CA1122342A - Vulcanizable silicon terminated polyurethane polymer compositions having improved cure speed - Google Patents
Vulcanizable silicon terminated polyurethane polymer compositions having improved cure speedInfo
- Publication number
- CA1122342A CA1122342A CA311,284A CA311284A CA1122342A CA 1122342 A CA1122342 A CA 1122342A CA 311284 A CA311284 A CA 311284A CA 1122342 A CA1122342 A CA 1122342A
- Authority
- CA
- Canada
- Prior art keywords
- sealant
- sealant composition
- polyurethane polymer
- psi
- radical
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
- C08L2666/44—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
Abstract
VULCANIZABLE SILICON TERMINATED POLYURETHANE POLYMER
COMPOSITION HAVING IMPROVED CURE SPEED
Abstract of the Disclosure Room-temperature-curable silicon-terminated organic sealant compositions having improved cure speeds, and metal and glass primer compositions for use therewith. These sealant compositions comprise a blend of a small amount of N-beta-amino-ethyl, gamma - aminopropyl trimethoxy silane with an organo-silicon-capped, isocyanate-terminated polyurethane polymer. The composition further comprises a carbon black filler containing less than 0.05% of water and preferably further comprises a moisture-curing catalyst such as dibutyl tin diacetate.
COMPOSITION HAVING IMPROVED CURE SPEED
Abstract of the Disclosure Room-temperature-curable silicon-terminated organic sealant compositions having improved cure speeds, and metal and glass primer compositions for use therewith. These sealant compositions comprise a blend of a small amount of N-beta-amino-ethyl, gamma - aminopropyl trimethoxy silane with an organo-silicon-capped, isocyanate-terminated polyurethane polymer. The composition further comprises a carbon black filler containing less than 0.05% of water and preferably further comprises a moisture-curing catalyst such as dibutyl tin diacetate.
Description
`` 112Z34Z
This invention relates to room-temperature-curable silicon terminated organic polymer sealant compositions having improved cure speeds, and to metal and glass primer compositions for use therewith. This invention also relates to the use of such compositions as fast-curing sealants for vehicles and other uses. These sealants are especially useful for sealing glass to metal, such as to secure the windshield to an automobile body.
The relevant prior art is believed to be fully described in U.S. Patents Nos. 3,632,557 and 3,979,344.
Patent 3,632,557 describes vulcanizable silicon-terminated organic polymers whose formula and preparation can be graphically described as follows:
~12Z34~, r--- Polyurethane I oontaining at least O=C=N two urethane linkages N=C=O
¦ per polymer molecule
This invention relates to room-temperature-curable silicon terminated organic polymer sealant compositions having improved cure speeds, and to metal and glass primer compositions for use therewith. This invention also relates to the use of such compositions as fast-curing sealants for vehicles and other uses. These sealants are especially useful for sealing glass to metal, such as to secure the windshield to an automobile body.
The relevant prior art is believed to be fully described in U.S. Patents Nos. 3,632,557 and 3,979,344.
Patent 3,632,557 describes vulcanizable silicon-terminated organic polymers whose formula and preparation can be graphically described as follows:
~12Z34~, r--- Polyurethane I oontaining at least O=C=N two urethane linkages N=C=O
¦ per polymer molecule
2 (RO)3 - Si-R' -ZH
O H H O
~¦ ¦ ' Polyurethane ~ l ll (RO)3 Si-R~-Z-C-N ¦ containing at least I N-C-Z-R' -Si-~OR)3 two urethane linkages r polymer moleeule , ,.
;'~ wherein R is a lower alkyl radical of from 1 to 6 carbon atoms; wherein R' is a divalent bridging radical selected from the groups consisting of a divalent hydrocarbon radical, a divalent hydrocarbon ether radical and a divalent hydrocarbon amino radical; and -. wherein Z is a member selected from the group consisting of -S and -NR", where R" is H or a lower alkyl radical of from 1 to 6 carbon atoms.
.. .
~lZ2342 Patent 3,979,344 describes a sealant comprised of vul-canizable silicon terminated polyurethane polymer, a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane and conventional sealant additives such as fillers, reinforcers, rheology modifiers and ultraviolet light screening compounds.
Conventional carbon black (anhydrous) is disclosed as a filler.
Summarv of the Invention Applicants in Patent 3~979~344 found that, by blending a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane with the above-described prior art vulcanizable polymers in patent 3,632,557, they obtained a sealant composition having out-standing cure speed. Amounts from about 0.5 to about 2.G%, based on the weight of the polymer, were -Eound to be particularly effec-tive.
As an example of the cure rate required for automotive windshield sealants, one of the large auto companies requires a cleavage strength of at least 56 pounds/in2 within 6 hours after the sealant is put in place. Use of the compositions disclosed in the above-mentioned U.S. patent have resulted in cure rates of 14 - 30 pounds within 6 hours, typically about 25 pounds. By contrast the sealants of the present invention have demonstrated 56 lbs/in2 cleavage at 3~ hours curing time. The cleavage test used is described in the Appendix.
Applicants have now found that sealant compositions similar to those of U.S. Patent 3,979,344 are greatly improved if a carbon black filler containing less than 0.05% by weight of water is used in the sealant. For instance, sealants containing . ..
high strength reinforcing carbon black dried to a moisture content ., , ' ~12Z3~LZ
of less than 0.05% produce sealants having suitable rheological properties and higher physical strengths. Commercial grades of carbon black, such as the Regal 300R, used in the examples of Patent 3,979,344, generally contain more than 0.05% moisture, e.g.
up to 1.0% moisture.
According to the present invention, in a sealant composition comprised of a prepolymer whlch is a blend of:
(a) a silicon terminated vulvanizable polyurethane polymer of the formula O H polyurethane H O
,. containing at l ll (R O)3Si-R' - Z-C-N - least two --N-C-Z-R'-S(O R)3 urethane link-ages per polymer molecule wherein R is a lower alkyl radical of from 1 to 6 carbon atoms, R' is a divalent bridging radical selected from the group consisting of a divalent hydrocarbon radical, and a divalent hydrocarbon ether radical, and wherein Z is a member selected from the group consisting of S and NR", where R" is H or a lower alkyl radical of from 1 to 6 carbons with (b) a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane, there is provided the improvement comprising adding, as a rein-forcing filler, a high strength carbon black containing less than0.05% of water to obtain a sealant having a viscosity as indicated by K value of less than 850, and a cure speed of at least 70 psi cleavage in three hours elapsed time.
