CA1127794A - Method for producing a urethane elastomer - Google Patents
Method for producing a urethane elastomerInfo
- Publication number
- CA1127794A CA1127794A CA298,079A CA298079A CA1127794A CA 1127794 A CA1127794 A CA 1127794A CA 298079 A CA298079 A CA 298079A CA 1127794 A CA1127794 A CA 1127794A
- Authority
- CA
- Canada
- Prior art keywords
- diamine
- prepolymer
- elastomer
- triazole
- benzotriazole
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
Abstract
Abstract of the Disclosure A method for producing a urethane elastomer is disclosed. The method involves mixing a suitable triazole with an isocyanate terminated prepolymer while the prepolymer is at a temperature sufficiently high that it is a liquid. The proportion of triazole used can range from 0.1 to 1.0 equivalent per equivalent of isocyanate in the prepolymer, and must be suf-ficient to increase that pot life of a mixture of the prepolymer with a diamine, but insufficient to cause substantial impairment of the physical properties of the cured elastomer. A substantially equivalent amount of a diamine is then mixed with the stabilized prepolymer, and the resulting composition is heated to produce the elastomer.
Description
11~77~, Urethane elastomers are produced in large quantities from various isocyanate terminated prepolymers by reaction with a hindered diamine.
Historically, 4,4'-methylene bis (o-chloroaniline) (hereinafter "MOCA") has probably been the most widely used hindered amine. However, MOCA is a carcinogen suspect agent, and, as a consequence, taking the necessary safety precautions to safeguard the health of workers substantially increases the cost involved in producing elastomers using MOCA as the hindered amine. An-other hindered amine that has also seen considerable use is 4,4'-methylene bis (methyl-anthranilate) (hereinafter '~BMA").
Furthermore so far as is known, unhindered diamines have not heretofore been used for reaction with an isocyanate terminated prepolymer to produce an elastomer. Pot life is short, only a few minutes, even when MOCA and MBMA are used as the diamines. In a recent experiment wherein an attempt was made to produce a urethane elastomer from an isocyanate terminat-ed prepolymer and an unhindered diamine the pot life was estimated to be five seconds; the specific unhindered diamine used was 4,4'-methylene di-aniline (hereinafter '~DA").
Accordingly, the present invention provides a method for producing a urethane elastomer from an isocyanate terminated prepolymer and a diamine reactive therewith to produce the elastomer, said method comprising, stabiliz-ing an isocyanate terminated prepolymer by mixing therewith while at a temperature sufficiently high that the prepolymer is a liquid, from 0.1 to 1.0 equivalent per equivalent of NCO in the prepolymer of a suitable triazole, with the proviso that the amount of triazole mixed with the prepolymer is sufficient to increase the pot life of a mixture of the prepolymer with the diamine but insufficient to cause substantial impairment of the physical properties of the cured elastomer, mixing a substantially equivalent amount of the diamine with the so stabilized prepolymer and heating the resulting composition to produce the elastomer.
In a preferred embodiment the triazole is selected from the group ~d~--' S3~
consisting of 1,2,3-benzotriazole, tolyltriazole and mixtures thereof.
In another aspect the present invention provides a urethane elastomer produced by reaction between a triazole stabilized isocyanate terminated prepolymer and a substantially equivalent amount of an unhindered diamine.
In particular the present invention is based upon the discovery that an isocyanate terminated prepolymer can be stabilized by reaction, for example, with 1,2,3-benzotriazole* or a tolyl triazole, and that a mixture of the stabilized prepolymer with a diamine has a longer pot life than does a mixture of the unstabilized prepolymer with that diamine. It is to be understood that the term tolyltriazole (hereinafter TT) is the same as methyl-1,2,3-benzotriazole. When a hindered diamine is used in producing a urethane elastomer according to the invention, e.g. MOCA or MBMA, the pot life is increased substantially so that the labor required for carrying out the mix-ing operation can be minimized, and the prepolymer is preferably stabilized with from 0.1 to 0.5 equivalent of the triazole per equivalent of isocyanate in the prepelymer. On the other hand, when the diamine is unhindered, urethane elastomers which, so far as is known, had not been made are the result of practicing the instant invention, and it is usually preferred that the prepolymer be stabilized with from 0.5 to 1.0 equivalent of the triazole per equivalent of isocyanate in the prepoly~ner.
The following Examples, which are presented solely for the pur-pose of illustrating and disclosing the invention, set forth the best present-ly known mode.
An isocyanate-terminated prepolymer was prepared from 1 mole of a poly~oxytetramethylene)glycol having a molecular weight of 1000 and a melting * The use of triazoles to stabilize urethanc powder coating compositions is suggested in U.S. Patent No.
3,721,645. Other blocking agents for urethanes, e.g.
phenol, garnma-butyrolactam and dimethylmalonate are also known; see, for example, U.S. Patent No.
3,947,426.
~12,779~
temperature of 50C. ~hereinafter "PTMG 1000") and 2 moles of tolylene di-isocyanate ~hereinafter "TDl"). The specific TDl used was an 80/20 blend of
Historically, 4,4'-methylene bis (o-chloroaniline) (hereinafter "MOCA") has probably been the most widely used hindered amine. However, MOCA is a carcinogen suspect agent, and, as a consequence, taking the necessary safety precautions to safeguard the health of workers substantially increases the cost involved in producing elastomers using MOCA as the hindered amine. An-other hindered amine that has also seen considerable use is 4,4'-methylene bis (methyl-anthranilate) (hereinafter '~BMA").
Furthermore so far as is known, unhindered diamines have not heretofore been used for reaction with an isocyanate terminated prepolymer to produce an elastomer. Pot life is short, only a few minutes, even when MOCA and MBMA are used as the diamines. In a recent experiment wherein an attempt was made to produce a urethane elastomer from an isocyanate terminat-ed prepolymer and an unhindered diamine the pot life was estimated to be five seconds; the specific unhindered diamine used was 4,4'-methylene di-aniline (hereinafter '~DA").
Accordingly, the present invention provides a method for producing a urethane elastomer from an isocyanate terminated prepolymer and a diamine reactive therewith to produce the elastomer, said method comprising, stabiliz-ing an isocyanate terminated prepolymer by mixing therewith while at a temperature sufficiently high that the prepolymer is a liquid, from 0.1 to 1.0 equivalent per equivalent of NCO in the prepolymer of a suitable triazole, with the proviso that the amount of triazole mixed with the prepolymer is sufficient to increase the pot life of a mixture of the prepolymer with the diamine but insufficient to cause substantial impairment of the physical properties of the cured elastomer, mixing a substantially equivalent amount of the diamine with the so stabilized prepolymer and heating the resulting composition to produce the elastomer.
In a preferred embodiment the triazole is selected from the group ~d~--' S3~
consisting of 1,2,3-benzotriazole, tolyltriazole and mixtures thereof.
In another aspect the present invention provides a urethane elastomer produced by reaction between a triazole stabilized isocyanate terminated prepolymer and a substantially equivalent amount of an unhindered diamine.
In particular the present invention is based upon the discovery that an isocyanate terminated prepolymer can be stabilized by reaction, for example, with 1,2,3-benzotriazole* or a tolyl triazole, and that a mixture of the stabilized prepolymer with a diamine has a longer pot life than does a mixture of the unstabilized prepolymer with that diamine. It is to be understood that the term tolyltriazole (hereinafter TT) is the same as methyl-1,2,3-benzotriazole. When a hindered diamine is used in producing a urethane elastomer according to the invention, e.g. MOCA or MBMA, the pot life is increased substantially so that the labor required for carrying out the mix-ing operation can be minimized, and the prepolymer is preferably stabilized with from 0.1 to 0.5 equivalent of the triazole per equivalent of isocyanate in the prepelymer. On the other hand, when the diamine is unhindered, urethane elastomers which, so far as is known, had not been made are the result of practicing the instant invention, and it is usually preferred that the prepolymer be stabilized with from 0.5 to 1.0 equivalent of the triazole per equivalent of isocyanate in the prepoly~ner.
The following Examples, which are presented solely for the pur-pose of illustrating and disclosing the invention, set forth the best present-ly known mode.
An isocyanate-terminated prepolymer was prepared from 1 mole of a poly~oxytetramethylene)glycol having a molecular weight of 1000 and a melting * The use of triazoles to stabilize urethanc powder coating compositions is suggested in U.S. Patent No.
3,721,645. Other blocking agents for urethanes, e.g.
phenol, garnma-butyrolactam and dimethylmalonate are also known; see, for example, U.S. Patent No.
3,947,426.
~12,779~
temperature of 50C. ~hereinafter "PTMG 1000") and 2 moles of tolylene di-isocyanate ~hereinafter "TDl"). The specific TDl used was an 80/20 blend of
2,4- and 2,6-isomers. The isocyanate (hereinafter "NC0") content of the prepolymer, determined by di-n-butyl amine titration, was 6.2 percent.
1,2,3-benzotriazole (hereinafter "BT") was then melted, vacuum degassed, and mixed with a sample of the prepolymer which had been preheated to 75C. The BT was added in the proportion of 0.25 equivalent (mole) thereof per iso-cyanate equivalent of the prepolymer. The resulting mixture was stirred at 80C. for one hour to insure complete reaction between the BT and the free NC0 groups of the prepolymer. The stabilized prepolymer which resultedJ at 80C., was mixed with MBMA, which had been vacuum degassed at 150C., mixing temperature 140C., at an NC0: NH2 ratio of substantially 1:1. The resulting composition was found to have a pot life of 20 minutes at 100C.; it was vacuum degassed and poured into a mold preheated to 100C. The mold, which had a central cavity 6 inches by 6 inches by 0.06 inch in depth, was then covered by a flat plate and placed in a hydraulic press where a compressive force of 10,000 pounds per square inch was applied to the mold and plate.
After approximately one hour in the mold at 100C. the partially cured elastomer was removed from the mold and transferred to an oven where it was cured for an additional 19 hours at 100C.
After conditioning at room temperature and 50 percent relative humidity for one week the elastomer was found to have the following physical properties:
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In examples 2 to 14, other urethane elastomers according to the invention, and controls in which no triazole was used, have been produced by the method described above in Example 1. The starting materials used, the ratio of equivalents of triazole used to equivalents of NCO, the mixing temperatures, the curing conditions, the pot life and the physical properties of the various elastomers, determined by the tests identified above, are set forth in Table 1, below. The following abbreviations, all used in Table 1, have the indicated meanings:
PTMG 650: A pol~J(oxytetramethylene)glycol having a molecular weight of 650 and a melting point of 30C.
PPG 1010: A poly(oxypropylene)glycol having a molecular weight of 1030.
H12 MDl: 4,4'-dicyclohexylmethane diisocyanate m-PDA: m-phenylene diamine 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane MXDA: _-xylylene diamine lPDA: isophorone diamine TT: tolyltriazole; the material used was a blend of approximately equal parts of 4-methylbenzotriazole and 5-methylbenzotriazole The curing was for approximately one hour in a mold at the temperature repor-ted in Table 1 followed by oven curing at that temperature for the remainder of the time for each elastomer. In each case, the prepolymer was produced by reacting two moles of the indicated isocyanate with one mole of the polyol.
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E~ ~ 3 u~ c c~ ~ O, _ ~ v v 77S~a Examples 15 to 17 were carried out using substantially the same procedure described above in Example 1, except that the prepolymer:diamine blend was merely poured into a pan mold after degassing~ was used to produce urethane elastomers according to the method of the invention from a prepolymer made from TDl and a polyester which was hydroxy-terminated. The specific prepolymer had an NCO content of approximately 3.5 percent by weight; it is commercially available under the trade designation ~'Vibrathane 60251lo Data concerning the elastomers are set forth in Table 11, below:
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It is known, e.g., in United States Patent No. 3,721,645, that triazoles other than BT and TT are capable of reaction with NC0 groups, and that the reaction is reversible in the sense that apparently normal cure occurs at an elevated temperatureO It will be apparent that an equivalent amount of any of ~he other triazoles could be substituted for BT and TT in each of the foregoing Examples, and with similar results. However, BT and TT are the preferred triazoles because of availability, low volatility, anti-corrosive properties and price.
The curing times reported in the foregoing Examples are those Whichwere actually used. It has been found, however, that the 18 to 20 hour curing times used in many instances are unnecessary in the sense that substan-tially the same physical properties result after a shorter cure. In most cases, a cure time of three to six hours has been found to be adequate.
Various changes and modifications can be made as will be apparent to one skilled in the art, from the specific embodiments described above without departing from the spirit and scope of the invention as defined in the following claims.
1,2,3-benzotriazole (hereinafter "BT") was then melted, vacuum degassed, and mixed with a sample of the prepolymer which had been preheated to 75C. The BT was added in the proportion of 0.25 equivalent (mole) thereof per iso-cyanate equivalent of the prepolymer. The resulting mixture was stirred at 80C. for one hour to insure complete reaction between the BT and the free NC0 groups of the prepolymer. The stabilized prepolymer which resultedJ at 80C., was mixed with MBMA, which had been vacuum degassed at 150C., mixing temperature 140C., at an NC0: NH2 ratio of substantially 1:1. The resulting composition was found to have a pot life of 20 minutes at 100C.; it was vacuum degassed and poured into a mold preheated to 100C. The mold, which had a central cavity 6 inches by 6 inches by 0.06 inch in depth, was then covered by a flat plate and placed in a hydraulic press where a compressive force of 10,000 pounds per square inch was applied to the mold and plate.
After approximately one hour in the mold at 100C. the partially cured elastomer was removed from the mold and transferred to an oven where it was cured for an additional 19 hours at 100C.
After conditioning at room temperature and 50 percent relative humidity for one week the elastomer was found to have the following physical properties:
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In examples 2 to 14, other urethane elastomers according to the invention, and controls in which no triazole was used, have been produced by the method described above in Example 1. The starting materials used, the ratio of equivalents of triazole used to equivalents of NCO, the mixing temperatures, the curing conditions, the pot life and the physical properties of the various elastomers, determined by the tests identified above, are set forth in Table 1, below. The following abbreviations, all used in Table 1, have the indicated meanings:
PTMG 650: A pol~J(oxytetramethylene)glycol having a molecular weight of 650 and a melting point of 30C.
PPG 1010: A poly(oxypropylene)glycol having a molecular weight of 1030.
H12 MDl: 4,4'-dicyclohexylmethane diisocyanate m-PDA: m-phenylene diamine 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane MXDA: _-xylylene diamine lPDA: isophorone diamine TT: tolyltriazole; the material used was a blend of approximately equal parts of 4-methylbenzotriazole and 5-methylbenzotriazole The curing was for approximately one hour in a mold at the temperature repor-ted in Table 1 followed by oven curing at that temperature for the remainder of the time for each elastomer. In each case, the prepolymer was produced by reacting two moles of the indicated isocyanate with one mole of the polyol.
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_ 3 o~
'- ~ ._ ~-- E
U~ I~ ~_ ~
_ O Cl ~ ~ 1 V
_ _ _ _ Cl O O O ~
E~ L ~~ o 1~, V o~ O _ _ _ O ~c o LLI O O O Z ~ z ~ C ~C ~C
1~ ~7~79~
.
v L
.' o~o _~
O ~ u~ Q c ~~ ~ 3 ~ _ ~ ~ z z Z Z 2 z z z z ~ ~ ~
O E
~ o~~ o o oE~
~ O
CO d~ ~ Z Z Z ~ Z Z Z Z Z Z Z ~ Z Z L
_ O
J .
a~ ~
~ , a~
c ._ G
C O
~ v O ~ r 0 1~ o c L V~ ~ 5 3 5 ~ e 'v O
_~ . ,c,c _~ E
O ~
q~ ~ o _ _ _ ~r~
.~ O O O
E~ ~ 3 u~ c c~ ~ O, _ ~ v v 77S~a Examples 15 to 17 were carried out using substantially the same procedure described above in Example 1, except that the prepolymer:diamine blend was merely poured into a pan mold after degassing~ was used to produce urethane elastomers according to the method of the invention from a prepolymer made from TDl and a polyester which was hydroxy-terminated. The specific prepolymer had an NCO content of approximately 3.5 percent by weight; it is commercially available under the trade designation ~'Vibrathane 60251lo Data concerning the elastomers are set forth in Table 11, below:
_ ~ _ 1~2~779~
C~
o al E
L cx) . E a a) ~ ~
a c-- o o o o ,, E -- O o o o o a~ E a ~
~ .~ v ~ c~ c~ 3 ._ ~
x O
._ .~
r o o O
z c u7 t, ~-- ~n _ ~ ~ o o O
O > . . . I Q
N ~--O
n~
._ ~J
_ ~ O
_ ~
J
cl ._ ~ c ~ a~
E ~ cl ~ ~ ~
~ o c~ I o c.
._ ,. ~ E ~ ,~
o c >
~ .~
~ ~
I_ a O
~J
- (n Lt~ L v~
~ _ O ~
a ~ ,~ ~J
E u~ ~ ~ _ ~ c ~ _ _ -- O
X L - L
L~ ~ O ~
Z ~1 o ~ ~:
7~
.
n ~ a~ ._ O C O ooO O
u~ L a~ ) co în E
r C) O ~ C
._ ~
.X O O O U~ 3 cn v ~ L~ o cc~
O L u~ o O
~ u~
~u ._ O
E
-v o -- cn O O O O v-._ C ._ O ~ v r~
u 1- ~n L
CL
J o a~ ' ~
a~ o v v~ ~ ~ a~~ ~ c O ~-- C _ ~
G._~ ._ G~
C~
~ .
0~ O
O _ I~ r~r-- o V
._ E o o o o ._ ~ O
.~ c o cn -- n _ L ~n _ _, V
E IJ~ v -X _ _-- o ~ C
Ul ~ ~ L
o Z
.:
'1~2177~9~
It is known, e.g., in United States Patent No. 3,721,645, that triazoles other than BT and TT are capable of reaction with NC0 groups, and that the reaction is reversible in the sense that apparently normal cure occurs at an elevated temperatureO It will be apparent that an equivalent amount of any of ~he other triazoles could be substituted for BT and TT in each of the foregoing Examples, and with similar results. However, BT and TT are the preferred triazoles because of availability, low volatility, anti-corrosive properties and price.
The curing times reported in the foregoing Examples are those Whichwere actually used. It has been found, however, that the 18 to 20 hour curing times used in many instances are unnecessary in the sense that substan-tially the same physical properties result after a shorter cure. In most cases, a cure time of three to six hours has been found to be adequate.
Various changes and modifications can be made as will be apparent to one skilled in the art, from the specific embodiments described above without departing from the spirit and scope of the invention as defined in the following claims.
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for producing a urethane elastomer from an isocyanate terminated prepolymer and a diamine reactive therewith to produce the elastomer, said method comprising, stabilizing an isocyanate terminated pre-polymer by mixing therewith while at a temperature sufficiently high that the prepolymer is a liquid, from 0.1 to 1.0 equivalent per equivalent of NCO
in the prepolymer of a suitable triazole, with the proviso that the amount of triazole mixed with the prepolymer is sufficient to increase the pot life of a mixture of the prepolymer with the diamine but insufficient to cause substantial impairment of the physical properties of the cured elastomer, mixing a substantially equivalent amount of the diamine with the so stabilized prepolymer and heating the resulting composition to produce the elastomer.
in the prepolymer of a suitable triazole, with the proviso that the amount of triazole mixed with the prepolymer is sufficient to increase the pot life of a mixture of the prepolymer with the diamine but insufficient to cause substantial impairment of the physical properties of the cured elastomer, mixing a substantially equivalent amount of the diamine with the so stabilized prepolymer and heating the resulting composition to produce the elastomer.
2. A method as defined in claim 1 wherein said triazole is selected from the group consisting of 1,2,3-benzotriazole, tolyltriazole and mixtures thereof.
3. A method as defined in claim 2 wherein said triazole is 1,2,3-benzotriazole.
4. A method as defined in claim 2 wherein said triazole is a mixture of 4-methyl-1,2,3-benzotriazole and 5-methyl-1,2,3-benzotriazole.
5. A method as defined in claim 1 wherein the diamine is a hindered diamine.
6. A method as defined in claim 1 wherein the diamine is an unhinder-ed diamine.
7. A method as defined in claim 2, 3 or 4 wherein the diamine is a hindered diamine.
8. A method as defined in claim 2, 3 or 4 wherein the diamine is an unhindered diamine.
9. A method as defined in claim 2 wherein the diamine is selected from the group consisting of 4,4'-methylene dianiline, m-phenylene diamine, 1,3-bis(amino-methyl)cyclohexane, m-xylylene diamine and isophorone diamine.
10. A method as defined in claim 3 wherein the diamine is m-phenylene diamine.
11. A method as defined in claim 4 wherein the diamine is selected from the group consisting of 4,4'-methylene dianiline, 1,3-bis(aminomethyl)cyclohexane, m-xylylene diamine and isophorone diamine.
12. A method as defined in claim 2, 3 or 4 wherein the diamine is selected from the group consisting of 4,4'-methylene bis(o-chloroaniline) and 4,4'-methylene bis(methylanthanilate).
13. A method as defined in claim 3 wherein the diamine is 4,4'-methylene bis(methylanthanilate).
14. A urethane elastomer produced by the method of claim 1.
15. A urethane elastomer as defined in claim 14 and produced by the method defined in claim 6 or 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US774,036 | 1977-03-03 | ||
| US05/774,036 US4096128A (en) | 1977-03-03 | 1977-03-03 | Polyurethane elastomer produced by reaction between a triazole-stabilized isocyanate prepolymer and a diamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127794A true CA1127794A (en) | 1982-07-13 |
Family
ID=25100052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA298,079A Expired CA1127794A (en) | 1977-03-03 | 1978-03-02 | Method for producing a urethane elastomer |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4096128A (en) |
| JP (1) | JPS53109599A (en) |
| BE (1) | BE864541A (en) |
| CA (1) | CA1127794A (en) |
| DE (1) | DE2808829A1 (en) |
| FR (1) | FR2382469B3 (en) |
| GB (1) | GB1563771A (en) |
| IT (1) | IT1095460B (en) |
| NL (1) | NL7801730A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4274997A (en) * | 1978-11-29 | 1981-06-23 | The Sherwin-Williams Company | Halogenated polymers stabilized with triazoles |
| US4931487A (en) * | 1988-03-04 | 1990-06-05 | Dow Chemical Company | Chain extenders for polyurethanes |
| US4845180A (en) * | 1988-03-21 | 1989-07-04 | Allergan, Inc. | Ultraviolet light absorbing compounds, compositions and methods for making same |
| DE4015302A1 (en) * | 1990-05-12 | 1991-11-14 | Bayer Ag | Amine prods. contg. urethane and urea gps. prepn. |
| US5157100A (en) * | 1991-09-20 | 1992-10-20 | The Sherwin-Williams Company | Method for extending the pot-life of polyol-polyisocyanate mixtures |
| JP3380226B2 (en) * | 2000-11-15 | 2003-02-24 | 大成化工株式会社 | Manufacturing method of weather resistant coating film |
| AU2003287530A1 (en) * | 2002-11-05 | 2004-06-07 | The Sherwin-Williams Company | Curable compositions |
| US20060217472A1 (en) * | 2005-03-11 | 2006-09-28 | Staunton Thomas J | Scratch resistant curable coating composition |
| EP3085748B1 (en) | 2015-04-20 | 2017-12-27 | Jotun A/S | Coatings |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3213058A (en) * | 1960-12-19 | 1965-10-19 | American Cyanamid Co | Polymers reacted with benzotriazole uv absorbers |
| US3379675A (en) * | 1964-07-30 | 1968-04-23 | Du Pont | Polyether urethane stabilized with a benzotriazole and a tris-phenol |
| CH489510A (en) * | 1967-02-07 | 1970-04-30 | Geigy Ag J R | Process for the preparation of substituted γ-triazoles |
| US3721645A (en) * | 1971-02-25 | 1973-03-20 | Liner Technology Inc | Polyurethanes stabilized with 1,2,3-,1,2,4-1,2,5-,and 1,3,4-triazoles |
| US3947426A (en) * | 1974-04-12 | 1976-03-30 | Story Chemical Corporation | Solid particle-form polymerizable polymeric material and compositions, structures and methods of employing and producing the same |
-
1977
- 1977-03-03 US US05/774,036 patent/US4096128A/en not_active Expired - Lifetime
-
1978
- 1978-02-16 NL NL7801730A patent/NL7801730A/en not_active Application Discontinuation
- 1978-02-24 FR FR7805371A patent/FR2382469B3/fr not_active Expired
- 1978-02-27 JP JP2102678A patent/JPS53109599A/en active Pending
- 1978-02-28 IT IT20759/78A patent/IT1095460B/en active
- 1978-03-01 DE DE19782808829 patent/DE2808829A1/en not_active Withdrawn
- 1978-03-02 CA CA298,079A patent/CA1127794A/en not_active Expired
- 1978-03-03 BE BE185652A patent/BE864541A/en not_active IP Right Cessation
- 1978-03-03 GB GB8599/78A patent/GB1563771A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL7801730A (en) | 1978-09-05 |
| US4096128A (en) | 1978-06-20 |
| GB1563771A (en) | 1980-04-02 |
| FR2382469A1 (en) | 1978-09-29 |
| JPS53109599A (en) | 1978-09-25 |
| BE864541A (en) | 1978-09-04 |
| IT7820759A0 (en) | 1978-02-28 |
| DE2808829A1 (en) | 1978-09-07 |
| FR2382469B3 (en) | 1980-11-21 |
| IT1095460B (en) | 1985-08-10 |
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