WO2006132656A2 - High use temperature nanocompositie resins - Google Patents
High use temperature nanocompositie resins Download PDFInfo
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- WO2006132656A2 WO2006132656A2 PCT/US2005/032613 US2005032613W WO2006132656A2 WO 2006132656 A2 WO2006132656 A2 WO 2006132656A2 US 2005032613 W US2005032613 W US 2005032613W WO 2006132656 A2 WO2006132656 A2 WO 2006132656A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
Definitions
- This invention relates generally to the methods and compositions of high temperature thermoset polymers and fiber reinforced composites. More particularly, it relates to methods for the incorporation and use of nanostructured chemicals to control the cure chemistry of the polymer which in turn impacts the thermal, mechanical, and related physical properties of thermoset polymers.
- This invention also relates to processing and applications of the nanoscopically controlled thermoset polymers into composite materials, coatings, adhesives, seals and molded articles.
- the resin and composite applications include improved composite resins, foams, fibers, paints, coatings, adhesives, and surface properties, which lead to fire resistance printability, biocompatibility, and permeability control, optical properties, and architectural coatings.
- thermoset polymers It has long been recognized that the properties of polymers can be tailored to a high degree through variables such as polymer sequence, structure, additive and filler incorporation, composition, morphology, thermodynamic and kinetic processing control. It is similarly known that various sizes and shapes of fillers, and particulates (e.g. Teflon ® , calcium carbonate, silica, carbon black etc.) can be incorporated into preformed polymers (prepolymers) or monomer mixtures to enhance physical and material properties of the resulting formulations.
- Prior art in thermoset polymers has also focused on property modifications through the formation of interpenetrating networks and crosslinks that is either partially or fully occur amongst the chains.
- the desired effect has been to reduce the motion of the polymer chains and segments relative to each other.
- the combination of reduced chain motion combined with more rigid and the thermally stable components ultimately enhances physical properties such as dimensional stability, strength, and thermal stability.
- all of the prior art suffers from process complexity and an inability to control the length scale in all three dimensions at the 1-50nm level.
- the 1-50nm length scale is important for polymeric materials since a typical polymer chain or crosslink has a 8 nm reptation diameter and a radius of gyration of 50nm.
- This invention utilizes nanostructure chemicals to accomplish process simplification, control over cure chemistry and rate, and nanoscopic reinforcement of polymer chains down to the 1 nm level.
- thermoset polymers interpenetrating networks, polymer morphology, and filler technology has not been able to adequately control polymer chain, coil and segmental motion and structure at the 1 nm-10 nm level.
- mismatch of chemical potential e.g., solubility, miscibility, etc.
- solubility, miscibility, etc. the mismatch of chemical potential between polymers and inorganic-based fillers and chemicals has traditionally resulted in a high level of heterogeneity in compounded polymers, which is akin to oil mixed with water. Therefore, there exists a need for appropriately sized chemical reinforcements, with controlled diameters (nanodimensions), distributions and with tailorable chemical functionality, to further refine the properties, of polymers.
- Recent developments in nanoscience have enabled the ability to cost effectively manufacture commercial quantities of materials that are best described as nanostructured chemicals due to their precise chemical formula, hybrid (inorganic-organic) chemical composition, large physical size relative to the size of traditional chemical molecules (0.3-0.5 nm), and small physical size relative to larger sized traditional fillers (>50 nm).
- the present invention describes methods of preparing improved high temperature polymer thermoset resin and composite compositions by controlling their cure chemistry, structure, and properties at the nanoscopic length scale.
- the resulting nano-polymers are wholly useful by themselves or in combination with other polymers or in combination with macroscopic reinforcements such as foam, screen, mesh, fiber, clay, glass mineral and other fillers and other chemicals including catalysts.
- the nano-alloyed polymers are particularly useful for producing polymeric compositions with desirable physical properties such as adhesion to fiberous reinforcement and metal surfaces, water repellency, reduced melt viscosity, resistance to fire and oxidation.
- compositions presented herein contain two primary material combinations: (1) vinyl or other olefinic R group on the POSS cage and (2) cages or partial cages bearing silanol groups (Figure 1).
- These material combinations may take the form of nanostructured oligomers, or nanostructured polymers, polyhedral oligomeric silsesquioxanes, polysilsesquioxanes, polyhedral oligomeric silicates, polysilicates, polyoxometallates, carboranes, boranes, and polymorphs of carbon; or be utilized as chemical crosslinking agents or cure accelerators with nanscopic dimensions.
