Stimuli-responsive product |
| US8679621B2 (en) * | 2010-06-18 | 2014-03-25 | Board Of Trustees Of The University Of Illinois | Materials and methods for autonomous restoration of electrical conductivity |
| US8846404B2 (en) | 2010-06-25 | 2014-09-30 | Board Of Trustees Of The University Of Illinois | System for visual indication of mechanical damage |
| JP5943392B2 (en) | 2011-04-07 | 2016-07-05 | 株式会社日立製作所 | Resin material, manufacturing method thereof, repairing method thereof, and members using the same |
| US20140134426A1 (en) * | 2011-06-23 | 2014-05-15 | Rok Investment Group Limited | Nano-based self-healing anti-corrosion coating |
| ES2395645B1 (en) * | 2011-07-29 | 2013-12-16 | Airbus Operations, S.L. | PROTECTIVE SHIELD AGAINST ICE IMPACTS IN AIRCRAFT. |
| US8685513B1 (en) | 2012-02-29 | 2014-04-01 | Carolyn M. Dry | Inflatable articles comprising a self-repairing laminate |
| US9694629B1 (en) | 2012-02-29 | 2017-07-04 | Carolyn Dry | Self-repairing inflatable articles incorporating an integrated self-repair system |
| US9605162B2 (en) | 2013-03-15 | 2017-03-28 | Honda Motor Co., Ltd. | Corrosion inhibiting compositions and methods of making and using |
| US9816189B2 (en) | 2013-03-15 | 2017-11-14 | Honda Motor Co., Ltd. | Corrosion inhibiting compositions and coatings including the same |
| UA117487C2 (en) * | 2013-07-19 | 2018-08-10 | Філіп Морріс Продактс С.А. | Smoking article having a particle containing wrapper |
| US9663610B2 (en) | 2014-10-03 | 2017-05-30 | International Business Machines Corporation | Catalyst-lean, microcapsule-based self-healing materials via ring-opening metathesis polymerization (ROMP) |
| US9943487B2 (en) | 2015-05-26 | 2018-04-17 | The Board Of Trustees Of The University Of Illinois | Polydopamine-coated capsules |
| WO2017011029A1 (en) | 2015-07-14 | 2017-01-19 | Iowa State University Research Foundation, Inc. | Stable undercooled metallic particles for engineering at ambient conditions |
| CN105199739B (en) * | 2015-09-15 | 2018-08-14 | 西安文理学院 | A kind of preparation method of selfreparing porous fibre |
| US10508204B2 (en) | 2015-12-02 | 2019-12-17 | The Board Of Trustees Of The University Of Illinois | Self-healing coating |
| US11008415B2 (en) | 2016-08-29 | 2021-05-18 | Hitachi, Ltd. | Resin cured product, electrical device, motor, transformer, cable sheath, mobile, structure, and method for healing resin cured product |
| US10377879B2 (en) | 2016-10-19 | 2019-08-13 | The Board Of Trustees Of The University Of Illinois | Chemical amplification in self-strengthening materials |
| US11241678B2 (en) | 2017-05-01 | 2022-02-08 | Iowa State University Research Foundation, Inc. | Metal oxide materials made using self-assembled coordination polymers |
| US10920002B2 (en) | 2017-05-15 | 2021-02-16 | The Board Of Trustees Of The University Of Illinois | 3D printing of thermoset polymers and composites |
| US11059098B2 (en) | 2017-06-09 | 2021-07-13 | SAFI-Tech, Inc. | Direct printing and writing using undercooled metallic core-shell particles |
| CN109467697B (en) * | 2018-11-05 | 2021-08-31 | 西南林业大学 | Branched polyamide-glyoxal resin adhesive, preparation method and application |
| US11543322B2 (en) * | 2020-05-01 | 2023-01-03 | Globalfoundries U.S. Inc. | Crack identification in IC chip package using encapsulated liquid penetrant contrast agent |
| US11718710B2 (en) | 2020-10-14 | 2023-08-08 | The Board Of Trustees Of The University Of Illinois | Method of light-promoted frontal ring-opening metathesis polymerization |