Applicants in U.S. Patent 3,979,344 found that particularly good results were obtained when the organosilicon compound used in the formula on page 2 to cap the polymer is gamma aminopropyl trimethoxy silane and also when the amount of silanol curing catalyst used in the sealant composition does not exceed 0.1% based on the polymer weight. The preferred silanol con-~Z~3~, densation curing catalyst is dibutyltin diacetate. Amounts of N-beta aminoethyl gamma aminopropyl trimethoxy silane from about 0.2 to about 2.0~ based on the weight of the polymer, have been found to be required to meet the particularly demanding specifica-tions of automotive windshield sealants, which are as follows:
Curing Speed at least 56 lbs/in2 cleavage at 6 hours after application - Adhesion excellent adhesion retention after prolonged weathering Odor no objectionable odor Viscosity (before and K value in the range of 450-after six months aging) 850 Slump freedom from slump Hardness Shore "A" Durometer reading of less than 65.
Description of the various tests for these specifications are set forth in the Appendix.
Applicants have now found that sealants described in U.S. Patent 3,979,344 which contain reinforcing fillers such as carbon black can be improved in physical strengths by using a reinforcing carbon filler, especially a high strength carbon, provided that the - 4a -, ~12Z3~2 filler has a moisture content o-E less than 0O05% by weight. Use of high strength reinforcing carbon blacks containing more than 0.05/O
of moisture, e.g. 0.05 to 0.10%~ produces sealants having viscos-ities that are too high for many applications, e.g., as windshield sealants, because the handling and pumping equipment cannot apply the high viscosity materials at a fast enough rate to be practical.
The use of especially dry carbon black in accordance with the present invention results in sealants having viscosities low enough for practical application as windshield sealants, while having higher solids, less shrinkage and lower cost Typical physical properties obtained using polymer des-cribed in Example 1 of U.S. Patent 3,979,344 containing high strength reinforcing carbon versus ordinary carbon black are:
.~ -High OrdinaryStrength Tensile strength (psi) 760 1100 Elongation at break (/O) 140 300 Thus the advantages oE using a high strength reinforcing carbon black are readily apparent. The improved physical properties are largely responsible for improvements in such properties as bond or cleavage strength.
~: High strength reinforcing carbon black used herein means carbon black with relatively high surEace area and small particle size, e.g. a surface area of 80 square meters or more per gram and a particle size of 27 ~illimicrons diameter or less.
Generally, for use in automobile windshield applications the sealant must have a K value of L~50 to 850, or viscosities of under 60 seconds at 60 psi. The K value requirement provides good non-slump (i.e., non-sag) properties and sealants having viscosities 1:~22:3~
under 60 seconds at 60 psi generally Eall within the required K value range, and have a viscosity low enough to be pumped at practical speeds through application equipment.
One disadvantage of sealants made in accordance with Patent
O H H O
~¦ ¦ ' Polyurethane ~ l ll (RO)3 Si-R~-Z-C-N ¦ containing at least I N-C-Z-R' -Si-~OR)3 two urethane linkages r polymer moleeule , ,.
;'~ wherein R is a lower alkyl radical of from 1 to 6 carbon atoms; wherein R' is a divalent bridging radical selected from the groups consisting of a divalent hydrocarbon radical, a divalent hydrocarbon ether radical and a divalent hydrocarbon amino radical; and -. wherein Z is a member selected from the group consisting of -S and -NR", where R" is H or a lower alkyl radical of from 1 to 6 carbon atoms.
.. .
~lZ2342 Patent 3,979,344 describes a sealant comprised of vul-canizable silicon terminated polyurethane polymer, a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane and conventional sealant additives such as fillers, reinforcers, rheology modifiers and ultraviolet light screening compounds.
Conventional carbon black (anhydrous) is disclosed as a filler.
Summarv of the Invention Applicants in Patent 3~979~344 found that, by blending a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane with the above-described prior art vulcanizable polymers in patent 3,632,557, they obtained a sealant composition having out-standing cure speed. Amounts from about 0.5 to about 2.G%, based on the weight of the polymer, were -Eound to be particularly effec-tive.
As an example of the cure rate required for automotive windshield sealants, one of the large auto companies requires a cleavage strength of at least 56 pounds/in2 within 6 hours after the sealant is put in place. Use of the compositions disclosed in the above-mentioned U.S. patent have resulted in cure rates of 14 - 30 pounds within 6 hours, typically about 25 pounds. By contrast the sealants of the present invention have demonstrated 56 lbs/in2 cleavage at 3~ hours curing time. The cleavage test used is described in the Appendix.
Applicants have now found that sealant compositions similar to those of U.S. Patent 3,979,344 are greatly improved if a carbon black filler containing less than 0.05% by weight of water is used in the sealant. For instance, sealants containing . ..
high strength reinforcing carbon black dried to a moisture content ., , ' ~12Z3~LZ
of less than 0.05% produce sealants having suitable rheological properties and higher physical strengths. Commercial grades of carbon black, such as the Regal 300R, used in the examples of Patent 3,979,344, generally contain more than 0.05% moisture, e.g.
up to 1.0% moisture.
According to the present invention, in a sealant composition comprised of a prepolymer whlch is a blend of:
(a) a silicon terminated vulvanizable polyurethane polymer of the formula O H polyurethane H O
,. containing at l ll (R O)3Si-R' - Z-C-N - least two --N-C-Z-R'-S(O R)3 urethane link-ages per polymer molecule wherein R is a lower alkyl radical of from 1 to 6 carbon atoms, R' is a divalent bridging radical selected from the group consisting of a divalent hydrocarbon radical, and a divalent hydrocarbon ether radical, and wherein Z is a member selected from the group consisting of S and NR", where R" is H or a lower alkyl radical of from 1 to 6 carbons with (b) a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane, there is provided the improvement comprising adding, as a rein-forcing filler, a high strength carbon black containing less than0.05% of water to obtain a sealant having a viscosity as indicated by K value of less than 850, and a cure speed of at least 70 psi cleavage in three hours elapsed time.
Applicants in U.S. Patent 3,979,344 found that particularly good results were obtained when the organosilicon compound used in the formula on page 2 to cap the polymer is gamma aminopropyl trimethoxy silane and also when the amount of silanol curing catalyst used in the sealant composition does not exceed 0.1% based on the polymer weight. The preferred silanol con-~Z~3~, densation curing catalyst is dibutyltin diacetate. Amounts of N-beta aminoethyl gamma aminopropyl trimethoxy silane from about 0.2 to about 2.0~ based on the weight of the polymer, have been found to be required to meet the particularly demanding specifica-tions of automotive windshield sealants, which are as follows:
Curing Speed at least 56 lbs/in2 cleavage at 6 hours after application - Adhesion excellent adhesion retention after prolonged weathering Odor no objectionable odor Viscosity (before and K value in the range of 450-after six months aging) 850 Slump freedom from slump Hardness Shore "A" Durometer reading of less than 65.
Description of the various tests for these specifications are set forth in the Appendix.
Applicants have now found that sealants described in U.S. Patent 3,979,344 which contain reinforcing fillers such as carbon black can be improved in physical strengths by using a reinforcing carbon filler, especially a high strength carbon, provided that the - 4a -, ~12Z3~2 filler has a moisture content o-E less than 0O05% by weight. Use of high strength reinforcing carbon blacks containing more than 0.05/O
of moisture, e.g. 0.05 to 0.10%~ produces sealants having viscos-ities that are too high for many applications, e.g., as windshield sealants, because the handling and pumping equipment cannot apply the high viscosity materials at a fast enough rate to be practical.
The use of especially dry carbon black in accordance with the present invention results in sealants having viscosities low enough for practical application as windshield sealants, while having higher solids, less shrinkage and lower cost Typical physical properties obtained using polymer des-cribed in Example 1 of U.S. Patent 3,979,344 containing high strength reinforcing carbon versus ordinary carbon black are:
.~ -High OrdinaryStrength Tensile strength (psi) 760 1100 Elongation at break (/O) 140 300 Thus the advantages oE using a high strength reinforcing carbon black are readily apparent. The improved physical properties are largely responsible for improvements in such properties as bond or cleavage strength.
~: High strength reinforcing carbon black used herein means carbon black with relatively high surEace area and small particle size, e.g. a surface area of 80 square meters or more per gram and a particle size of 27 ~illimicrons diameter or less.
Generally, for use in automobile windshield applications the sealant must have a K value of L~50 to 850, or viscosities of under 60 seconds at 60 psi. The K value requirement provides good non-slump (i.e., non-sag) properties and sealants having viscosities 1:~22:3~
under 60 seconds at 60 psi generally Eall within the required K value range, and have a viscosity low enough to be pumped at practical speeds through application equipment.
One disadvantage of sealants made in accordance with Patent
3,979,344 is that the viscosity tends to vary from batch to batch, presumably due to variations in the water content of the carbon black used. This variation in viscosity and corresponding K values is illustrated in the following data for four different batches of sealant:
60 psi Viscosity K Value 1. 16 519 3. 49 433 ~. 62 455 These data show that the viscosity varies considerably using the invention of Patent 3,979,344. By using the present invention, a higher grade of carbon black can be used to obtain more consistent viscosities from batch to batch and still maintain the required low K value.
Further, sealants made in accordance with the present invention show improved cleavage properties over those/Patent 3,979,344. For example, the cleavage value of the sealant ~f Example 2 of said patent is 60 psi after 3% hours of cure and 326 psi after 48 hours; the same formulation using high strength reinforcing carbon black containing less than OO05% water had cleavage values of 70 psi after 3% hours and 500 psi aEter 48 hoursO This improvement in cleavage values is related to an improvement in the basic physical properties such as tensile and elongation propertiesO
1~12~342 The manner of preparing a typical sealant composition of this invention is set forth in the Eollowing examples.
A polymer of the type described in U.S. Patent 3,632,557 was prepared as follows:
A. Niax PPG 2025 ONE 2001.00 g.
(2000 Molecular Weight Polyether Diol from Union Carbide Corporation) Hylené TM 204.00 ~80:20 Grade Toluene Diisocyanate from DuPont) Glacial Acetic Acid 0.55 Dibutyltin Diacetate 0.45 ' B. Anhydrous Toluene 110,00 C. Anhydrous Toluene 81.00 ~ - Silane A 1110 ; (Gamma Aminopropyl trimethoxy silane from Union Carbide Corp.) 68.30 D. Anhydrous Methanol 273.00 2738.30 g.
A was heated to 155 degrees F. under anhydrous conditions and maintained at that temperature for 55 minutes, at the end of which time B was added, Over the next 45 minutes the temperature was gradually reduced to 105 degrees F. Heating was continued at about 105 degrees F. for the next 2.25 hours, at the end of which time C was added. Over the next 2.25 hours, the temperature was maintained in the range of 150-165 degrees F., checking for NCO
until none was found. The resultant material was refluxed with D
for a short time and then allowed to foam to achieve deaeration, and finally cooled.
llZ2342 EX~PLE 2 A sealant was prepared as follows:
Parts by Weight Polymer of Example 1 100 High Strength reinforcing carbon black e.g.
Regal 300 R, dried to a moisture content less than 0.05% 35 Thixseal 1084 (NL Industries - an inorganically 10 modified derivative of castor oil) 0.50 Dibutyltin diacetate (DBTDA) 0.08 Antioxidant (AO2246) (American Cyanamid Co.
--2,2'-methylenebis(4-methyl-6-t-butylphenol) 0.65 N-beta aminoethyl, gamma aminopropyl trimethoxy silane (A 1120) 0.50 The polymer of Example 1, Thixseal 1084, DBTDA, anti-oxidant AO2246 and A1120 silane were added to a dual shaft (sweep blade plus high speed disperser) mixer under anhydrous conditions and mixed for about 5-10 minutes. The mixer is kept at all times under a slight pressure (about 1 psi) of dry nitrogen. The car-bon black dried to less than 0.05%, moisture is then added and the resultant mixture is then mixed 3/4 - 1 hour. The resultant sealer is allowed to cool 10-15 minutes, degassed under reduced ; pressure and packaged under anhydrous conditions.