- crosslinking agents may in turn be utilized with hydrocarbon enes, or silanes and silicones, or phosphines, or thiols or sulfur and copolymers, phenolics, novalacs, resoles, epoxy, cyanate esters, urethanes, polyimides, bismaleimides, etc., and combinations thereof.
- thermosets are accomplished via dissolving or blending of the nanostructured chemicals into the chemical crosslinking agents without the use of solvent. All types and techniques of blending however, including melt blending, dry blending, solution blending, reactive and nonreactive blending are effective.
- thermoset and 'chemical crosslink' are used because chain entanglements or entanglements between a nanostructured chemical and polymer chain can behave as physical crosslinks which are similar in behavior to traditional chemical crosslinks.
- POSS nanostructured chemicals bearing R olefin (vinyl, allyl, cyclopentene, cyclohexene, norborene etc and higher carbon groups) react with silanes to render themoset resins which show desirable thermal, mechanical, electrical and optical properties.
- a variety of hydride containing silanes, .silicones, and silsesquioxanes can be utilized to cure these systems via the hydrosilation method (See Lichtenhan et. al. USP 5,939,576). Particularly useful are trisilanes and cyclic silanes (Figure 2) as these aid in solubilizing the vinyl resin.
- organosilanes and siloxanes are also useful but not shown in Figure 2.
- the hydrosilation reaction process involves the oxidative addition of a Si-H bond across a carbon-carbon double bond and produces no by products ( Figure 3). The reaction is catalyzed by all known hydrosilation catalysts and by free radical initiators.
- POSS nanostructured chemicals bearing R olefin groups react with sulfur and thiols to' also show remarkable thermal, mechanical, electrical and optical properties.
- a variety of sulfur containing curatives accelerants and solubilizing agents can be utilized to cure these systems via the vulcanization and thiolation method (see Lichtenhan et. al. USP 5,939,576). Particularly useful are disulfides and cyclic sulfur ( Figure 4) as these aid in solubilizing the vinyl resin. Part or all of the sulfur may be replaced by a sulfur donor such as a thiuram disulfide.
- the accelerator determines the rate of vulcanization, whereas the accelerator to sulfur ratio dictates the efficiency of cure and, in turn, the thermal stability of the resulting polymer.
- an accelerator to sulfur ratio typically of 1 : 5 is preferred and it gives a network in which about 20 sulfur atoms for each inserted chemical crosslink.
- the reaction process involves the oxidative addition of a S-H or S-S bond across a carbon-carbon double bond and produces no by products ( Figure 5).
- the reaction is catalyzed by all known free radical, UV and thermal initiators.
- activation of the cure process by zinc oxide and stearic acid and the process is "accelerated" by the addition of small quantities of complex sulfur-based chemicals, typically sulphenamides which not only speed up the process, but also influence the properties of the resin, such as its resistance to ageing. It is not possible to list all the chemicals used as accelerators, but some of the main groups used include thiazoles, sulphenamides, and guanidines.
- POSS nanostructured chemicals bearing R olefin groups react with phosphines show remarkable thermal, mechanical, electrical and optical properties.
- a variety of hydride containing phosphines, and phosphates can be utilized to cure these systems via the phosphorylation method (see Lichtenhan et. al. USP 5,939,576). Particularly useful are bis and trisphosphines and oligorneric phosphines ( Figure 6) as these aid in solubilizing the vinyl system.
- the reaction process involves the oxidative addition of a P-H bond across a carbon-carbon double bond and produces no by products. (Figure 7). The reaction is catalyzed by all known by free radical initiators and UV sources.
- POSS nanostructured chemicals bearing R olefin groups react with enes show remarkable thermal, mechanical, electrical and optical properties.
- a variety of hydride containing enes, and including acetylenes can be utilized to cure these systems via the 2+2 and 4+2 addition method (also commonly known as Diels Alder). Particularly useful are linear and cyclic dienes (Figure 8) as these aid in solubilizing the vinyl system.
- the reaction process involves the addition of a c-c double bond across a carbon-carbon double bond and produces no by products ( Figure 9). The reaction is catalyzed by all known by free radical initiators and UV sources.
- Variations to the cure methods and olefin bearing POSS nanostructured chemicals listed can similarily be utilized.
- partial derivatization of the olefinic groups contained on the structures shown in Figure 1 may be carried out by oxidation and substitution methods described by Lichtenhan et al in USP 5,942,638 and 6,100,417, and by Heck methods described by Laine et. al.
- the derivatization of one or more of the vinyl groups in Figure 1 may be desirable for increasing adhesion,, dissolution in base or acid conditions or for increasing or decreasing hydrophobicity and biochemical compatibility.
- the epoxidation of the vinyl systems in Figure 1 is deemed particularly useful for improving adhesion.
- POSS silanols and other reactive or non reactive POSS systems will be useful as reinforcements of olefin polymers to include bismaleimide and olefin terminated polyimides.
- the physical properties of non-olefin containing polymers such as polyimides, epoxy, urethanes can also be desirably enhanced through the incorporation of POSS silanols and other POSS systems capable of interacting with one or more polymer chains.
- Silanol POSS nanostrucutred chemicals are capable of interacting with epoxy and cyanate ester groups through hydrogen bonding of the polar silanol with the oxygen and nitrogen groups in the epoxy and cyanate ester polymer • ( Figure 10).
- Figure 10 Silanol POSS nanostrucutred chemicals
- Different chemical compositions and curing kinetics can permit the user to process over a wide range of temperatures and control the degree of crosslinking.
- the acidic POSS-silanol promotes additional epoxy-amine crosslinking in the post-vitrification stage, which is dominated by diffusion-control mechanisms.
- This can be advantageously utilized in the fabrication of fiber-reinforced composites using the resin transfer molding process, where maintaining the low viscosity for a period of time is required to eliminate porosity and to produce higher Tg materials at a lower post-cure temperature.
- the nanoscopic size of POSS is also useful in controlling the volume of the reactive group which increases the propensity for reaction of the secondary hydrogen atom of the epoxy- amine. This ultimately renders a more completely formed network.
- a similar associative mechanism is operative in cyanate ester systems. These resin crosslink via cyclotrimerization of the OCN functions.
- silanol POSS or related POSS systems e.g. amines, siloxide anions etc
- the POSS increases the volume of the reactive group and subsequently increases the propensity for more complete reaction.
- the silanol groups can also add across the CN triple bond of the cyanate ester groups but this secondary cure mechanism requires a higher temperature in order to reach completion.
- a similar associative mechanism is operative in polyimide systems. These resins crosslink via the generation of a polyamic acid intermediate which is strongly hydrogen bonded and to which POSS can associate via hydrogen bonding. The polyamic acid is subsequently converted into cyclic imide by heating and the loss of water.
- silanol POSS or related POSS systems e.g. amines, siloxide anions etc
- the POSS increases the volume of the amic-acid reactive groups and through the acidity of the silanol increases the rate of water loss and subsequently increases the propensity for more complete reaction and reduced the need for high temperature curing.
- a similar associative mechanism is operative in bismaleimide systems. These resins crosslink via the reaction of diallylbisphenol A with an maleimide to form a cyclic crosslink.
- the POSS is able to strongly hydrogen bond to the diallylbisphenol A and increase the volume of the reactive groups and subsequently increases the propensity for more complete reaction and reduces the need for high temperature curing.
- a similar mechanism is also available for acetylene termated polyimided through the association of the POSS with the imide group.
- a similar associative mechanism is operative in phenolic, resorcinol, and novolac systems. These resins crosslink via the reaction of phenols to form a methylene crosslinked network through the loss of water.
- the POSS is able to strongly hydrogen bond to the phenol and increase the volume of the reactive groups and subsequently increases the propensity for more complete reaction and reduces the need for high temperature curing.
- a similar associative mechanism is operative in polyurethane systems. These resins crosslink via the condensation and addition reaction of an alcohol or amine with an isocyanate to form a urethane crosslink.
- the POSS is able to strongly hydrogen bond to the alcohol and isocyanate and increase the volume of the reactive groups and subsequently increases' the propensity for more complete reaction and reduces the need for high temperature curing.
- FIG. 1 illustrates some representative examples of polyvinyl containing nanostructured chemicals (lower vinyl functionality are also included).
- FIG. 2 illustrates some different silanes useful in forming therm ⁇ sets via the hydrosilation reaction.
- FIG. 3 illustrates the hydrosilation process
- FIG. 4 illustrates some different sulfur curatives useful in forming thermosets.
- FIG. 5 illustrates an aspect of the sulfur cure process.
- FIG. 6. illustrates some different phosphorylation -curatives.
- - ii FIG. 7 the phosphorylation process.
- FIG. 8 illustrates some different ene curatives.
- FIG. 9 illustrates a 2+2 ene curing process.
- FIG. 10 illustrates crosslinked network formation through association of silanol with reactive epoxy groups. Similar mechanism for imide and cyante ester, and urethane polymers.
- Polysilsesquioxanes are materials represented by the formula [RSiO 1 5 ] x
- Polysilsesquioxanes may be either homoleptic or heteroleptic. Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group.
- POSS and POS nanostructure compositions are represented by the formula:
- R is the same as defined above and X includes but is not limited to OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR2) isocyanate (NCO), and R.
- X includes but is not limited to OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR2) isocyanate (NCO), and R.
- m and n refer to the stoichiometry of
- composition The symbol ⁇ indicates that the composition forms a
- the present invention teaches the use of nanostructured chemicals as building blocks for the reinforcement of polymer coils, domains, chains, and segments at the molecular level in thermoset resins.
- nanostructured chemicals can be tailored to exhibit preferential affinity/compatibility with some polymer microstructures through variation of the R groups on each nanostructure.
- the nanostructured chemicals can be tailored to be incompatible with other microstructures within the same polymer, thus allowing for seleotive reinforcement of specific polymer microstructure. Therefore, the factors to effect a selective nanoreinforcement include specific nanosizes of nanostructured chemicals, distributions of nanosizes, and compatabilities and disparities between the nanostrucutured chemical and the polymer system.
- Nanostructured chemicals such as the monoscopic sized POSS structures illustrated in Figure 1 , are available as both solids and oils. Both forms dissolve in solvents, or coreagents thus solving the long-standing dispersion problem associated with traditional particulate fillers or the mixing complexities associated with interpenetrating networks. Moreover, because POSS nanocages dissolve into plastics at the molecular level, the forces (i.e., free energy) from solvati ⁇ n/mixing are sufficient to prevent POSS from coalescing and forming agglomerated domains as 'occurs with traditional and other organofunctionalized fillers. Agglomeration of particulate fillers has been a problem that has traditionally plagued formulators and molders.
- a relative comparison between the size of POSS cages relative to polymer dimensions and filler diameters/ length scales is as follows: Amorphous Segments 0.5 - 5 nm , Octacyclohexyl POSS 1.5 nm, Random Polymer Coils 5 - 10 nm, Particulate Silica 9 - 80 nm, Crystalline Lamellae 1.0 - 9,000 nm, Fillers / Organoclays 2 - 100,000 nm.
- the size of POSS is roughly equivalent to that of most polymer dimensions, thus at a molecular level POSS can effectively alter the motion of polymer chains.
- the ability of POSS to control chain motion is particularly apparent when POSS is incorporated into a polymer chain or network. See U.S. Pat. No.
- POSS nanostructured chemicals possess spherical shapes (per single crystal X-ray diffraction studies), like molecular spheres, and because they dissolve, they are also effective at reducing the viscosity of polymer systems. This benefit is similar to what is produced through the incorporation of plasticizers into polymers, yet with the added benefits of reinforcement of the individual polymer chains due to the nanoscopic nature of the chemicals.
- nanostructured chemicals e.g. POSS, POS
- POSS Solvent Assisted Formulation.
- POSS can be added to a vessel containing the desired polymer, prepolymer, or monomers and dissolved in a sufficient amount of an organic solvent (e.g. hexane, toluene, dichlormethane, etc.) or fluorinated solvent to effect the formation of one homogeneous phase.
- an organic solvent e.g. hexane, toluene, dichlormethane, etc.
- fluorinated solvent e.g. hexane, toluene, dichlormethane, etc.
- the mixture is then stirred under high shear at sufficient temperature to ensure adequate mixing for 30 minutes and the volatile solvent is then removed and recovered under vacuum or using a similar type of process including distillation.
- supercritical fluids such as CO 2 can also be utilized as a replacement for the flammable hydrocarbon solvents.
- the resulting formulation may then be used directly or for subsequent processing.
- ViSi(OMe) 3 (184.72 g, 1.246 mole), PhSi(OMe) 3 (82.37 g, 0.415 mole) and EpCyEtSi(OMe) 3 (102.19 g, 0,415 mole) were dissolve in MEK (1.5 L) and methanol (205 ml_) in a 3 L 3-neck round bottom flask fitted with mechanical starrier and reflux condenser.
- KOH [0.6 g, dissolve in water (149.5 ml_)] was added slowly with stirring. The reaction mixture was heated to reflux and continued for 30 h. After the reaction HCI was added and stir for 30 min. Then 1.5 kg ice/water and 400 ml_ hexane was added and stir for 30 min. Hexane/MEK layer was separated and solvent was removed in the rotavapor to afford solid PM 1285 derivatives.
- a vinyl POSS cage/resin mixture (5.01 g), Sulfur (0.0516 g), Captax (0.025 g), Butyl zimate (0.0255 g) and Methyl tuads (0.0254 g) were mechanically mixed , at room temperature. The mixture then cured at 110 0 C for 24 and to produced an optically , clear resin plaque which was found to have thermal and mechanical properties similar to those of epoxy resins.
- the epoxy (E) to amine (H) ratio used was stoichiometric, [E]/[H] 1/4 1.
- phenyltrisilanol POSS POSS-triol
- the resin was then heated and stirred at 50 °C for 30 min and then degassed in vacuum for 10 min at room temperature.
- the resin was poured in a mold and cured in a mechanical convection air oven set at a specified temperature for 12 h. Compositions, thermomechanical, and processing parameters are given below.
- the procedure of 5a is also applicable to conventional epoxy and anhydride cured systems.
- a three part epoxide was formulated using a 45:55, weight ratio of a Part A POSS epoxide, a Part B anhydride.
- a 3wt% imidazole catalyst was added to this mixture.
- the resin was suitable for molding or infusion.
- Cure was carried out at 70 °C for 120 minutes as was followed by curing the molded part to room temperature before removal from the mold.
- the POSS epoxy had the following desirable properties:
- polyamic acid utilized for the formation of Kapton ® film was utilized to demonstrate the effectiveness of this approach.
- POSS silanol is dissolved into a solution of polyamic acid in NMP solvent.
- the soluble range of POSS in this mixture is from 0.1-60wt% with a preferred range from 5-15wt%.
- the solution of poly (amic acid) and POSS ® in NMP can then be cast into films or coatings and subsequently imidized at 100°C for 2 hours, then 200°C for 2 hours and 300°C for 1 hour.
- POSS results in excellent optical properties, increase modulus (E') at elevated temperature, increased toughness (elongation x ' tensile) and greatly improved resistance to oxidation through the formation of a protective silica glass upon the film surface upon exposure to oxygen plasma or other oxidizing agents.
- the range of POSS silanols can be from 0.1 wt% to 50wt% with a preferred range from 1-10wt%.
- the DABPA was first heated to 100 0 C, and then POSS silanols were dissolved prior to the addition of the BMPA. All mixtures of BMI POSS silanol were optically clear which indicated the full dispersion of the POSS silanol.
- BMPM dimethyl ether modified DABPA
- me-DABPA dimethyl ether modified DABPA
- the POSS BMI affords a T 9 of 365 0 C using a lower temperature, faster, and simplified cure cycle (1 hr at 177 0 C, 2 hrs at 200 0 C 1 and 6 hrs at 25O 0 C). Furthermore, the fact that modulus of the POSS-BMI is not significantly degraded at 400 0 C provides a major enablement for high temperature composites.
- telechelic polyimide resins involves dissolving dialkylester, diamine and monoalkylester (end-capper) in a low boiling alky! alcohol (i.e., methanol). To this mixture is added POSS silanol in various wt percentages from 0.1-50wt% with a preferred loading range from 1-15wt%. Because the POSS silanols and PMR are soluble in the alcohol the resulting viscosity solution can be used to impregnate fibers or fabric to provide a prepreg. The prepreg, upon removal of the solvent, contains a homogeneous mixture of the PMR and POSS reactants.
- the PMR When heated to temperatures between 15O 0 C to 200 0 C, the PMR underg ⁇ s an in- situ condensation reaction to form end-capped imide oligomers. Depending on the reaction conditions (temperature/pressure) of end-capper used, the final cure (thermosetting) is usually performed at temperatures between 315 0 C (600 0 F; nadic ester, NE) to 371 0 C (700 0 F; phenylethynylphthalic acid, metyl ester, PEPE).
- Commercial PMR resins were utilized to confirm the value of POSS in this system. To a HFPE-ll-52 PMR resin, a NASA second generation resin) was added POSS silanols such as trisilanol phenyl POSS and trisilanol ethyl POSS.
- POSS triol is less than HFPE PMR which leads to POSS-containing composite to have a lower density which is a benefit in obtaining "light weight" composite structures.
- the composite samples were exposed to thermal aging, and their mechanical properties were evaluated using three-point bending tests. Testing at 315 0 C (600 0 F), showed an average of 10% improvement in the flexural strength for composites made with 15 wt% additions of trisilanol ethyl POSS and a 15% improvement in the flexural strength for composites made with 15 wt% additions of trisilanol phenyl POSS.
Abstract
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JP2007531456A JP2008512559A (en) | 2004-09-10 | 2005-09-12 | High temperature nanocomposite resin |
EP05857944A EP1789254A4 (en) | 2004-09-10 | 2005-09-12 | High use temperature nanocompositie resins |
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WO2009002660A2 (en) * | 2007-06-15 | 2008-12-31 | Mayaterials, Inc. | Multi-functional silsesquioxanes for novel coating applications |
JP2009509030A (en) * | 2005-08-19 | 2009-03-05 | ハイブリッド・プラスティックス・インコーポレイテッド | Metallized nanostructured chemicals alloyed into polymers |
US7868198B2 (en) | 2007-06-15 | 2011-01-11 | Laine Richard M | Multi-functional silsesquioxanes for novel coating applications |
JP2011084672A (en) * | 2009-10-16 | 2011-04-28 | Fujifilm Corp | Composition for optical material |
EP2875947A1 (en) * | 2013-11-25 | 2015-05-27 | Essex Safety Glass Limited | Laminated glazings |
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KR101208460B1 (en) * | 2005-03-07 | 2012-12-05 | 하이브리드 플라스틱스 인코포레이티드 | Process for assembly of poss monomers |
CN103172870B (en) * | 2011-12-26 | 2015-04-29 | 北京化工大学 | Polyhedral oligomeric silsesquioxane (POSS) modified double-bond containing elastomer and preparation method thereof |
CN109180941B (en) * | 2018-08-23 | 2021-04-23 | 哈尔滨工业大学 | Preparation method of organic-inorganic hybrid octafunctional epoxy POSS resin and preparation method of carbon fiber reinforced composite material |
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US6194485B1 (en) * | 1999-04-01 | 2001-02-27 | Bridgestone Corporation | Compounding process for achieving uniform, fine particle size dispersion of curing agents with minimal use of solvents |
FR2811670B1 (en) * | 2000-07-13 | 2004-05-14 | Rhodia Chimie Sa | STABILIZATION OF POLYMERIC, ORGANOSILICIC OR SILICONE COMPOSITIONS |
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2005
- 2005-09-12 KR KR1020077008072A patent/KR20070110254A/en not_active Application Discontinuation
- 2005-09-12 JP JP2007531456A patent/JP2008512559A/en active Pending
- 2005-09-12 RU RU2007113187/04A patent/RU2007113187A/en not_active Application Discontinuation
- 2005-09-12 EP EP05857944A patent/EP1789254A4/en not_active Withdrawn
- 2005-09-12 WO PCT/US2005/032613 patent/WO2006132656A2/en active Application Filing
- 2005-09-12 CN CNA2005800338746A patent/CN101142332A/en active Pending
- 2005-09-12 TW TW094131334A patent/TW200631998A/en unknown
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009509030A (en) * | 2005-08-19 | 2009-03-05 | ハイブリッド・プラスティックス・インコーポレイテッド | Metallized nanostructured chemicals alloyed into polymers |
WO2009002660A2 (en) * | 2007-06-15 | 2008-12-31 | Mayaterials, Inc. | Multi-functional silsesquioxanes for novel coating applications |
WO2009002660A3 (en) * | 2007-06-15 | 2009-09-24 | Mayaterials, Inc. | Multi-functional silsesquioxanes for novel coating applications |
JP2010530911A (en) * | 2007-06-15 | 2010-09-16 | マヤテリアルズ インク | New multifunctional silsesquioxanes for painting |
US7868198B2 (en) | 2007-06-15 | 2011-01-11 | Laine Richard M | Multi-functional silsesquioxanes for novel coating applications |
JP2011084672A (en) * | 2009-10-16 | 2011-04-28 | Fujifilm Corp | Composition for optical material |
US8506853B2 (en) | 2009-10-16 | 2013-08-13 | Fujifilm Corporation | Composition for optical materials |
EP2875947A1 (en) * | 2013-11-25 | 2015-05-27 | Essex Safety Glass Limited | Laminated glazings |
Also Published As
Publication number | Publication date |
---|---|
TW200631998A (en) | 2006-09-16 |
RU2007113187A (en) | 2008-10-20 |
WO2006132656A3 (en) | 2007-10-04 |
CN101142332A (en) | 2008-03-12 |
EP1789254A2 (en) | 2007-05-30 |
EP1789254A4 (en) | 2011-04-06 |
JP2008512559A (en) | 2008-04-24 |
KR20070110254A (en) | 2007-11-16 |
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