| WO2022147079A1 (en) | 2021-01-04 | 2022-07-07 | SAFI-Tech, Inc. | System and method for manufacture of undercooled metallic core-shell particles |
| CN115354495A (en) * | 2022-09-14 | 2022-11-18 | 中粮工程装备（张家口）有限公司 | Felt filling sealing impregnation medium and preparation and application methods thereof |
Family Cites Families (76)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3069370A (en) | 1958-12-22 | 1962-12-18 | Upjohn Co | Coacervation process for encapsulation of lipophilic materials |
| BE585460A (en) | 1959-01-02 | 1900-01-01 | ||
| US3868199A (en) | 1971-06-04 | 1975-02-25 | Jose Fera | Apparatus for producing powered paraffin |
| US4080238A (en) | 1976-07-14 | 1978-03-21 | Pratt & Lambert, Inc. | One-liquid cold setting adhesive with encapsulated catalyst initiator |
| DE2910560A1 (en) | 1979-03-17 | 1980-09-25 | Bayer Ag | THIXOTROP ADJUSTED SILICONE PASTE FOR TOOTH AND MUCUTINE IMPRESSIONS |
| EP0020123A1 (en) | 1979-05-31 | 1980-12-10 | A.O.C.M. Limited | Raney catalyst compositions and their preparation |
| US4301306A (en) | 1980-03-27 | 1981-11-17 | The B. F. Goodrich Company | Norbornenyl phenolic compounds |
| US4324717A (en) | 1980-06-23 | 1982-04-13 | The B. F. Goodrich Company | Norbornene polymers stabilized with hindered aromatic alcohols |
| US4380617A (en) | 1982-01-20 | 1983-04-19 | The B. F. Goodrich Company | Preparation of polymers from cycloolefins |
| US4461854A (en) | 1982-08-11 | 1984-07-24 | General Electric Company | Room temperature vulcanizable polysiloxane having a heat-activated catalyst |
| US4708969A (en) | 1984-11-16 | 1987-11-24 | Hercules Incorporated | Cycloolefin composition and method for making high TG fiber reinforced polymeric product |
| US4940645A (en) | 1985-07-16 | 1990-07-10 | The Mead Corporation | Imaging material employing photosensitive microcapsules containing tertiary amines as coinitiators |
| US4755588A (en) | 1986-08-22 | 1988-07-05 | General Electric Company | Composition and method for controlling polymerization rate of cyclic polycarbonate oligomer with encapsulated catalyst |
| DE3634084A1 (en) | 1986-10-07 | 1988-04-21 | Hanse Chemie Gmbh | MODIFIED REACTION RESIN, METHOD FOR PRODUCING IT AND ITS USE |
| US4804427A (en) | 1986-11-05 | 1989-02-14 | Allied-Signal Inc. | Composites via in-situ polymerization of composite matrices using a polymerization initiator bound to a fiber coating |
| US4758400A (en) | 1987-01-27 | 1988-07-19 | Ashland Oil, Inc. | Thermosetting molding compounds |
| GB8708982D0 (en) | 1987-04-14 | 1987-05-20 | Interox Chemicals Ltd | Curing polyester resins |
| US4902560A (en) | 1988-06-01 | 1990-02-20 | Hercules Incorporated | Improving the physical properties of glass composite polydicyclopentadiene by heat treatment |
| JPH0757811B2 (en) | 1988-06-21 | 1995-06-21 | 日本ゼオン株式会社 | Glass fiber reinforced norbornene-based polymer and method for producing the same |
| EP0349855A3 (en) | 1988-06-27 | 1991-01-23 | Hercules Incorporated | Molded article of metathesis polymerized polymer containing fillers and process for its preparation |
| WO1990000005A1 (en) | 1988-06-30 | 1990-01-11 | Redding Bruce K Jr | Microencapsulated pesticides with a lure |
| US4943621A (en) | 1988-08-04 | 1990-07-24 | The B. F. Goodrich Company | Storage stable components of reactive formulations for bulk polymerization of cycloolefin monomers |