The following properties were obtained by testing re-presentative examples of sealants made according to Example 2:
Viscosity 37 sec.
Tensile strength 1100 psi `~ Elongation 300 %
Slump none Curing speed (cleavage assemblies) 87 psi at 3 hrs.
Hardness (Shore A Durometer) 60 112;~3~Z
Although the sealant of this invention exhibits sealant and adhesive properties under normal conditions, in order to achieve the outstanding properties set forth above for automotive windshield use it is necessary to employ the glass and metal primers described below.
Percent Glass Primer by Weight Chlorinated Rubber 5 - 35%
Carbon Black tfurnace type) 2 - 20 Silane A1120 (See Example 2) 0.1 - 2.0 Tinuvin 327 - - 0.1 - 2O0 (2-(3', 5' - ditert-butyl-2'-hydroxy phenyl) - 5 chlorobenzotriazole from Ciba-Giegy) Conventional anhydrous solvent for ~ chlorinated rubber 20 - 80 `' Conventional plasticizer for chlorinated rubber 25 - 200% of amount of chlor-inated rubber used The chlorinated rubber used in the glass primer should be a 5,000 - 20,000 molecular weight rubber having a 64-65% chlorine content. The chemistry and molecular structure of such rubbers is - described in Treatise In Coatings, Vol. 1, Part 1 by Myers and Long (Dekker, 1967). Such rubbers can be obtained from ICI, for example Alloprene X-20, and Hercules (Parlon). Viscosity grades such as 5, 10, 20 or 125 can be used but grade 20 is preferred Conventional anhydrous aromatic hydrocarbon solvents for chlorinated rubber can be employed as solvent in the glass primer.
The solvent employed must be anhydrous or the silane will be hydro-lyzed and ruined.
~1~1223~LZ
The plasticizer employed in the glass primer should be selected from the group of polymeric polyester plasticizers which are compatible with chlorinated rubber. That group will be familiar to those skilled in the art Paraplex G-56, a polymeric polyester plasticizer from Rohm & Haas, is preferred.
The pre~erred glass primer composition is:
Weight Percent Range Alloprene X-20 chlorinated rubber 15 - 20%
Paraple~ G-56 plasticizer 15 - 20 Sterling R carbon black 4 - 10 Silane A-1120 0.5 - 1.0 Tinuvin 327 U.V. screening agent 1 - 2 Anhydrous toluene 50 - 60 100/~
Metal Primer - For Acrylic Lacquered Steel The metal primer is broadly the same as the broad glass primer composition, but with the following exceptions:
1) omit the U. V. screening agent, 2~ as plasticizer, a conventional monomeric plasticizer for chlorinated rubber~ such as diisodecyl phthalate, is preferred. ~owever, the class of polymeric plasti-cizers described for the glass primer may also be usedO
Weight Percent Range Alloprene X-20 chlorinated rubber 16 - 23%
Diisodecyl phthalate plasticizer 5 - 15 Sterling R carbon black 0.5 - 1.0 Anhydrous toluene 60 - 70 100%
11223~' -lL-The normal manner of use of -the primers and sealant is to brush the glass primer on the perimeter of the windshield, air dry it for a few minutes and then deposit a bead of the sealant on the primed area. The acrylic lacquered body steel is also primed by brushing on the metal primer and allowing it to air dry for a few minutes. The sealant bead on the windshield is then firmly pressed against the body steel.
The adhesive properties of the sealant of this inven-tion applied as described have proved to contribute substantially to the strength ~resistance to crushing) of the roof oE the automobiles on which they are used.
The sealant of this invention may also contain conven-tional sealant additives such as additional fillers, reinforcers, rheology modifiers and ultraviolet light screening compounds.
The especially dry carbon black of the examples of this applica-tion is necessary to achieve the particular viscosity, slump and 'I hardness properties required for the automotive windshield uses mentioned herein. The Thixseal rheology modifier, although not necessary to the broad invention, is necessary to provide the particularly demanding slump and viscosity properties of windshield sealants. Determination of effective amounts of these materials to achieve the desired properties will be within the skill o those skilled in the art.
It has been found that when the silanol condensation catalyst, such as dibutyltin diacetate is employed in amounts greater than 0.1%, based on the polymer weight, the adhesive properties of the sealant sufEer degradation upon aging.
Use of the closely related material gamma aminopropyl trimethoxy silane (A-lllO) in place of A-1120 has resulted in very significantly longer cure times. For example, the time re-quired to reach 56 lbs/in2 was 8 hours using A-lllO versus 2 hours with A-1120.
1~2;;:342 When the preEerred polymer capping organosilicon (gamma aminopropyl trimethoxy silane) is used in the reaction on page 2, R is CH3 R' is C3H6 and Z is NH.
Although this specification has largely concerned itself with achieving the demanding properties required for automotive windshield sealants, those skilled in the art will appreciate that sealants for less demanding applications can be made outside the ranges specified herein.
APPENDIX
Test Methods Cure Rate ~Cleavage) A L~t- X ~tl bead is extruded on one primed, acrylic lacquered plate. Then another plate is placed on top. The plates are pulled in a plane perpendicular to the plane of the bead.
Viscosity Viscosity is determined by timing the flow of 20 gms.
of sealant through a 0.104" orifice at 60 psi pressure. K value is determined by measuring the viscosity at 60 psi and again at 30 psi pressure and inserting the two values thus obtained into the equation for K value:
n ~g P1 - log P2 K = P x tn where = log t2 ~ log t Slump or Sag Characteristics A ~" x ~" cross section sealant bead is appl;ed to a glass plate and allowed to cure in the vertical plane. The sealant should not move downward or "slump" or "sag" but rather should remain in the original position.
Hardness -Hardness of the cured sealant is measured by a Shore "A" - 2 Durometer.
Tensile and Elongation Tensile strength and elongation at break are determined according to ASTM method D412 (using Die C).
..
60 psi Viscosity K Value 1. 16 519 3. 49 433 ~. 62 455 These data show that the viscosity varies considerably using the invention of Patent 3,979,344. By using the present invention, a higher grade of carbon black can be used to obtain more consistent viscosities from batch to batch and still maintain the required low K value.
Further, sealants made in accordance with the present invention show improved cleavage properties over those/Patent 3,979,344. For example, the cleavage value of the sealant ~f Example 2 of said patent is 60 psi after 3% hours of cure and 326 psi after 48 hours; the same formulation using high strength reinforcing carbon black containing less than OO05% water had cleavage values of 70 psi after 3% hours and 500 psi aEter 48 hoursO This improvement in cleavage values is related to an improvement in the basic physical properties such as tensile and elongation propertiesO
1~12~342 The manner of preparing a typical sealant composition of this invention is set forth in the Eollowing examples.
A polymer of the type described in U.S. Patent 3,632,557 was prepared as follows:
A. Niax PPG 2025 ONE 2001.00 g.
(2000 Molecular Weight Polyether Diol from Union Carbide Corporation) Hylené TM 204.00 ~80:20 Grade Toluene Diisocyanate from DuPont) Glacial Acetic Acid 0.55 Dibutyltin Diacetate 0.45 ' B. Anhydrous Toluene 110,00 C. Anhydrous Toluene 81.00 ~ - Silane A 1110 ; (Gamma Aminopropyl trimethoxy silane from Union Carbide Corp.) 68.30 D. Anhydrous Methanol 273.00 2738.30 g.
A was heated to 155 degrees F. under anhydrous conditions and maintained at that temperature for 55 minutes, at the end of which time B was added, Over the next 45 minutes the temperature was gradually reduced to 105 degrees F. Heating was continued at about 105 degrees F. for the next 2.25 hours, at the end of which time C was added. Over the next 2.25 hours, the temperature was maintained in the range of 150-165 degrees F., checking for NCO
until none was found. The resultant material was refluxed with D
for a short time and then allowed to foam to achieve deaeration, and finally cooled.
llZ2342 EX~PLE 2 A sealant was prepared as follows:
Parts by Weight Polymer of Example 1 100 High Strength reinforcing carbon black e.g.
Regal 300 R, dried to a moisture content less than 0.05% 35 Thixseal 1084 (NL Industries - an inorganically 10 modified derivative of castor oil) 0.50 Dibutyltin diacetate (DBTDA) 0.08 Antioxidant (AO2246) (American Cyanamid Co.
--2,2'-methylenebis(4-methyl-6-t-butylphenol) 0.65 N-beta aminoethyl, gamma aminopropyl trimethoxy silane (A 1120) 0.50 The polymer of Example 1, Thixseal 1084, DBTDA, anti-oxidant AO2246 and A1120 silane were added to a dual shaft (sweep blade plus high speed disperser) mixer under anhydrous conditions and mixed for about 5-10 minutes. The mixer is kept at all times under a slight pressure (about 1 psi) of dry nitrogen. The car-bon black dried to less than 0.05%, moisture is then added and the resultant mixture is then mixed 3/4 - 1 hour. The resultant sealer is allowed to cool 10-15 minutes, degassed under reduced ; pressure and packaged under anhydrous conditions.
The following properties were obtained by testing re-presentative examples of sealants made according to Example 2:
Viscosity 37 sec.
Tensile strength 1100 psi `~ Elongation 300 %
Slump none Curing speed (cleavage assemblies) 87 psi at 3 hrs.
Hardness (Shore A Durometer) 60 112;~3~Z
Although the sealant of this invention exhibits sealant and adhesive properties under normal conditions, in order to achieve the outstanding properties set forth above for automotive windshield use it is necessary to employ the glass and metal primers described below.
Percent Glass Primer by Weight Chlorinated Rubber 5 - 35%
Carbon Black tfurnace type) 2 - 20 Silane A1120 (See Example 2) 0.1 - 2.0 Tinuvin 327 - - 0.1 - 2O0 (2-(3', 5' - ditert-butyl-2'-hydroxy phenyl) - 5 chlorobenzotriazole from Ciba-Giegy) Conventional anhydrous solvent for ~ chlorinated rubber 20 - 80 `' Conventional plasticizer for chlorinated rubber 25 - 200% of amount of chlor-inated rubber used The chlorinated rubber used in the glass primer should be a 5,000 - 20,000 molecular weight rubber having a 64-65% chlorine content. The chemistry and molecular structure of such rubbers is - described in Treatise In Coatings, Vol. 1, Part 1 by Myers and Long (Dekker, 1967). Such rubbers can be obtained from ICI, for example Alloprene X-20, and Hercules (Parlon). Viscosity grades such as 5, 10, 20 or 125 can be used but grade 20 is preferred Conventional anhydrous aromatic hydrocarbon solvents for chlorinated rubber can be employed as solvent in the glass primer.
The solvent employed must be anhydrous or the silane will be hydro-lyzed and ruined.
~1~1223~LZ
The plasticizer employed in the glass primer should be selected from the group of polymeric polyester plasticizers which are compatible with chlorinated rubber. That group will be familiar to those skilled in the art Paraplex G-56, a polymeric polyester plasticizer from Rohm & Haas, is preferred.
The pre~erred glass primer composition is:
Weight Percent Range Alloprene X-20 chlorinated rubber 15 - 20%
Paraple~ G-56 plasticizer 15 - 20 Sterling R carbon black 4 - 10 Silane A-1120 0.5 - 1.0 Tinuvin 327 U.V. screening agent 1 - 2 Anhydrous toluene 50 - 60 100/~
Metal Primer - For Acrylic Lacquered Steel The metal primer is broadly the same as the broad glass primer composition, but with the following exceptions:
1) omit the U. V. screening agent, 2~ as plasticizer, a conventional monomeric plasticizer for chlorinated rubber~ such as diisodecyl phthalate, is preferred. ~owever, the class of polymeric plasti-cizers described for the glass primer may also be usedO
Weight Percent Range Alloprene X-20 chlorinated rubber 16 - 23%
Diisodecyl phthalate plasticizer 5 - 15 Sterling R carbon black 0.5 - 1.0 Anhydrous toluene 60 - 70 100%
11223~' -lL-The normal manner of use of -the primers and sealant is to brush the glass primer on the perimeter of the windshield, air dry it for a few minutes and then deposit a bead of the sealant on the primed area. The acrylic lacquered body steel is also primed by brushing on the metal primer and allowing it to air dry for a few minutes. The sealant bead on the windshield is then firmly pressed against the body steel.
The adhesive properties of the sealant of this inven-tion applied as described have proved to contribute substantially to the strength ~resistance to crushing) of the roof oE the automobiles on which they are used.
The sealant of this invention may also contain conven-tional sealant additives such as additional fillers, reinforcers, rheology modifiers and ultraviolet light screening compounds.
The especially dry carbon black of the examples of this applica-tion is necessary to achieve the particular viscosity, slump and 'I hardness properties required for the automotive windshield uses mentioned herein. The Thixseal rheology modifier, although not necessary to the broad invention, is necessary to provide the particularly demanding slump and viscosity properties of windshield sealants. Determination of effective amounts of these materials to achieve the desired properties will be within the skill o those skilled in the art.
It has been found that when the silanol condensation catalyst, such as dibutyltin diacetate is employed in amounts greater than 0.1%, based on the polymer weight, the adhesive properties of the sealant sufEer degradation upon aging.
Use of the closely related material gamma aminopropyl trimethoxy silane (A-lllO) in place of A-1120 has resulted in very significantly longer cure times. For example, the time re-quired to reach 56 lbs/in2 was 8 hours using A-lllO versus 2 hours with A-1120.
1~2;;:342 When the preEerred polymer capping organosilicon (gamma aminopropyl trimethoxy silane) is used in the reaction on page 2, R is CH3 R' is C3H6 and Z is NH.
Although this specification has largely concerned itself with achieving the demanding properties required for automotive windshield sealants, those skilled in the art will appreciate that sealants for less demanding applications can be made outside the ranges specified herein.
APPENDIX
Test Methods Cure Rate ~Cleavage) A L~t- X ~tl bead is extruded on one primed, acrylic lacquered plate. Then another plate is placed on top. The plates are pulled in a plane perpendicular to the plane of the bead.
Viscosity Viscosity is determined by timing the flow of 20 gms.
of sealant through a 0.104" orifice at 60 psi pressure. K value is determined by measuring the viscosity at 60 psi and again at 30 psi pressure and inserting the two values thus obtained into the equation for K value:
n ~g P1 - log P2 K = P x tn where = log t2 ~ log t Slump or Sag Characteristics A ~" x ~" cross section sealant bead is appl;ed to a glass plate and allowed to cure in the vertical plane. The sealant should not move downward or "slump" or "sag" but rather should remain in the original position.
Hardness -Hardness of the cured sealant is measured by a Shore "A" - 2 Durometer.
Tensile and Elongation Tensile strength and elongation at break are determined according to ASTM method D412 (using Die C).
..
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a sealant composition comprised of a prepolymer which is a blend of:
(a) a silicon terminated vulcanizable polyurethane polymer of the formula wherein R is a lower alkyl radical of from 1 to 6 carbon atoms, R' is a divalent bridging radical selected from the group con-sisting of a divalent hydrocarbon radical, and a divalent hydro-carbon ether radical, and wherein Z is a member selected from the group consisting of S and NR', where R" is H or a lower alkyl radical of from 1 to 6 carbons with (b) a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane, the improvement comprising adding, as a reinforcing filler, a high strength carbon black containing less than 0.05% of water to obtain a sealant having a viscosity as indicated by K value of less than 850, and a cure speed of at least 70 psi cleavage in three hours elapsed time.
(a) a silicon terminated vulcanizable polyurethane polymer of the formula wherein R is a lower alkyl radical of from 1 to 6 carbon atoms, R' is a divalent bridging radical selected from the group con-sisting of a divalent hydrocarbon radical, and a divalent hydro-carbon ether radical, and wherein Z is a member selected from the group consisting of S and NR', where R" is H or a lower alkyl radical of from 1 to 6 carbons with (b) a small amount of N-beta aminoethyl, gamma aminopropyl trimethoxy silane, the improvement comprising adding, as a reinforcing filler, a high strength carbon black containing less than 0.05% of water to obtain a sealant having a viscosity as indicated by K value of less than 850, and a cure speed of at least 70 psi cleavage in three hours elapsed time.
2. The sealant composition of claim 1 containing up to 25% by weight of plasticizer based on weight of polymer.
3. The sealant composition of claim 1 having a tensile strength of at least 900 psi and an elongation at break of at least 250%.
4. The sealant composition of claim 1, 2 or 3 wherein the catalyst is dibutyl tin diacetate.
5. The sealant composition of claim 1, 2 or 3 wherein R
is CH3, R' is C3H6 and Z is NH.
is CH3, R' is C3H6 and Z is NH.
6. The sealant composition of claim 1, 2 or 3 wherein R
is CH3, R' is C3H6 and Z is NH, and the catalyst is dibutyl tin diacetate.
is CH3, R' is C3H6 and Z is NH, and the catalyst is dibutyl tin diacetate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US930,309 | 1978-08-02 | ||
| US05/930,309 US4222925A (en) | 1978-08-02 | 1978-08-02 | Vulcanizable silicon terminated polyurethane polymer compositions having improved cure speed |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122342A true CA1122342A (en) | 1982-04-20 |
Family
ID=25459180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA311,284A Expired CA1122342A (en) | 1978-08-02 | 1978-09-14 | Vulcanizable silicon terminated polyurethane polymer compositions having improved cure speed |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4222925A (en) |
| CA (1) | CA1122342A (en) |
Families Citing this family (63)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4345053A (en) * | 1981-07-17 | 1982-08-17 | Essex Chemical Corp. | Silicon-terminated polyurethane polymer |
| US4374237A (en) * | 1981-12-21 | 1983-02-15 | Union Carbide Corporation | Silane-containing isocyanate-terminated polyurethane polymers |
| DE3203687A1 (en) * | 1982-02-04 | 1983-08-11 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | ELASTIC RESIN MATERIALS WITH IMPROVED ADHESIVE EFFECT |
| US4429082A (en) | 1982-05-10 | 1984-01-31 | Ppg Industries, Inc. | Film-forming resins containing alkoxy silane groups |
| DE3220866A1 (en) * | 1982-06-03 | 1983-12-08 | Dynamit Nobel Ag, 5210 Troisdorf | CROSSLINKABLE RESIN MIXTURES |
| US4430486A (en) | 1982-11-29 | 1984-02-07 | Ppg Industries, Inc. | Film-forming urethane resins containing alkoxy silane groups and acrylyl groups |
| US4468492A (en) * | 1983-07-15 | 1984-08-28 | Ppg Industries, Inc. | Polymeric organo functional silanes as reactive modifying materials |
| US4582873A (en) * | 1984-05-21 | 1986-04-15 | Ppg Industries, Inc. | Process for producing aqueous dispersions, internally silylated and dispersed polyurethane resins, and surfaces containing same |
| US4542065A (en) * | 1984-05-21 | 1985-09-17 | Ppg Industries, Inc. | Chemically treated glass fibers and strands and dispersed products thereof |
| US4645816A (en) * | 1985-06-28 | 1987-02-24 | Union Carbide Corporation | Novel vulcanizable silane-terminated polyurethane polymers |
| US4625012A (en) * | 1985-08-26 | 1986-11-25 | Essex Specialty Products, Inc. | Moisture curable polyurethane polymers |
| DE3737245A1 (en) * | 1987-11-03 | 1989-05-18 | Bayer Ag | AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYURETHANES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS COATING AGENTS OR FOR THE PRODUCTION OF COATING AGENTS |
| US4847319A (en) * | 1988-05-23 | 1989-07-11 | The B. F. Goodrich Company | Sealant compositions or coating mixtures containing functional silane or siloxane adhesion promotors nonreactive with blocked isocyanates |
| US4882003A (en) * | 1988-07-19 | 1989-11-21 | Basf Corporation | Sealant primer composition and method |
| US4889903A (en) * | 1988-08-03 | 1989-12-26 | Basf Corporation | Fast-cure polyurethane sealant composition containing titanium ester accelerators |
| US5354808A (en) * | 1992-12-08 | 1994-10-11 | Minnesota Mining And Manufacturing Company | Polyurethanes including pendant hindered amines and compositions incorporating same |
| US5840800A (en) | 1995-11-02 | 1998-11-24 | Dow Corning Corporation | Crosslinked emulsions of pre-formed silicon modified organic polymers |
| US6001946A (en) * | 1996-09-23 | 1999-12-14 | Witco Corporation | Curable silane-encapped compositions having improved performances |
| US5976669A (en) * | 1996-12-20 | 1999-11-02 | 3M Innovative Properties Company | Retroreflective article having launderably durable bead-bond |
| US5990257A (en) * | 1998-01-22 | 1999-11-23 | Witco Corporation | Process for producing prepolymers which cure to improved sealants, and products formed thereby |
| US6828403B2 (en) * | 1998-04-27 | 2004-12-07 | Essex Specialty Products, Inc. | Method of bonding a window to a substrate using a silane functional adhesive composition |
| KR100607839B1 (en) | 1998-04-27 | 2006-08-04 | 더 다우 케미칼 캄파니 | A cure on demand adhesive composition, a process for binding substrates using the same and a window module on which the composition is applied |
| US6124387A (en) * | 1998-12-22 | 2000-09-26 | Adco Products, Inc. | Fast-cure silylated polymer adhesive |
| US6310170B1 (en) | 1999-08-17 | 2001-10-30 | Ck Witco Corporation | Compositions of silylated polymer and aminosilane adhesion promoters |
| US6197912B1 (en) | 1999-08-20 | 2001-03-06 | Ck Witco Corporation | Silane endcapped moisture curable compositions |
| JP2001311056A (en) * | 2000-04-28 | 2001-11-09 | Kanegafuchi Chem Ind Co Ltd | Method for bonding adherend |
| US6498210B1 (en) | 2000-07-13 | 2002-12-24 | Adco Products, Inc. | Silylated polyurethanes for adhesives and sealants with improved mechanical properties |
| EP1256595A1 (en) * | 2001-05-10 | 2002-11-13 | Sika AG, vorm. Kaspar Winkler & Co. | Adhesive filled with surface-treated chalk and carbon black |
| DE10130889A1 (en) * | 2001-06-27 | 2003-01-30 | Henkel Teroson Gmbh | Adhesives / sealants with high electrical resistance |
| US6649016B2 (en) | 2002-03-04 | 2003-11-18 | Dow Global Technologies Inc. | Silane functional adhesive composition and method of bonding a window to a substrate without a primer |
| CA2547767A1 (en) * | 2003-12-10 | 2005-06-30 | Dow Global Technologies Inc. | System for bonding glass into a structure |
| US7060750B2 (en) * | 2004-04-28 | 2006-06-13 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes and their use in sealant, adhesive and coating compositions |
| US20050288415A1 (en) * | 2004-06-23 | 2005-12-29 | Beers Melvin D | Highly elastomeric and paintable silicone compositions |
| US7888425B2 (en) * | 2004-07-16 | 2011-02-15 | Reichhold, Inc. | Low volatile organic compound stable solvent-based polyurethane compositions for coatings |
| US7494540B2 (en) * | 2004-12-15 | 2009-02-24 | Dow Global Technologies, Inc. | System for bonding glass into a structure |
| US7417105B2 (en) | 2005-02-15 | 2008-08-26 | Momentive Performance Materials Inc. | Crosslinkable silane-terminated polymer and sealant composition made with same |
| US7605203B2 (en) * | 2005-05-26 | 2009-10-20 | Tremco Incorporated | Polymer compositions and adhesives, coatings, and sealants made therefrom |
| US7976951B2 (en) | 2006-11-14 | 2011-07-12 | Momentive Performance Materials Inc. | Laminate containing an adhesive-forming composition |
| US7829116B2 (en) * | 2006-11-14 | 2010-11-09 | Momentive Performance Materials Inc. | Adhesive-forming composition and blend of adhesives obtained therefrom |
| DE102006059473A1 (en) | 2006-12-14 | 2008-06-19 | Henkel Kgaa | Silyl-containing mixture of prepolymers and their use |
| US7819964B2 (en) * | 2007-02-16 | 2010-10-26 | Dow Global Technologies Inc. | System for bonding glass into a structure |
| US7989651B2 (en) * | 2007-03-09 | 2011-08-02 | Momentive Performance Materials Inc. | Epoxysilanes, processes for their manufacture and curable compositions containing same |
| CN101663341B (en) * | 2007-04-24 | 2013-11-27 | 陶氏环球技术公司 | Improved primer adhesion promoters, compositions and methods |
| EP2014314A1 (en) * | 2007-07-10 | 2009-01-14 | Bayer Innovation GmbH | Method for manufacturing polyurethane foams for treating wounds |
| WO2009009654A1 (en) * | 2007-07-12 | 2009-01-15 | Dow Global Technologies Inc. | Room temperature curable polymers and precursors thereof |
| DE102007058344A1 (en) | 2007-12-03 | 2009-06-04 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes |
| DE102007058483A1 (en) | 2007-12-04 | 2009-06-10 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes |
| DE102008003743A1 (en) * | 2008-01-10 | 2009-07-16 | Henkel Ag & Co. Kgaa | Curable compositions containing soft elastic silylated polyurethanes |
| DE102008020979A1 (en) * | 2008-04-25 | 2009-10-29 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes |
| DE102008020980A1 (en) * | 2008-04-25 | 2009-10-29 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes based on polyether block polymers |
| DE102008021221A1 (en) * | 2008-04-28 | 2009-10-29 | Henkel Ag & Co. Kgaa | Curable composition based on silylated polyurethanes |
| DE102008038399A1 (en) | 2008-08-19 | 2010-02-25 | Henkel Ag & Co. Kgaa | Preparing crosslinkable preparations, useful as e.g. adhesive, comprises reacting bifunctional organic polymers and silane compound with catalyst and mixing obtained silylterminated polymers, silane condensation catalyst and acid catalyst |
| DE102008021222A1 (en) | 2008-04-28 | 2009-12-24 | Henkel Ag & Co. Kgaa | Preparing crosslinkable preparations, useful as e.g. adhesive, comprises reacting bifunctional organic polymers and silane compound with catalyst and mixing obtained silylterminated polymers, silane condensation catalyst and acid catalyst |
| DE102008025575A1 (en) * | 2008-05-28 | 2009-12-03 | Evonik Röhm Gmbh | Water-crosslinkable sealant |
| DE102009001771A1 (en) | 2009-03-24 | 2010-09-30 | Henkel Ag & Co. Kgaa | Solidifying adhesives with silane crosslinking |
| DE102009046190A1 (en) | 2009-10-30 | 2011-05-05 | Henkel Ag & Co. Kgaa | Laminating adhesive with silane crosslinking |
| DE102009046269A1 (en) | 2009-10-30 | 2011-05-05 | Henkel Ag & Co. Kgaa | Urea-bound alkoxysilanes for use in sealants and adhesives |
| DE102011087604A1 (en) * | 2011-12-01 | 2013-06-06 | Wacker Chemie Ag | Crosslinkable compositions based on organyloxysilane-terminated polyurethanes |
| US9682886B1 (en) * | 2014-06-17 | 2017-06-20 | Amazon Technologies, Inc. | Ink coating application system and method |
| EP3067375B1 (en) | 2015-03-11 | 2017-08-30 | Henkel AG & Co. KGaA | Silylated polyurethanes, their preparation and use |
| DE102016202196A1 (en) * | 2016-02-12 | 2017-08-17 | Wacker Chemie Ag | Crosslinkable compositions based on organyloxysilane-terminated polymers |
| CA3070490A1 (en) | 2017-07-21 | 2019-01-24 | Henkel Ag & Co. Kgaa | Silylated polyurethanes and methods for preparing thereof |
| CN110982036A (en) * | 2019-12-20 | 2020-04-10 | 上海东大化学有限公司 | High-temperature-resistant silane modified polymer and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1207594A (en) * | 1967-03-16 | 1970-10-07 | Union Carbide Corp | One component room temperature vulcanizable silicon terminated polymers |
| US3979344A (en) * | 1974-11-19 | 1976-09-07 | Inmont Corporation | Vulcanizable silicon terminated polyurethane polymer composition having improved cure speed |
| US4067844A (en) * | 1976-12-22 | 1978-01-10 | Tremco Incorporated | Urethane polymers and sealant compositions containing the same |
-
1978
- 1978-08-02 US US05/930,309 patent/US4222925A/en not_active Expired - Lifetime
- 1978-09-14 CA CA311,284A patent/CA1122342A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4222925A (en) | 1980-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1122342A (en) | Vulcanizable silicon terminated polyurethane polymer compositions having improved cure speed | |
| US3979344A (en) | Vulcanizable silicon terminated polyurethane polymer composition having improved cure speed | |
| AU638855B2 (en) | Reactive hot-melt elastic sealant composition | |
| CN1054148C (en) | Polyurethane sealant compositions | |
| KR101295020B1 (en) | Polymer compositions and adhesives, coatings and sealants made therefrom | |
| CA2041532C (en) | Urethane sealant having improved sag properties | |
| CA1163039A (en) | Polyurethane sealant system | |
| CA1237848A (en) | One-part moisture-curable polyurethane adhesive, coating, and sealant compositions | |
| EP0070475B1 (en) | Method of making a moisture-curable silicon terminated polymer | |
| US7589134B2 (en) | Adhesive filled with surface-treated chalk and soot | |
| JP5546619B2 (en) | Cured adhesive with silane crosslinking | |
| CN1715356B (en) | Novel adhesive composition | |
| EP1462500A1 (en) | Single component, chemically curing warm applied sealant for durable insulating glazing units | |
| CN109575870B (en) | Modified siloxane-terminated polyurethane sealant and preparation method thereof | |
| KR101148418B1 (en) | Prepolymer compositions and sealants made therefrom | |
| KR102277661B1 (en) | Reactive hot melt adhesives with improved adhesion | |
| JP2005501165A (en) | Moisture crosslinkable elastic composition | |
| US20110118387A1 (en) | Sealer compositions | |
| CN115785850A (en) | Tackifying promoter, preparation method and application thereof, waterproof bonding single-component polyurethane sealant, preparation method and application thereof | |
| CN114479741A (en) | Single-component organic silicon modified sealant capable of being rapidly and deeply cured at low temperature and preparation method thereof | |
| JP3853254B2 (en) | Polyether plasticizer and resin composition thereof | |
| KR100277524B1 (en) | Urethane adhesive to dry some moisture | |
| CN114702935A (en) | Modified silane sealant and preparation method thereof | |
| CN112646108A (en) | Composition of basic polymer containing hydroxyl | |
| CN117247759A (en) | Single-component primer-free polyurethane sealant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |