Patent US4471295A successfully refreshed from Google Patents.
Patent US4526905A successfully refreshed from Google Patents.
US4526905A
Expired / Lapsed
US
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Polyurethanes from dialkyl diaminobenzenes and processes therefor
Assignee: Ethyl Corp
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Filing: 1984-05-23
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Granted: 1985-07-02
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Expires: 2004-05-23
Abstract
Abstract Dialkyl diamines for use with polyols and polyisocyanates in cast elastomer and reaction injection molding polyurethane processes. The dialkyl diamines are prepared by nitration and reduction of dialkylbenzenes or alkylation of meta-phenylenediamine. The chain extenders have the following structure: ##STR1## where R 1 is C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl. Contrary to the teachings of the prior art the novel diamines have surprisingly good reaction times to form polyurethanes with excellent physical properties. Furthermore, little or no mold release is required in RIM and other processes using the chain extenders of the invention.
Inventors
- 👤 Donald H. Lucast
- 👤 Ronald L. Shubkin
- 👤 Allen H. Filbey
- 👤 John C. Wollensak
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 08:36
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/65; C08G18/66; C08G18/6603; C08G18/6614; C08G18/6618; C08G18/08; C08G18/10; C08G18/30; C08G18/32; C08G18/3225; C08G18/3234; C08G18/3237; C08G18/324; C08G2120/00
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
50 words
A polyurethane formed from an organic polyol, an organic polyisocyanate, and a 4,6-dialkyl-m-phenylenediamine chain extender of structure: ##STR9## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 2
Dependent Claim
50 words
A polyurethane formed from an organic polyol, an organic polyisocyanate, and a 4,6-dialkyl-m-phenylenediamine chain extender of structure: ##STR9## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 3
Dependent Claim
11 words
An article of manufacture formed from the polyurethane of claim 1.
Claim 4
Dependent Claim
21 words
A polyurethane of claim 1 wherein at least one of R 1 and R 2 has at least three carbon atoms.
Claim 5
Dependent Claim
22 words
A polyurethane of claim 1 wherein at least one of R 1 and R 2 has a secondary or tertiary carbon atom.
Claim 6
Dependent Claim
29 words
A polyurethane of claim 4 wherein at least one of R 1 and R 2 contains a secondary or tertiary carbon atom which is bonded to the aromatic nucleus.
Claim 7
Dependent Claim
22 words
A polyurethane of claim 1 wherein said chain extender is selected from the group consisting of 4,6-di-isopropyl-m-phenylenediamine; 4,6-di-tert-butyl-m-phenylenediamine; 4,6-di-ethyl-m-phenylenediamine; 4,6-di-sec-butyl-m-phenylenediamine; and 4-isopropyl-6-methyl-m-phenylenediamine.
Claim 8
Dependent Claim
11 words
A polyurethane of claim 1 wherein said chain extender is 4,6-diisopropyl-m-phenylenediamine.
Claim 9
Dependent Claim
70 words
An active hydrogen-containing blend for use in the production of polyurethane moldings, said blend comprising: (a) an organic polyol of molecular weight 400-7,000; and (b) a 4,6-dialkyl-m-phenylenediamine chain extender miscible with said polyol and having the structure: ##STR10## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 10
Dependent Claim
70 words
An active hydrogen-containing blend for use in the production of polyurethane moldings, said blend comprising: (a) an organic polyol of molecular weight 400-7,000; and (b) a 4,6-dialkyl-m-phenylenediamine chain extender miscible with said polyol and having the structure: ##STR10## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 11
Dependent Claim
17 words
The blend of claim 8 and further comprising a catalyst for reaction between polyol and isocyanate groups.
Claim 12
Dependent Claim
22 words
The blend of claim 8 wherein said chain extender is selected from the group consisting of 4,6-diisopropyl-m-phenylenediamine; 4,6-di-tert-butyl-m-phenylenediamine; 4,6-diethyl-m-phenylenediamine; 4,6-di-sec-butyl-m-phenylenediamine; and 4-isopropyl-6-methyl-m-phenylenediamine.
Claim 13
Dependent Claim
19 words
The blend of claim 8 wherein said chain extender comprises 5 to 50 percent by weight of the polyol.
Claim 14
Dependent Claim
209 words
A process for preparing a RIM polyurethane molded product, said process comprising the steps of: (a) at a temperature in the range of about 15°-100° C., subjecting to static impingement mixing at least two liquid streams, a first stream comprising (i) an organic polyol in the molecular weight range 400-7,000, and (ii) a 4,6-dialkyl-m-phenylenediamine chain extender of structure: ##STR11## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl; and a second stream comprising (iii) an organic polyisocyanate, or prepolymer or quasi-prepolymer formed from an organic polyisocyanate and an organic polyol, at least one of said first stream and said second stream containing a catalyst, whereby a liquid mixture is produced; (b) subsequently injecting a shot of said liquid mixture into a closed mold preheated to a temperature in the range about 15°-100° C.; (c) opening the mold and removing the formed polyurethane molded product; and (d) optionally subjecting said molded product to a post-cure at a temperature in the range about 50°-150° C., said process being conducted such that the amount of chain extender is about 5-30 weight percent of the total weight of components (i)-(iii).
Claim 15
Dependent Claim
209 words
A process for preparing a RIM polyurethane molded product, said process comprising the steps of: (a) at a temperature in the range of about 15°-100° C., subjecting to static impingement mixing at least two liquid streams, a first stream comprising (i) an organic polyol in the molecular weight range 400-7,000, and (ii) a 4,6-dialkyl-m-phenylenediamine chain extender of structure: ##STR11## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl; and a second stream comprising (iii) an organic polyisocyanate, or prepolymer or quasi-prepolymer formed from an organic polyisocyanate and an organic polyol, at least one of said first stream and said second stream containing a catalyst, whereby a liquid mixture is produced; (b) subsequently injecting a shot of said liquid mixture into a closed mold preheated to a temperature in the range about 15°-100° C.; (c) opening the mold and removing the formed polyurethane molded product; and (d) optionally subjecting said molded product to a post-cure at a temperature in the range about 50°-150° C., said process being conducted such that the amount of chain extender is about 5-30 weight percent of the total weight of components (i)-(iii).
Claim 16
Dependent Claim
26 words
The process of claim 12 wherein said chain extender is a dialkyl aromatic diamine selected from the group consisting of 4,6-diisopropyl-m-phenylenediamine; 4,6-di-tert-butyl-m-phenylenediamine; 4-isopropyl-6-methyl-m-phenylenediamine; 4,6-di-sec-butyl-m-phenylenediamine; and 4,6-diethyl-m-phenylenediamine.
Claim 17
Dependent Claim
85 words
A polyurethane elastomer prepared by reacting: (a) one equivalent of an intermediate containing about 0.5-15.0 percent free--NCO groups prepared by reacting an organic polyisocyanate with an organic compound having at least two active hydrogen atoms as determined by the Zerewitinoff test with (b) about 0.5-1.2 equivalents of 4,6-dialkyl-m-phenylenediamine chain extender of structure: ##STR12## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 18
Dependent Claim
85 words
A polyurethane elastomer prepared by reacting: (a) one equivalent of an intermediate containing about 0.5-15.0 percent free--NCO groups prepared by reacting an organic polyisocyanate with an organic compound having at least two active hydrogen atoms as determined by the Zerewitinoff test with (b) about 0.5-1.2 equivalents of 4,6-dialkyl-m-phenylenediamine chain extender of structure: ##STR12## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 19
Dependent Claim
25 words
The process of claim 14 wherein said chain extender is a dialkyl diamine selected from the group consisting of 4,6-diisopropyl-m-phenylenediamine; 4,6-di-tert-butyl-m-phenylenediamine; 4-isopropyl-6-methyl-m-phenylenediamine; 4,6-di-sec-butyl-phenylenediamine; and 4,6-diethyl-m-phenylenediamine.
Claim 20
Dependent Claim
134 words
A process for applying a coating of elastomer polyurethane to a substrate, said process comprising the steps of: (a) delivering to a mixing chamber an isocyanate-terminated prepolymer or quasi-prepolymer; (b) also delivering to said mixing chamber a resin stream comprising an organic polyol and a curing agent comprising 4,6-dialkyl-m-phenylenediamine of structure: ##STR13## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl; (c) if necessary for fluid transfer or intimate admixing, heating the components of (a) and (b) to about 130°-200° F.; (d) intimately admixing said prepolymer or quasi-prepolymer with said resin stream; and (e) spraying the admixture of (d) through an atomizing nozzle onto a substrate to form a polyurethane coating.
Claim 21
Dependent Claim
134 words
A process for applying a coating of elastomer polyurethane to a substrate, said process comprising the steps of: (a) delivering to a mixing chamber an isocyanate-terminated prepolymer or quasi-prepolymer; (b) also delivering to said mixing chamber a resin stream comprising an organic polyol and a curing agent comprising 4,6-dialkyl-m-phenylenediamine of structure: ##STR13## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl; (c) if necessary for fluid transfer or intimate admixing, heating the components of (a) and (b) to about 130°-200° F.; (d) intimately admixing said prepolymer or quasi-prepolymer with said resin stream; and (e) spraying the admixture of (d) through an atomizing nozzle onto a substrate to form a polyurethane coating.
Claim 22
Dependent Claim
15 words
The process of claim 16 wherein a solvent is also admixed with the polyurethane-forming components.
Claim 23
Dependent Claim
126 words
A process for the successive preparation of polyurethane reaction injection molded articles without successive applications of external mold release agent, said process comprising: (a) injecting into a closed mold (i) an organic polyisocyanate, (ii) an organic polyol, (iii) a catalyst, and (iv) a chain extender comprising at least about 5% by weight of an aromatic diamine reactive internal mold release agent of structure: ##STR14## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 -cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl; (b) removing the molded article from the mold upon solidification; and (c) after an optional post-cure period, repeating steps (a) and (b) without application of an external mold release agent.
Claim 24
Dependent Claim
126 words
A process for the successive preparation of polyurethane reaction injection molded articles without successive applications of external mold release agent, said process comprising: (a) injecting into a closed mold (i) an organic polyisocyanate, (ii) an organic polyol, (iii) a catalyst, and (iv) a chain extender comprising at least about 5% by weight of an aromatic diamine reactive internal mold release agent of structure: ##STR14## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 -cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl; (b) removing the molded article from the mold upon solidification; and (c) after an optional post-cure period, repeating steps (a) and (b) without application of an external mold release agent.
Claim 25
Dependent Claim
13 words
The process of claim 18 wherein said aromatic diamine is 4,6-diisopropyl-m-phenylenediamine or 4,6-di-sec-butyl-m-phenylenediamine.
Claim 26
Dependent Claim
20 words
The process of claim 19 wherein said aromatic diamine reactive internal mold release agent comprises 10-50% of said chain extender.
Claim 27
Dependent Claim
19 words
The process of claim 18 wherein said chain extender comprises 0-95% by weight methylenebis(2,6-diisopropylaniline); methylenebis(2,6-diethylaniline); 1-methyl-3,5-diethyl-2,4-diaminobenzene; 1-methyl-3,5-diethyl-2,6-diaminobenzene; or 1,3,5-triethyl-2,4-diaminobenzene.
Claim 28
Dependent Claim
16 words
The process of claim 21 wherein said chain extender comprises a mixture of 1-methyl-3,5-diethyl-2,4-diaminobenzene; and 1-methyl-3,5-diethyl-2,6-diaminobenzene.
Claim 29
Dependent Claim
14 words
The process of claim 22 wherein said reactive internal mold release agent is 4,6-diisopropyl-m-phenylenediamine.
Claim 30
Dependent Claim
18 words
The process of claim 18 wherein the closed mold of step (a) is maintained at about 115°-145° F.
Claim 31
Dependent Claim
14 words
The process of claim 24 wherein said mold is maintained at about 120°-130° F.
Claim 32
Dependent Claim
71 words
A reactive internal mold release composition comprising a first chain extender suitable for use in the formation of RIM or cast polyurethane elastomers and a 4,6-dialkyl-m-phenylenediamine chain extender different from said first chain extender and having the structure: ##STR15## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 33
Dependent Claim
71 words
A reactive internal mold release composition comprising a first chain extender suitable for use in the formation of RIM or cast polyurethane elastomers and a 4,6-dialkyl-m-phenylenediamine chain extender different from said first chain extender and having the structure: ##STR15## wherein R 1 is a C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl and R 2 is a C 2 -C 6 alkyl or C 3 -C 6 cycloalkyl.
Claim 34
Dependent Claim
19 words
The composition of claim 26 wherein said first chain extender is 1-methyl-3,5-diethyl-2,4-diaminobenzene; 1-methyl-3,5-diethyl-2,6-diaminobenzene; or a mixture of said diaminobenzenes.
Claim 35
Dependent Claim
10 words
The composition of claim 26 wherein said 4,6-dialkyl-m-phenylenediamine is 4,6-diisopropyl-m-phenylenediamine.
Claim 36
Dependent Claim
10 words
The process of claim 27 wherein said 4,6-dialkyl-m-phenylenediamine is 4,6-diisopropyl-m-phenylenediamine.
Claim 37
Dependent Claim
25 words
The composition of claim 26 wherein said composition contains at least about one mole part 4,6-dialkyl-m-phenylenediamine per nine mole parts of said first chain extender.
Claim 38
Dependent Claim
25 words
The composition of claim 30 wherein said composition contains at least about one mole part 4,6-dialkyl-m-phenylenediamine per four mole parts of said first chain extender.
Claim 39
Dependent Claim
24 words
The composition of claim 31 wherein said 4,6-dialkyl-m-phenylenediamine is 4,6-diisopropyl-m-phenylenediamine and said first chain extender is 1-methyl-3,5-diethyl-2,4-diaminobenzene; 1-methyl-3,5-diethyl-2,6-diaminobenzene; or a mixture of said diaminobenzenes.
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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) | 1988-07-01 | 1988-12-31 | 1989-07-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-07-01 | 1992-12-31 | 1993-07-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-07-01 | 1996-12-31 | 1997-07-02 | $7700.00 | Window Closed / Lapsed |