| JP2833111B2 (en) | 1989-03-09 | 1998-12-09 | 日立化成工業株式会社 | Circuit connection method and adhesive film used therefor |
| CA2028239A1 (en) | 1989-10-24 | 1991-04-25 | Brian L. Goodall | Coated reinforcing material |
| US5575841A (en) | 1990-06-19 | 1996-11-19 | Carolyn M. Dry | Cementitious materials |
| US5561173A (en) | 1990-06-19 | 1996-10-01 | Carolyn M. Dry | Self-repairing, reinforced matrix materials |
| US7022179B1 (en) | 1990-06-19 | 2006-04-04 | Dry Carolyn M | Self-repairing, reinforced matrix materials |
| US6527849B2 (en) | 1990-06-19 | 2003-03-04 | Carolyn M. Dry | Self-repairing, reinforced matrix materials |
| US5803963A (en) | 1990-06-19 | 1998-09-08 | Dry; Carolyn M. | Smart-fiber-reinforced matrix composites |
| US5529914A (en) | 1990-10-15 | 1996-06-25 | The Board Of Regents The Univeristy Of Texas System | Gels for encapsulation of biological materials |
| US5185108A (en) | 1991-07-10 | 1993-02-09 | The B. F. Goodrich Company | Method for producing wax microspheres |
| US5413924A (en) | 1992-02-13 | 1995-05-09 | Kosak; Kenneth M. | Preparation of wax beads containing a reagent for release by heating |
| DE4209031A1 (en) | 1992-03-20 | 1993-09-23 | Basf Ag | Impact-modified polyphenylene ether (PPE) moulding materials - contain impact-modified polystyrene with encapsulated particle morphology, and opt. additives |
| US5324616A (en) | 1992-04-01 | 1994-06-28 | Xerox Corporation | Encapsulated toner compositions and processes thereof |
| US5312940A (en) | 1992-04-03 | 1994-05-17 | California Institute Of Technology | Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization |
| US5427880A (en) | 1993-02-01 | 1995-06-27 | Ricoh Company, Ltd. | Electrophotographic Photoconductor |
| JP3024432B2 (en) | 1993-04-23 | 2000-03-21 | 信越化学工業株式会社 | Silicone rubber composition and curing method thereof |
| DE4405745C2 (en) | 1994-02-23 | 1998-05-14 | Rehau Ag & Co | Thermoplastics containing in-situ encapsulated fillers and their use |
| BR9509784A (en) | 1994-11-17 | 1997-10-21 | Ciba Geigy Ag | Thermal metastasis polymerization process and polymerizable composition |
| RU2168518C2 (en) | 1994-12-23 | 2001-06-10 | Циба Спешиалти Чемикалс Холдинг Инк. | Composition able to polymerization |
| US5932285A (en) | 1995-02-17 | 1999-08-03 | Medlogic Global Corporation | Encapsulated materials |
| US5958325A (en) | 1995-06-07 | 1999-09-28 | Tpi Technology, Inc. | Large composite structures and a method for production of large composite structures incorporating a resin distribution network |
| DE59610089D1 (en) | 1995-11-02 | 2003-03-06 | Ciba Sc Holding Ag | Curable composition containing cycloolefin, silane and filler |
| ES2179224T3 (en) | 1996-01-11 | 2003-01-16 | Essex Specialty Prod | CURABLE POLYURETHANE ADHESIVE IN A COMPONENT. |
| ES2146452T3 (en) | 1996-03-07 | 2000-08-01 | Ciba Sc Holding Ag | RETICULABLE COMPOSITION CONTAINING A CYCLOPENTADIENE DIELS-ALDER ADDUCT AND A LOAD OF FILLING. |
| ES2166059T3 (en) | 1996-05-14 | 2002-04-01 | Ciba Sc Holding Ag | PROCEDURE FOR OBTAINING COMPOSITE MATERIALS REINFORCED WITH FIBERS. |
| US6048488A (en) | 1997-04-04 | 2000-04-11 | The United States Of America As Represented By The Secretary Of The Army | One-step resin transfer molding of multifunctional composites consisting of multiple resins |
| WO1999011454A1 (en) | 1997-09-05 | 1999-03-11 | A. O. Smith Corporation | Metathesis polymerized olefin composites including sized reinforcement material |
