US4242250A
Expired / Lapsed
US
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Organopolysiloxane resins formed with catalysts of formic acid and hydrocarbyl substituted ammonium hydroxide
Assignee: Techneglas LLC
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Filing: 1979-06-25
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Granted: 1980-12-30
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Expires: 1999-06-25
Abstract
Abstract A process for forming organopolysiloxanes from trialkoxysilanes and the resulting resinous products are disclosed, characterized in that the organopolysiloxane resins have increased abrasion and solvent resistance with good shelf life. The organopolysiloxanes are formed by dual catalysts that operate preferably in sequence. Hydrolysis and condensation of the trialkoxysilanes are carried out in an aqueous solution and catalyzed by formic acid at a relatively high strength, such as an amount greater than 700 ppm. Cross-linking of the resulting partially condensed, curable organopolysiloxane is then catalyzed by a hydrocarbyl substituted ammonium hydroxide in which the hydrocarbyl substituent may be alkyl or alkenyl up to about 6 carbon atoms. The resinous products are especially useful as coating compositions.
Inventors
- 👤 Donald W. Gagnon
- 👤 James J. Tillman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 14:02
CPC Classifications
C; C08; C08G; C08G77/00; C08G77/04; C08G77/06; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31507; Y10T428/31551; Y10T428/31609; Y10T428/31612; Y10T428/31652; Y10T428/31663
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
102 words
In a process for preparing an organopolysiloxane by hydrolyzing a trialkoxysilane in aqueous solution containing at least the stoichiometric amount of water required for said hydrolysis, condensing the hydrolyzed silane to an organopolysiloxane, and then cross-linking the oganopolysiloxane; the improvements comprising catalyzing at least some of said condensation by formic acid present in said solution at a strength greater than 700 ppm, and catalyzing cross-linking of said organopolysiloxane by a hydrocarbyl substituted ammonium hydroxide, said hydrocarbyl substituent being selected from alkyl, isoalkyl, and cycloalkyl up to about six carbon atoms, and from alkenyl, isoalkenyl, and cycloalkenyl up to about six carbon atoms.
Claim 2
Dependent Claim
102 words
In a process for preparing an organopolysiloxane by hydrolyzing a trialkoxysilane in aqueous solution containing at least the stoichiometric amount of water required for said hydrolysis, condensing the hydrolyzed silane to an organopolysiloxane, and then cross-linking the oganopolysiloxane; the improvements comprising catalyzing at least some of said condensation by formic acid present in said solution at a strength greater than 700 ppm, and catalyzing cross-linking of said organopolysiloxane by a hydrocarbyl substituted ammonium hydroxide, said hydrocarbyl substituent being selected from alkyl, isoalkyl, and cycloalkyl up to about six carbon atoms, and from alkenyl, isoalkenyl, and cycloalkenyl up to about six carbon atoms.
Claim 3
Dependent Claim
21 words
The process of claim 1 in which any alkoxy substituent of said trialkoxysilane contains from one to about six carbon atoms.
Claim 4
Dependent Claim
34 words
The process of claim 1 in which said trialkoxysilane is selected from the group consisting of alkyl trialkoxysilane, in which said alkyl group contains from one to about six carbon atoms, and phenyl trialkoxysilane.
Claim 5
Dependent Claim
40 words
The process of claim 1 in which said trialkoxysilane corresponds to the formula: RSi(OR.sub.1).sub.3 in which R is alkyl from one to about six carbon atoms and phenyl, and R 1 is alkyl from one to about six carbon atoms.
Claim 6
Dependent Claim
27 words
The process of claim 1 in which the molar ratio of said water to said trialkoxysilane is within the range of about 1.5:1 to about 10:1, respectively.
Claim 7
Dependent Claim
43 words
The process of claim 1 including heating the solution at a temperature within the range of about 40° C. to about 300° C. for about one hour to about 10 hours to effect said condensation of the silane and cross-linking of the organopolysiloxane.
Claim 8
Dependent Claim
26 words
The process of claim 1 in which said formic acid is present in an amount within the range of about 750 ppm to about 80,000 ppm.
Claim 9
Dependent Claim
26 words
The process of claim 1 in which said formic acid is present in an amount within the range of about 750 ppm to about 45,500 ppm.
Claim 10
Dependent Claim
26 words
The process of claim 1 in which said formic acid is present in an amount within the range of about 2,400 ppm to about 4,800 ppm.
Claim 11
Dependent Claim
17 words
The process of claim 1 in which said hydrocarbyl substituent has up to about four carbon atoms.
Claim 12
Dependent Claim
15 words
The process of claim 1 in which said cross-linking catalyst is a tetraalkyl ammonium hydroxide.
Claim 13
Dependent Claim
24 words
The process of claim 1 in which said cross-linking catalyst is tetraalkyl ammonium hydroxide, said alkyl substituent having up to about four carbon atoms.
Claim 14
Dependent Claim
14 words
The process of claim 1 in which said cross-linking catalyst is tetramethyl ammonium hydroxide.
Claim 15
Dependent Claim
35 words
The process of claim 1 including coating a substrate with said solution any time prior to complete cross-linking of said organopolysiloxane, and then heating to form a coating of said cross-linked polysiloxane on said substrate.
Claim 16
Dependent Claim
16 words
The process of claim 14 in which said substrate is a resinous plastic body of polycarbonate.
Claim 17
Dependent Claim
21 words
The process of claim 1 in which said condensation of said hydrolyzed silane is also carried out by a mineral acid.
Claim 18
Dependent Claim
175 words
A process for preparing at relatively high acid concentration without premature gelation an organopolysiloxane having increased abrasion resistance, comprising: (a) hydrolyzing in aqueous solution a trialkoxy silane corresponding to the formula RSi(OR.sub.1).sub.3 in which R is alkyl from one to about six carbon atoms and phenyl, and R 1 may be the same or different and is alkyl from one carbon atom to about six carbon atoms, (b) said aqueous solution having a molar ratio of water to trialkoxysilane within the range of about 1.5:1 to about 5:1, respectively, (c) said aqueous solution containing formic acid in an amount greater than 700 ppm, (d) heating said solution to condense the hydrolyzed silane and form an organo polysiloxane, (e) adding to said aqueous solution a catalytic amount of a tetrahydrocarbyl substituted ammonium hydroxide, said hydrocarbyl substituent being selected from alkyl, isoalkyl, and cycloalkyl up to about four carbon atoms and from alkenyl, isoalkenyl, and cycloalkenyl up to about four carbon atoms, and (f) continuing to heat said solution to cross-link said organopolysiloxane to a thermoset form.
Claim 19
Dependent Claim
175 words
A process for preparing at relatively high acid concentration without premature gelation an organopolysiloxane having increased abrasion resistance, comprising: (a) hydrolyzing in aqueous solution a trialkoxy silane corresponding to the formula RSi(OR.sub.1).sub.3 in which R is alkyl from one to about six carbon atoms and phenyl, and R 1 may be the same or different and is alkyl from one carbon atom to about six carbon atoms, (b) said aqueous solution having a molar ratio of water to trialkoxysilane within the range of about 1.5:1 to about 5:1, respectively, (c) said aqueous solution containing formic acid in an amount greater than 700 ppm, (d) heating said solution to condense the hydrolyzed silane and form an organo polysiloxane, (e) adding to said aqueous solution a catalytic amount of a tetrahydrocarbyl substituted ammonium hydroxide, said hydrocarbyl substituent being selected from alkyl, isoalkyl, and cycloalkyl up to about four carbon atoms and from alkenyl, isoalkenyl, and cycloalkenyl up to about four carbon atoms, and (f) continuing to heat said solution to cross-link said organopolysiloxane to a thermoset form.
Claim 20
Dependent Claim
40 words
The process of claim 17 in which said heating of the solution, including steps d and f, is at a temperature within the range of about 40° C. to about 300° C. for about one hour to about 10 hours.
Claim 21
Dependent Claim
26 words
The process of claim 17 in which said formic acid is present in an amount within the range of about 750 ppm to about 80,000 ppm.
Claim 22
Dependent Claim
35 words
The process of claim 17 including coating a substrate with said solution any time prior to complete cross-linking of said organopolysiloxane, and then heating to form a coating of said cross-link polysiloxane on said substrate.
Claim 23
Dependent Claim
25 words
The process of claim 17 in which the amount of hydrocarbyl substituted ammonium hydroxide added is insufficient to neutralize all of the formic acid present.
Claim 24
Dependent Claim
28 words
The process of claim 17 in which said substituted ammonium hydroxide is dissolved in a non-reactive organic solvent, and the resulting solution is added to said aqueous solution.
Claim 25
Dependent Claim
9 words
An organopolysiloxane resulting from the process of claim 1.
Claim 26
Dependent Claim
9 words
An organopolysiloxane resulting from the process of claim 17.
Claim 27
Dependent Claim
128 words
A coating composition of a partially cured organopolysiloxane adapted to be further cured including cross-linking to a solid form, said coating composition comprising: (a) an organopolysiloxane condensation product capable of further cure resulting from hydrolysis of a trialkoxysilane in aqueous solution, containing at least the stoichiometric amount of water required for said hydrolysis and condensation of the hydrolyzed silane to the organopolysiloxane, (b) formic acid present at a strength greater than 700 ppm, and (c) a catalytic amount of a catalyst to effect cross-linking of the organopolysiloxane to a solid form, said cross-linking catalyst comprising a hydrocarbyl substituted ammonium hydroxide, said hydrocarbyl substituenet being selected from alkyl, isoalkyl, and cycloalkyl up to about six carbon atoms, and from alkenyl, isoalkenyl, and cycloalkenyl up to about six carbon atoms.
Claim 28
Dependent Claim
128 words
A coating composition of a partially cured organopolysiloxane adapted to be further cured including cross-linking to a solid form, said coating composition comprising: (a) an organopolysiloxane condensation product capable of further cure resulting from hydrolysis of a trialkoxysilane in aqueous solution, containing at least the stoichiometric amount of water required for said hydrolysis and condensation of the hydrolyzed silane to the organopolysiloxane, (b) formic acid present at a strength greater than 700 ppm, and (c) a catalytic amount of a catalyst to effect cross-linking of the organopolysiloxane to a solid form, said cross-linking catalyst comprising a hydrocarbyl substituted ammonium hydroxide, said hydrocarbyl substituenet being selected from alkyl, isoalkyl, and cycloalkyl up to about six carbon atoms, and from alkenyl, isoalkenyl, and cycloalkenyl up to about six carbon atoms.
Claim 29
Dependent Claim
18 words
The coating composition of claim 25 in which said hydrocarbyl substituent has up to about four carbon atoms.
Claim 30
Dependent Claim
15 words
The coating composition of claim 25 in which said cross-linking catalyst is tetraalkyl ammonium hydroxide.
Claim 31
Dependent Claim
25 words
The coating composition of claim 25 in which said cross-linking catalyst is tetraalkyl ammonium hydroxide, said alkyl substituent having up to about four carbon atoms.
Claim 32
Dependent Claim
15 words
The coating composition of claim 25 in which said cross-linking catalyst is tetramethyl ammonium hydroxide.
Claim 33
Dependent Claim
14 words
A coating composition of claim 25 in which said solution contains an organic solvent.
Claim 34
Dependent Claim
41 words
A coating composition of claim 25 in which said trialkoxysilane corresponds to the formula: RSi(OR.sub.1).sub.3 in which R i alkyl from one to about six carbon atoms and phenyl, and R 1 is alkyl from one to about six carbon atoms.
Claim 35
Dependent Claim
13 words
A substrate having a coating formed from the coating composition of claim 25.
References Cited (Backward Citations)
US3433764A
Cited
US3457221A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-12-30 | 1984-06-30 | 1984-12-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-12-30 | 1988-06-30 | 1988-12-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-12-30 | 1992-06-30 | 1992-12-30 | $7700.00 | Window Closed / Lapsed |