US3945981A
Expired / Lapsed
US
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Light stable polyurethane elastomer prepared from aliphatic isocyanate using thio tin organic compound containing sulfur attached to tin as heat activated catalyst
Assignee: Uniroyal Chemical Co Inc
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Filing: 1974-11-08
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Granted: 1976-03-23
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Expires: 1994-11-08
Abstract
Abstract A light stable polyurethane elastomer is prepared in the absence of solvent from a polyol, a chain extender and an aliphatic polyisocyanate using a thio tin organic compound, containing sulfur directly attached to the tin, as a heat activated catalyst. E.g., a solventless liquid composition comprising an hydroxy-terminated polyester, a chain extender, and hydrogenated MDI, containing dibutyltin S,S-bis(isooctyl mercaptoacetate) as a catalyst, has a pot life in excess of 25 minutes at room temperature but upon heating 1 minute at 375°F. gels to a solid state. Because of this combination of long pot life and rapid cure, the composition is suitable for such applications as making coated fabrics and films, and in other liquid processing techniques, e.g., rotational casting, liquid injection molding, and the like.
Inventors
- 👤 John R. Robertson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 10:39
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/16; C08G18/22; C08G18/24; C08G18/242; C08G18/70; C08G18/72; C08G18/73; C08G18/74; C08G18/75; C08G18/76; C08G18/7614; C08G18/7628; C08G18/7642
Claims Analysis
Total Claims: 42
Claim 1
Independent Claim
194 words
A curable solvent-free liquid polyurethane composition having a pot life of at least 25 minutes at room temperature consisting essentially of a mixture of a polyol and a monomeric hydrocarbon-containing aliphatic polyisocyanate containing, as a heat-activatable catalyst, a thio tin organic compound having sulfur directly attached to the tin, in an amount effective to catalyze the cure of the composition, the said catalyst having the formula (R-).sub.a Sn [-S(R.sup.1)x].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms: R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 )n, n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2; the equivalence ratio or isocyanate groups to hydroxyl groups in said composition being from 0.90:1 to 1.1:1, and the said composition being capable of curing in from 30 seconds to 3 minutes at corresponding temperatures of from 375° to 300°F to form a solid, chain extended lightstable polyurethane elastomer.
Claim 2
Dependent Claim
194 words
A curable solvent-free liquid polyurethane composition having a pot life of at least 25 minutes at room temperature consisting essentially of a mixture of a polyol and a monomeric hydrocarbon-containing aliphatic polyisocyanate containing, as a heat-activatable catalyst, a thio tin organic compound having sulfur directly attached to the tin, in an amount effective to catalyze the cure of the composition, the said catalyst having the formula (R-).sub.a Sn [-S(R.sup.1)x].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms: R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 )n, n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2; the equivalence ratio or isocyanate groups to hydroxyl groups in said composition being from 0.90:1 to 1.1:1, and the said composition being capable of curing in from 30 seconds to 3 minutes at corresponding temperatures of from 375° to 300°F to form a solid, chain extended lightstable polyurethane elastomer.
Claim 3
Dependent Claim
29 words
A composition as in claim 1 in which the said polyisocyanate is selected from the group consisting of methylene bis(4-cyclohexylisocyanate), isophorone diisocyanate and mixtures of para-xylene and meta-xylene diisocyanate.
Claim 4
Dependent Claim
33 words
A curable solvent-free liquid polyurethane composition as in claim 1 consisting essentially of a mixture of a macropolyol, a monomeric hydrocarbon-containing cycloaliphatic diisocyanate, and, as a chain extender, a low molecular weight diol.
Claim 5
Dependent Claim
19 words
A composition as in claim 3 in which the said macropolyol is a polyester glycol or a polyether glycol.
Claim 6
Dependent Claim
22 words
A composition as in claim 3 in which the said chain extender is an alkane diol having 3 to 6 carbon atoms.
Claim 7
Dependent Claim
14 words
A composition as in claim 3 in which the said diisocyanate is methylene bis(4-cyclohexylisocyanate).
Claim 8
Dependent Claim
231 words
A curable solvent-free liquid composition consisting essentially of a mixture of a macropolyol which is a polyester or polyether glycol having a molecular weight of from 500 to 2000, a monomeric hydrocarbon-containing aliphatic diisocyanate, and, as a chain extender, an alkane diol having from 3 to 6 carbon atoms, the equivalence ratio of isocyanate groups to hydroxyl groups in the said composition being from 0.90:1 to 1.1.:1 and the equivalence ratio of said macropolyol to said chain extender being from 1:1 to 1:3, the said mixture containing, in amount effective to catalyze the cure of the mixture, a thio tin organic compound of the formula (R-).sub.a Sn [-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2, the said composition have a pot life of at least 25 minutes at room temperature and being capable of curing in from 30 seconds to 3 minutes at corresponding temperatures of from 375° to 300°F. to form a solid, chain extended light-stable polyurethane elastomer.
Claim 9
Dependent Claim
231 words
A curable solvent-free liquid composition consisting essentially of a mixture of a macropolyol which is a polyester or polyether glycol having a molecular weight of from 500 to 2000, a monomeric hydrocarbon-containing aliphatic diisocyanate, and, as a chain extender, an alkane diol having from 3 to 6 carbon atoms, the equivalence ratio of isocyanate groups to hydroxyl groups in the said composition being from 0.90:1 to 1.1.:1 and the equivalence ratio of said macropolyol to said chain extender being from 1:1 to 1:3, the said mixture containing, in amount effective to catalyze the cure of the mixture, a thio tin organic compound of the formula (R-).sub.a Sn [-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2, the said composition have a pot life of at least 25 minutes at room temperature and being capable of curing in from 30 seconds to 3 minutes at corresponding temperatures of from 375° to 300°F. to form a solid, chain extended light-stable polyurethane elastomer.
Claim 10
Dependent Claim
14 words
A composition as in claim 7 in which the said diisocyanate is methylene bis(4-cyclohexylisocyanate.
Claim 11
Dependent Claim
14 words
A composition as in claim 7 in which the said diisocyanate is isophorone diisocyanate.
Claim 12
Dependent Claim
19 words
A composition as in claim 7 in which the said diisocyanate is a mixture of para-xylene and metaxylene diisocyanate.
Claim 13
Dependent Claim
15 words
A composition as in claim 7 in which the said catalyst is dibutyltin S,S-bis(isooctyl thioglycolate).
Claim 14
Dependent Claim
15 words
A composition as in claim 7 in which the said catalyst is dibutyltin S,S-bis(dodecyl mercaptide).
Claim 15
Dependent Claim
15 words
A composition as in claim 7 in which the said catalyst is di(n-octyl)tin S,S-bis(isooctyl thioglycolate).
Claim 16
Dependent Claim
14 words
A composition as in claim 7 in which the said catalyst is dibutyltin sulfide.
Claim 17
Dependent Claim
14 words
A composition as in claim 7 in which the said chain extender is 1,4-butanediol.
Claim 18
Dependent Claim
14 words
A composition as in claim 7 in which the said chain extender is 1,6-hexanediol.
Claim 19
Dependent Claim
16 words
A cured composition as in claim 1 which is a solid, light-stable, chain extended polyurethane elastomer.
Claim 20
Dependent Claim
20 words
A shaped object which is a composition as in claim 7 cured to a solid, light-stable, chain extended polyurethane elastomer.
Claim 21
Dependent Claim
221 words
In a method of making a shaped object by reacting a composition consisting essentially of a mixture of a macroglycol, a monomeric hydrocarbon-containing aliphatic polyisocyanate, a bifunctional chain extender, and a catalyst effective to cure the mixture to form a solid chain extended light-stable polyurethane elastomer, wherein the composition is mixed in liquid form and is thereafter shaped and cured in the desired shape, the improvement comprising effecting the reaction in the presence of an effective amount of a thio tin organic compound having sulfur directly attached to the tin, the said organic compound having the formula: (R-).sub.a SN[-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2; the equivalence ratio or isocyanate groups to hydroxyl groups in said composition being from 0.9:1 to 1.1:1, whereby the composition has a pot life of at least 25 minutes at room temperature but cures rapidly at corresponding temperatures of from 300° to 375°F.
Claim 22
Dependent Claim
221 words
In a method of making a shaped object by reacting a composition consisting essentially of a mixture of a macroglycol, a monomeric hydrocarbon-containing aliphatic polyisocyanate, a bifunctional chain extender, and a catalyst effective to cure the mixture to form a solid chain extended light-stable polyurethane elastomer, wherein the composition is mixed in liquid form and is thereafter shaped and cured in the desired shape, the improvement comprising effecting the reaction in the presence of an effective amount of a thio tin organic compound having sulfur directly attached to the tin, the said organic compound having the formula: (R-).sub.a SN[-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2; the equivalence ratio or isocyanate groups to hydroxyl groups in said composition being from 0.9:1 to 1.1:1, whereby the composition has a pot life of at least 25 minutes at room temperature but cures rapidly at corresponding temperatures of from 300° to 375°F.
Claim 23
Dependent Claim
21 words
A method as in claim 19 wherein the said shaped object is a coating of the said composition on a fabric.
Claim 24
Dependent Claim
236 words
In a method of making a solid polyurethane article by reacting a curable liquid composition consisting essentially of a polyester or polyether glycol, a monomeric hydrocarbon-containing cycloaliphatic diisocyanate, a chain extender which is an alkane diol having 3 to 6 carbon atoms, and an effective amount of a heat activatable catalyst for the cure of the composition, wherein the said liquid is first shaped at ambient temperature and thereafter heated to an elevated temperature to cure the composition in a desired shape, the improvement comprising effecting the reaction in the presence of, as the catalyst, an organo tin compound of the formula (R-).sub.a Sn[-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2; the equivalence ratio of isocyanate groups to hydroxyl groups in the said mixture being from 0.90:1 to 1.1:1 whereby the said liquid has a pot life of at least 25 minutes at 22°C. but cures rapidly at a temperature of from 300° to 375°F. to form a solid, chain extended light-stable polyurethane elastomer.
Claim 25
Dependent Claim
236 words
In a method of making a solid polyurethane article by reacting a curable liquid composition consisting essentially of a polyester or polyether glycol, a monomeric hydrocarbon-containing cycloaliphatic diisocyanate, a chain extender which is an alkane diol having 3 to 6 carbon atoms, and an effective amount of a heat activatable catalyst for the cure of the composition, wherein the said liquid is first shaped at ambient temperature and thereafter heated to an elevated temperature to cure the composition in a desired shape, the improvement comprising effecting the reaction in the presence of, as the catalyst, an organo tin compound of the formula (R-).sub.a Sn[-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R 3 is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2; the equivalence ratio of isocyanate groups to hydroxyl groups in the said mixture being from 0.90:1 to 1.1:1 whereby the said liquid has a pot life of at least 25 minutes at 22°C. but cures rapidly at a temperature of from 300° to 375°F. to form a solid, chain extended light-stable polyurethane elastomer.
Claim 26
Independent Claim
247 words
A method of making a light-stable polyurethane coated fabric comprising providing a solvent-free liquid mixture of a macropolyol selected from the group consisting essentially of polyester and polyether glycols having a molecular weight of from 500 to 2000, a monomeric hydrocarbon-containing aliphatic diisocyanate, a chain extender which is an alkane diol having 3 to 6 carbon atoms, and a catalyst in amount effective to catalyze the cure of the said mixture at a curing temperature of from 300° to 375°F. the said catalyst being an organotin compound of the formula (R-).sub.a Sn[-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2, the equivalence ratio of isocyanate groups to hydroxyl groups in the said mixture being from 0.90:1 to 1.1:1 and the equivalence ratio of said macropolyol to said alkane diol being from 1:1 to 1:3, the said mixture being characterized by a pot life of at least 25 minutes at 22°C., thereafter applying the said liquid mixture to a fabric, and heating the resulting assembly to curing temperature to cure the applied mixture to a solid elastomeric state.
Claim 27
Independent Claim
247 words
A method of making a light-stable polyurethane coated fabric comprising providing a solvent-free liquid mixture of a macropolyol selected from the group consisting essentially of polyester and polyether glycols having a molecular weight of from 500 to 2000, a monomeric hydrocarbon-containing aliphatic diisocyanate, a chain extender which is an alkane diol having 3 to 6 carbon atoms, and a catalyst in amount effective to catalyze the cure of the said mixture at a curing temperature of from 300° to 375°F. the said catalyst being an organotin compound of the formula (R-).sub.a Sn[-S(R.sup.1).sub.x ].sub.b wherein: R is an alkyl radical having 3 to 10 carbon atoms; R 1 is an alkyl radical having 4 to 20 carbon atoms or a radical of the formula --R 2 COOR 3 where R 2 is (CH 2 ) n , n being from 1 to 5, and R is an alkyl radical having 4 to 18 carbon atoms; x is zero or 1, a is 2 or 3, and b is 1 or 2, the equivalence ratio of isocyanate groups to hydroxyl groups in the said mixture being from 0.90:1 to 1.1:1 and the equivalence ratio of said macropolyol to said alkane diol being from 1:1 to 1:3, the said mixture being characterized by a pot life of at least 25 minutes at 22°C., thereafter applying the said liquid mixture to a fabric, and heating the resulting assembly to curing temperature to cure the applied mixture to a solid elastomeric state.
Claim 28
Dependent Claim
80 words
A method as in claim 22 in which the liquid mixture is first spread as a coating on a release paper, then heated to gel the liquid to a state in which it is tacky to the touch, the fabric to be coated is applied to the surface of the liquid, the assembly is then heated to cure the liquid to a solid state, and the thus-coated fabric is thereafter cooled to room temperature and separated from the release paper.
Claim 29
Dependent Claim
15 words
A method as in claim 22 in which the said macropolyol is a polyester glycol.
Claim 30
Dependent Claim
15 words
A method as in claim 22 in which the said macropolyol is a polyether glycol.
Claim 31
Dependent Claim
15 words
A method as in claim 22 in which the said diisocyanate is a cycloaliphatic diisocyanate.
Claim 32
Dependent Claim
13 words
A method as in claim 22 in which the said diisocyanate is methylenebis(4-cyclohexylisocyanate).
Claim 33
Dependent Claim
14 words
A method as in claim 22 in which the said diisocyanate is isophorone diisocyanate.
Claim 34
Dependent Claim
19 words
A method as in claim 22 in which the said diisocyanate is a mixture of para-xylene and meta-xylene diisocyanate.
Claim 35
Dependent Claim
15 words
A method as in claim 22 in which the said catalyst is dibutyltin S,S-bis(isooctyl thioglycolate).
Claim 36
Dependent Claim
15 words
A method as in claim 22 in which the said catalyst is dibutyltin S,S-bis(dodecyl mercaptide).
Claim 37
Dependent Claim
16 words
A method as in claim 22 in which the said catalyst is di(n-octyl) tin S,S-bis(isooctyl thioglycolate).
Claim 38
Dependent Claim
14 words
A method as in claim 22 in which the said catalyst is dibutyltin sulfide.
Claim 39
Dependent Claim
14 words
A method as in claim 22 in which the said chain extender is 1,4-butanediol.
Claim 40
Dependent Claim
14 words
A method as in claim 22 in which the said chain extender is 1,6-hexanediol.
Claim 41
Dependent Claim
35 words
A method as in claim 22 in which the said macropolyol is a polyester glycol, the said diisocyanate is methylene bis(4-cyclohexylisocyanate), the said chain extender is 1,4-butanediol, and the said catalyst is dibutyltin S,S-bis(isooctyl thioglycolate).
Claim 42
Dependent Claim
35 words
A method as in claim 22 in which the said macropolyol is a polyether glycol, the said diisocyanate is methylene bis(4-cyclohexylisocyanate), the said chain extender is 1,4-butanediol, and the said catalyst is dibutyltin S,S-bis(isooctyl thioglycolate).
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-03-23 | 1979-09-22 | 1980-03-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-03-23 | 1983-09-22 | 1984-03-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-03-23 | 1987-09-22 | 1988-03-23 | $7700.00 | Window Closed / Lapsed |