| US6388865B1 (en) | 1997-11-18 | 2002-05-14 | Matsushita Electric Industrial Co., Ltd. | Laminate and capacitor |
| US6075072A (en) | 1998-03-13 | 2000-06-13 | 3M Innovative Properties Company | Latent coating for metal surface repair |
| US6287992B1 (en) | 1998-04-20 | 2001-09-11 | The Dow Chemical Company | Polymer composite and a method for its preparation |
| AU3966999A (en) | 1998-04-27 | 1999-11-16 | Dow Chemical Company, The | Cure on demand adhesives for assembling shoe soles |
| ATE252611T1 (en) | 1998-04-27 | 2003-11-15 | Essex Specialty Prod | METHOD FOR FIXING A WINDOW TO A SUBSTRATE USING A SILANE FUNCTIONAL ADHESIVE COMPOSITION |
| AU3666799A (en) | 1998-04-27 | 1999-11-16 | Dow Chemical Company, The | Encapsulated active materials |
| CA2279084C (en) | 1998-09-11 | 2013-12-03 | Steven G. Keener | Method for coating faying surfaces of aluminum-alloy components and faying surfaces coated thereby |
| US6316194B1 (en) | 1999-12-16 | 2001-11-13 | Ribotargets | Methods and kits for discovery of RNA-binding antimicrobials |
| JP3736611B2 (en) | 2000-02-01 | 2006-01-18 | 信越化学工業株式会社 | Flip chip type semiconductor device sealing material and flip chip type semiconductor device |
| JP5178982B2 (en) | 2000-05-18 | 2013-04-10 | セリックス， インコーポレイテッド | Encapsulation of the toxic core in a non-toxic region in an oral dosage form |
| DE50013562D1 (en) | 2000-06-20 | 2006-11-16 | Abb Research Ltd | Potting compounds for the production of electrical insulation |
| CA2419115C (en) | 2000-08-15 | 2011-03-08 | Board Of Trustees Of The University Of Illinois | Microparticles, and method and apparatus for forming same |
| US6518330B2 (en) | 2001-02-13 | 2003-02-11 | Board Of Trustees Of University Of Illinois | Multifunctional autonomically healing composite material |
| US6808461B2 (en) | 2001-06-22 | 2004-10-26 | Acushnet Company | Golf ball compositions with microencapsulated healing agent |
| US7125915B2 (en) | 2001-06-22 | 2006-10-24 | Acushnet Company | Lipid-based nanotubules for controlled release of healing agents in golf ball layers |
| DE10157123A1 (en) | 2001-11-21 | 2003-01-23 | Petra Frieser | Pneumatic tire or inner tube for a vehicle consists in part of a self-repairing plastic material |
| US6783709B2 (en) | 2002-07-10 | 2004-08-31 | The Regents Of The University Of California | Self-healing organosiloxane materials containing reversible and energy-dispersive crosslinking domains |
| US7108914B2 (en) | 2002-07-15 | 2006-09-19 | Motorola, Inc. | Self-healing polymer compositions |
| US20040055686A1 (en) | 2002-07-22 | 2004-03-25 | Cowger Katharine M. | Tire components having improved durability |
| US7192993B1 (en) | 2003-03-04 | 2007-03-20 | The United States Of America As Represented By The Secretary Of The Army | Self-healing coating and microcapsules to make same |
| JP2007528286A (en) | 2003-07-03 | 2007-10-11 | エルジー・ケム・リミテッド | Method for producing microcapsules through miniemulsion polymerization |
| US7045562B2 (en) | 2003-10-16 | 2006-05-16 | International Business Machines Corporation | Method and structure for self healing cracks in underfill material between an I/C chip and a substrate bonded together with solder balls |
| US7566747B2 (en) | 2004-05-07 | 2009-07-28 | The Board Of Trustees Of The University Of Illinois | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
| US20060025852A1 (en) * | 2004-08-02 | 2006-02-02 | Armstrong Joseph R | Bioabsorbable self-expanding endolumenal devices |
| US7612152B2 (en) | 2005-05-06 | 2009-11-03 | The Board Of Trustees Of The University Of Illinois | Self-healing polymers |
| US8822024B2 (en) | 2005-07-15 | 2014-09-02 | Prospective Concepts Ag | Method of producing a self-healing membrane |
| US7723405B2 (en) | 2006-01-05 | 2010-05-25 | The Board Of Trustees Of The University Of Illinois | Self-healing coating system |
| US7569625B2 (en) | 2006-06-02 | 2009-08-04 | The Board Of Trustees Of The University Of Illinois | Self-healing elastomer system |
-
2004
- 2004-05-07 US US10/840,937 patent/US7566747B2/en active Active
-
2005
- 2005-05-06 CA CA002565969A patent/CA2565969A1/en not_active Abandoned
- 2005-05-06 WO PCT/US2005/015783 patent/WO2005118703A1/en active Application Filing
- 2005-05-06 EP EP05804808A patent/EP1751224A1/en not_active Withdrawn
- 2005-05-06 JP JP2007511617A patent/JP2007536410A/en not_active Withdrawn
- 2005-05-06 CN CNA2005800145955A patent/CN1950441A/en active Pending
- 2005-05-06 KR KR1020067025642A patent/KR20070011575A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007536410A (en) | 2007-12-13 |
| KR20070011575A (en) | 2007-01-24 |
| WO2005118703A1 (en) | 2005-12-15 |
| US7566747B2 (en) | 2009-07-28 |
| US20050250878A1 (en) | 2005-11-10 |
| CN1950441A (en) | 2007-04-18 |
| EP1751224A1 (en) | 2007-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7566747B2 (en) | Wax particles for protection of activators, and multifunctional autonomically healing composite materials | |
| US7612152B2 (en) | Self-healing polymers | |
| US6518330B2 (en) | Multifunctional autonomically healing composite material | |
| AU605089B2 (en) | Controlled release formulations employing resilient microbeads | |
| EP1288272B1 (en) | Heat-expandable microsphere and production process thereof | |
| CN110997736B (en) | Method for producing latex | |
| Then et al. | Performance of melamine modified urea–formaldehyde microcapsules in a dental host material | |
| ITMI941065A1 (en) | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS | |
| US7829622B2 (en) | Methods of making polymer composites containing single-walled carbon nanotubes | |
| JP2014514400A (en) | Microcapsule curing agent | |
| JP5798113B2 (en) | Resin fine powder comprising 4-methyl-1-pentene polymer, composition containing the same, and method for producing the same | |
| CN108912383B (en) | Ultrahigh-temperature expandable thermoplastic microspheres and application thereof | |
| KR20220031557A (en) | Method for producing hollow resin particles | |
| US9663610B2 (en) | Catalyst-lean, microcapsule-based self-healing materials via ring-opening metathesis polymerization (ROMP) | |
| CN110724299A (en) | Heat expansion microcapsule not easy to shrink and application thereof | |
| CN115532185A (en) | Polyaniline double-layer microcapsule with barrier property | |
| Dorresteijn et al. | Metallocene supported on porous and nonporous polyurethane particles for ethylene polymerization | |
| Li et al. | Microencapsulation of sulfur in poly (urea–formaldehyde) | |
| Rule | Polymer chemistry for improved self-healing composite materials | |
| JP7134489B2 (en) | Method for producing microcapsules or beads | |
| Naundorf et al. | Hard versus soft materials as supports for metallocene and post‐metallocene catalysts | |
| WO2022268546A1 (en) | Material system for 3d printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |