CA1129581A - Ambient temperature curable hydroxyl containing polymer - Google Patents
Ambient temperature curable hydroxyl containing polymerInfo
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- CA1129581A CA1129581A CA338,026A CA338026A CA1129581A CA 1129581 A CA1129581 A CA 1129581A CA 338026 A CA338026 A CA 338026A CA 1129581 A CA1129581 A CA 1129581A
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- 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
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
-
- 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
Abstract
ABSTRACT
Ambient temperature curable compositions comprising a hydroxyl containing organic polymer and an aminoorganosilicon acylamino compound, said compo-sitions being useful as protective coating compositions.
Ambient temperature curable compositions comprising a hydroxyl containing organic polymer and an aminoorganosilicon acylamino compound, said compo-sitions being useful as protective coating compositions.
Description
:~ ' ~ S~ ~ 12363 . .
BACKGROUND OF THE INVENTION_ This invention relates to novel room temperature curable compositions comprising a hydroxyl containing organic , thermoplastic polymer and an aminoorganosilicon acylamino compound, as well as to the crosslinked products derived from said compositions.
The employment of organosilanes to aid in the crosslinking of polymeric materials is well known in the art. However, heretofore in order to obtain room temperature curable compositions the prior art has had to pre-react the starting organic polymer with the organosilane at elevated temperatures. One exception to such methods has been the use - of halosilanes which are known to react at room temperature with hydroxyl containing polymers, however, this procedure has the disadvantage of also producing an undesirable acid by-product, e.g. hydrogen chloride, which if not removed may have a deleterious effect on the performanc~ of the cured ~ ;
composition.
': ~
SUMMARY OF THE INVENTION
It has now been discovered that room temperature ; curable polymer compositions can also be easily prepared at , room temperature by simply mixing a hydroxyl containing ;~ organic thermoplastic polymer with certain hydrolyzable ;
aminoorganosilicon acylamino compounds without also resulting in undesirable by-products.
~Z9~ 12353 Thus, it is an object of this invention to pro-vide room t~mperature cura~le c~mpositions comprising a hydrox~tl containing organic thermoplastic polymer and a hydrolyzab`le aminoorganosilicon acylamino compound. It is anot~er object of this invention to provide cured cross-linked products, e.g. solvent resistant coatings, derived from the c~rable composit~ons of this invention. Other objects and advantages of this invention will ~ecome readily apparent from the following description and appended claims.
More specifically one aspect of this invention may be described as a substantially anhydrous, acid-free, ro~m temperature curable composition ~hic~ com~rises (A) an organic thermoplastic polymer containing at least two hydro~yL radicals which are directly ~onded to non-carboxylic carbon atoms of said polymer; and CB) a hydro-lyzable aminoor~anosilicon acylamino compound having the formula Rl R3 R3 Q Q O R3 Cl~ X3_aSi ~ R~T CR2~t CEC~CNE - CR2~)XR4 and mixtures thereof wherein:
X is an alkoxy radical having 1 to 6 carbon atoms;
R is a divalent alkylene radical having 1 to 4 carbon atoms;
Rl is hydrogen or an alkyl radical having 1 to 4 carbon atoms; R2 is a divalent alkylene radical having 2 to 4 carbon atoms; R3 is a radical selected from the group con-sisting of hydrogen, an alkyl radical having 1 to 20 carbon ato~s or a p~enyl radical; R4 is a radical selected from the group consistin~ of an alkyl radical having 1 to 20 carbon atoms, a phenyl radical or a silyl radical of the formula:
~ llZ958~ 12363 .,,;
Rl , la -R - Si - X3_a wherein ~, R and Rl are the same as defined above; Q is a radical selected from the group consîsting of hydrogen, an alkyl radical o~ 1 to 4 car~on atoms, a ~henyl radical or an ester radical of the formula -CooR5 wherein R5 is an alkyl radical having 1 to 4 carbon atoms; and wherein a has a value of 0 to 2 and t and Y~ each ~ave a value of 0 to 4, with the proviso tE~at T~en ~ is at least 1, R4 can also be hydrogen; and wherein said composition contains a~out 5 to 50 parts by ~eight of said ~drolyza~le aminoorganosilicon ;
acylamino compound C3~ per 100 parts by weight of said organic polymer CA~.
Any hydroxyl containing organic thermoplastic polymer having at least two hvdroxyl radicals which are . directly ~onded to non-carboxylic 0 car~on atoms Ci.e. -C ) ~' 20 can be employed as the organic polymer component of the room temperature ci.e. ambient~ curable compositions of this invention. Such types of hydroxyl containîng organic ~;~
polymers and/or methods for their preparation are well known in the polymer art. Of course it is to ~e understood ~hat the hydroxyl containing organic themoplastic polymers employable in this inventîon include homopoly~ers, copolymers, terpolymers and the like and that mixtures of more than one type or class of polymers can b.e employed if desired.
Likewise, it is to ~e understood that the particular proportions of polymer unîts and molecular weights of the hydroxy containing organic thermoplastic polymer components 4.
~Z~58~ 1'363 : . ~
of this invention are not generally critical to the inven-- tion. Illustrati~e ex~mples of such hydro~yl containing organic t~ermopla~tic polymers include:
(a) Hydroxyalkyl acrylate modified vinyl chloride polymers such as the uniformly random hydroxyl-functional copolymers or terpolymers of (i) vinyl chlorlde;
(ii) hydroxyalkyl acrylate having 2 eo 4 carbons in the al~yl segment; and, optionally, (iii) a polymerizable - monomer chosen from alkyl (1-8 carbon) esters of poly-merizable alpha, beta-ethylenically unsaturated acids such as acrylic, methacrylic, maleic, fumaric, itaconic and the like, and vinyl esters of saturated fatty acids of 1-6 carbon atoms, such as vinyl acetate, vinyl propionate and -~ the like. Suitable hydroxyl-functional copolymers and terpolymers are described in U.S. 3,884,887 and U.S.
3,755,~71.
(b) PolyPther polyol polymers such as the al~ylene oxide adducts of water or a polyhydric organic compound as the initiator or starter, e.g. illustrative initiators which may be used individually or in com~ination include ethylene glycol; diethylene glycol; propylene glycol; 1,5-pentanediol; hexylene glycol; dipropylene glycol; trimethylene glycol; 1,2-cyclohexaned~ol; 3-cyclo-. .
hexane~ dimethanol and dibromo-terivative thereof;
glycerol; 1,2,6-hexanetriol; l,l,l-trimethyolethane;
l,l,l-trimethyolpropane; 3-(2-hydroxyethoxy)- and 3-(2-hydroxypropoxy)-1,3-propanediols; 2,4-dimethyl-
BACKGROUND OF THE INVENTION_ This invention relates to novel room temperature curable compositions comprising a hydroxyl containing organic , thermoplastic polymer and an aminoorganosilicon acylamino compound, as well as to the crosslinked products derived from said compositions.
The employment of organosilanes to aid in the crosslinking of polymeric materials is well known in the art. However, heretofore in order to obtain room temperature curable compositions the prior art has had to pre-react the starting organic polymer with the organosilane at elevated temperatures. One exception to such methods has been the use - of halosilanes which are known to react at room temperature with hydroxyl containing polymers, however, this procedure has the disadvantage of also producing an undesirable acid by-product, e.g. hydrogen chloride, which if not removed may have a deleterious effect on the performanc~ of the cured ~ ;
composition.
': ~
SUMMARY OF THE INVENTION
It has now been discovered that room temperature ; curable polymer compositions can also be easily prepared at , room temperature by simply mixing a hydroxyl containing ;~ organic thermoplastic polymer with certain hydrolyzable ;
aminoorganosilicon acylamino compounds without also resulting in undesirable by-products.
~Z9~ 12353 Thus, it is an object of this invention to pro-vide room t~mperature cura~le c~mpositions comprising a hydrox~tl containing organic thermoplastic polymer and a hydrolyzab`le aminoorganosilicon acylamino compound. It is anot~er object of this invention to provide cured cross-linked products, e.g. solvent resistant coatings, derived from the c~rable composit~ons of this invention. Other objects and advantages of this invention will ~ecome readily apparent from the following description and appended claims.
More specifically one aspect of this invention may be described as a substantially anhydrous, acid-free, ro~m temperature curable composition ~hic~ com~rises (A) an organic thermoplastic polymer containing at least two hydro~yL radicals which are directly ~onded to non-carboxylic carbon atoms of said polymer; and CB) a hydro-lyzable aminoor~anosilicon acylamino compound having the formula Rl R3 R3 Q Q O R3 Cl~ X3_aSi ~ R~T CR2~t CEC~CNE - CR2~)XR4 and mixtures thereof wherein:
X is an alkoxy radical having 1 to 6 carbon atoms;
R is a divalent alkylene radical having 1 to 4 carbon atoms;
Rl is hydrogen or an alkyl radical having 1 to 4 carbon atoms; R2 is a divalent alkylene radical having 2 to 4 carbon atoms; R3 is a radical selected from the group con-sisting of hydrogen, an alkyl radical having 1 to 20 carbon ato~s or a p~enyl radical; R4 is a radical selected from the group consistin~ of an alkyl radical having 1 to 20 carbon atoms, a phenyl radical or a silyl radical of the formula:
~ llZ958~ 12363 .,,;
Rl , la -R - Si - X3_a wherein ~, R and Rl are the same as defined above; Q is a radical selected from the group consîsting of hydrogen, an alkyl radical o~ 1 to 4 car~on atoms, a ~henyl radical or an ester radical of the formula -CooR5 wherein R5 is an alkyl radical having 1 to 4 carbon atoms; and wherein a has a value of 0 to 2 and t and Y~ each ~ave a value of 0 to 4, with the proviso tE~at T~en ~ is at least 1, R4 can also be hydrogen; and wherein said composition contains a~out 5 to 50 parts by ~eight of said ~drolyza~le aminoorganosilicon ;
acylamino compound C3~ per 100 parts by weight of said organic polymer CA~.
Any hydroxyl containing organic thermoplastic polymer having at least two hvdroxyl radicals which are . directly ~onded to non-carboxylic 0 car~on atoms Ci.e. -C ) ~' 20 can be employed as the organic polymer component of the room temperature ci.e. ambient~ curable compositions of this invention. Such types of hydroxyl containîng organic ~;~
polymers and/or methods for their preparation are well known in the polymer art. Of course it is to ~e understood ~hat the hydroxyl containing organic themoplastic polymers employable in this inventîon include homopoly~ers, copolymers, terpolymers and the like and that mixtures of more than one type or class of polymers can b.e employed if desired.
Likewise, it is to ~e understood that the particular proportions of polymer unîts and molecular weights of the hydroxy containing organic thermoplastic polymer components 4.
~Z~58~ 1'363 : . ~
of this invention are not generally critical to the inven-- tion. Illustrati~e ex~mples of such hydro~yl containing organic t~ermopla~tic polymers include:
(a) Hydroxyalkyl acrylate modified vinyl chloride polymers such as the uniformly random hydroxyl-functional copolymers or terpolymers of (i) vinyl chlorlde;
(ii) hydroxyalkyl acrylate having 2 eo 4 carbons in the al~yl segment; and, optionally, (iii) a polymerizable - monomer chosen from alkyl (1-8 carbon) esters of poly-merizable alpha, beta-ethylenically unsaturated acids such as acrylic, methacrylic, maleic, fumaric, itaconic and the like, and vinyl esters of saturated fatty acids of 1-6 carbon atoms, such as vinyl acetate, vinyl propionate and -~ the like. Suitable hydroxyl-functional copolymers and terpolymers are described in U.S. 3,884,887 and U.S.
3,755,~71.
(b) PolyPther polyol polymers such as the al~ylene oxide adducts of water or a polyhydric organic compound as the initiator or starter, e.g. illustrative initiators which may be used individually or in com~ination include ethylene glycol; diethylene glycol; propylene glycol; 1,5-pentanediol; hexylene glycol; dipropylene glycol; trimethylene glycol; 1,2-cyclohexaned~ol; 3-cyclo-. .
hexane~ dimethanol and dibromo-terivative thereof;
glycerol; 1,2,6-hexanetriol; l,l,l-trimethyolethane;
l,l,l-trimethyolpropane; 3-(2-hydroxyethoxy)- and 3-(2-hydroxypropoxy)-1,3-propanediols; 2,4-dimethyl-
2-(2~hydroxyetho..y)methylpentanediol-1,5; 1,1,1-tris[2-hydroxyethoxy)methyl]ethane; l,l,l-tris~2-hydroxypropoxy)
3~ methyl]propane; pentaerythritol; sorbitol; sucrose; alpha-- . ' :: ' .. ~:
~z95~ 12363 methyl glucoside; and other such polyhydric ccmpounds consisting of carbon, hydrogen and oxygen and having usually not more than about 15 carbon atoms per molecule. Illustra-tive alkylene oxides include ethylene oxide, propylene oxide, butylene oxide as well as various mixtures of such oxides. Also included among the polyether polyol polymers useful herein are poly(hydroxyethers) derived from diphenols and epichlorohydrin, e.g. phenvxy resins, as well as those polymers commonly referred to in the art as polymer/poly-ether polyols which may be produced by polymerizing one ormore ethylenically unsaturated monomers dissolved or dispersed in any of the above described alkylene oxide adduct polyols. Illustrative of such unsaturated monomers which may be employed individually or in combination include - ethylene, propylene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene, butadiene, and the like.
~ c) Polyhydroxy containing ac~ylic polymers such as the copolymers and terpolymers of hydroxyalkyl acrylates having 2 to 4 carbon atoms in the alkyl segments and alkyl acrylates andtor alkyl methacrylates having 1 to 6 carbon atoms in the aLkyl segments.
(d) Polyvinyl alcohol polymers such as the hydrolyzed or partially hydrolyzed polymers derived from the homopolymers of vinyl esters of saturated fatty acids of 1-6 carbon atoms or the copolymers of said vinyl esters and one or more ethylenically unsaturated monomers such as 6.
- , ... ..
i.. ; , - ~295~1 123~3 . ~
ethylene, propylene, butylene, acrylonitrile, methacrylo-~- ni~rile, vinyl chloride, vinylidene chlo~ide, styrene, alpha-methylstyrene, butadiene, and the like.
(e) Polyhydroxy containinO polyvinyl acetal polymers such as polyvinylbutyral resins and the like.
(f) Polyester polyol polymers such as the reaction products of polyfuncti.onal organic carboxylic ~` acids and polyhydric alcohols, which reaction products contain at least tWQ hydroxyl groups (as alcoholic OH) per molecule, and cyclic ester polymers containing at least two hydroxyl groups per molecule prepared from epsilon capro-lactone or other lactones and the copolymers of such lactones with polyhydric alcohols.
Typical of the polyfunctional organic carboxylic ; acids that can be employed in producing polyester polyols useful in this invention are: dicarboxylic aliphatic acids such as succinic, adipic, sebacic, azelaic, glutaric, pimelic, malonic and suberic acids; and dicarboxylic aromatic acids such as phthalic acid, terephthalic acid, isophthalic acid and the like. Other polycarboxylic acids that can be employed are the "dimer acids" such as the dimer of linoleic acid. Hydroxyl-containing monocarboxylic acids (such as ricinoleic acid) can also be used. Alternatively, the a~hydrides of any of these various acids can be employed in producing the polyester polyols.
The polyhydric alcohols (organic polyols) that can be employed in producing the polyester polyol starting 7.
~ 1 Z 9 5 8 1 12363 material useful in this invention include the monomeric polyhydric alcohols such as, for example, glycerol; 1,2,6~
hexanetriol; ethylene glycol; diethylene glycol; trimethylol propane; trimethyolethane; pentaerythritol; propylene glycol; 1,2-, 1,3- and 1,4-butylene glycols; 1,5-pentanediol;
sorbitol; and the like, including mixtures thereo.
Other polyhydric alcohols that can be employed in producing the polyester polyols useful in this invention are the polymeric polyhydric alcohols which include the linear and branched chain polyethers having a plurality of acycl~c ether oxygens and at least two alcoholic hydroxyl radicals.
Illustrative of such polyether polyols are the poly(oxyalkylene) polyols containing one or more chains of connected oxyalkylene radicals which are prepared by the reaction of one or more alkylene oxides with acyclic and alicyclic polyols. Examples of the poly(oxyalkylene) polyols include the poly(oxyethylene) glycols prepared by the addition of ethylene oxide to water, ethylene glycol or diethylene glycol; poly(oxypropylene) glycols prepared by the addition of propylene oxide to water, propylene glycol or dipropylene glycol; m~xed oxy-ethylene-oxypropylene polyglycols prepared in a similar manner utilizing a mixture of ethylene oxide or a sequential addition of ethylene oxide and propylene oxide; and the poly(oxybutylene) glycols and copolymers such as poly(oxy-ethylene-oxybutylene) glycols and poly(oxypropylene-oxy-butylene) glycols. Included in the term "poly(oxybutylene) glycols" are polymers of 1,2-butyleneoxide and 2,3-butyleneoxide.
8 . -i .. . ..
3L~ Z 9 S 8 ~ 12363 , Illustrative of further polyester polyols are the re-~ction products of any of the aforesaid polycarboxylic acids and the polyhydric alcohols prepared by the reaction of one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, with any of the following: glycerol; trimethylolpropane9 1,2,6-he~anetriol; pentaerythritol; sorbitol; glycosides such as methyl, ethyl, propyl, butyl cmd 2-ethyLhexyl arabinoside, xyloside, fructoside, glucoside, and rhammoside; sucrose;
mononuclear polyhydroxybenzenes such as resorcinoL, pyro-- gallol, phloroglucinol, hydroquinone, 4,6-di-tertiary-butylcatechol, and catechol; polynuclear hydroxybenæenes ("polynuclear" designating at least two benzene nuclei) such as the di-, tri- and tetraphenylol compounds in which two to four hydroxybenzene groups are attached either ~ directly by means of single bonds or through an aliphatic ; hydrocarbon radical containinO one to twelve carbon atoms, such compounds being typically illustrated by 2,2-bis(p-hydroxyphenyl)-propane, bis(p-hydroxyphenyl)-methane and the various diphenols and diphenol methanes disclosed in United States Patent ~os. 2,506,486 and 2,744,882, respectively. Another type of polyester polyol is that produced by reaction of a polycarboxylic acid and the polyether adducts formed by reaction of ethylene oxide, propylene oxide or butylene oxide with phenol-formaldehyde condensation products such as the novolaks.
` 1~2~581 12363 (g) Phenolic resin polymers such as the solid resoles and novolak resins disclosed in U.S. Patent 4,116,921 and British Patent 1,417,437. The phenol of the resin can be unsubstituted phenol or substituted such as c~esol, bi-phenol-A, para-substituted phenols and the like while for-maldehyde or a material that generates formaldehyde in situ is the aldehyde employed in making phenol resins. The preferred phenolic resins are resoles produced by reacting formaldehyde with bisphenol-A at elevated temperatures in the presence of a base-catalyst and having a neutralized pH
of about 3 to 8.
The preferred hydroxyl containing organic thermo-plastic polymer components of this invention are the hydro-xylalkyl acrylate modified vinyl chloride polymers described above having (a) from abou~ 50 to 85 weight percent vinyl chloride derived mer units; (b) from 0 to 10 weight percent mer units derived from a polymerizable monomer selected from the class consisting of alkyl esters of alpha, beta-ethyleni- `~
cally unsaturated carboxylic acids as described above and vinyl esters of saturated fatty acids as described above, the preferred polymerizable monomer being vinyl acetate, and (c) from 10 to 30 weight percent mer units derived from hydroxy-alkyl acrylate as described above, preferably hydroxypropyl acrylate. The most preferred polymer being a uniformly hydroxyl-functional random terpolymer of about 80 weight percent vinyl chloride mer units, about 5 weight percent vinyl acetate mer units and about 15 weight percent hydroxypropyl acrylate mer units. ~
:
.
~- `'' .
~z9~ 12363 , .
~ ith regard to the aminoorganosilicon acylamino compounds and m~xtures thereof of Formula I a~ove it is to be understood tXat each X, R, Rl, R2, R3, R4, a, t and x may ~e the same or different in any given silicon compound and mixtures thereof. ~oreover, îllustrat;ve radicals represented by X above inclucle alkoxy radicals ~aving 1 ~o 6 carDon atoms, such as methoxy, ethoxy, propoxy, 2-methoxyethoxy, isopropoxy, Qexyloxy and the like, the pre~erred alkoxy radîcal being methoxy. Illustrative divalent alkylene radicals represented ~y R a~ove include - methylene, ethylene, propylene, isopropylene, butylene and the like, the preferred divalent alkylene groups ~eing eth~lene C-C2H4-~ and propylene C-C3H6-~. Illustrative radicals represented ~y Rl above include alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl and the ~.
like. Illustrative divalent alkylene radicals represented by R2 above include ethylene, ~ropylene, isopropylene, butylene, and the lîke, the preferred divalent alkylene groups being ethylene and propylene. Illustrative radicals represented ~y R3 above include hydrogen, phenyl and alkyl radicals having from 1 to 20 carbon atoms suc~ as methyl, ethvl, propyl, octyl, octadecyl, eicosyl and the like.
Preferably R3 is hydrogen. Illustrative radicals repre-- sented by R4 above include hydrogen, phenyl, alkyl radicals having from l to 20 carbon atoms such as methvl, ethyl, propyl, octyl, octadecyl, eicosyl, and the like as well as silyl groups of the formula '' Ra -R-Si.-X3_a 1 1 . :
- ~2958~ 12363 wherein R, Rl, X and a are the same as defined above.
; Preferably R4 represents a silyl group. Illustrative radicals represented by Q above include hydrogen, phenyl, alkyl radicals having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl and the like, as well as ~ster radicals of the formula Il~
-C-o-R5 wherein R5 represents an alkyl radical having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, and the like. Preferably Q is hydrogen. In the more preferred aminoorganosilicon acylamino compounds of this invention a is preferably 0.
. For instance, the aminoorganosilicon acylamino compounds can be prepared by following simple processing procedures involving the use of Michael addition products as the starting materials. For example, aminosilane compounds of the formula Rl R3 la (II) X3-a-Si-R-N-(R2N)tH -wherein X, R, Rl, R2, R3, a and t are the same as defined i above can be reacted with an olefinic carboxylate ester by ` the Michael addition method to form the corresponding . . . . . .
~ 1~29~8~ 12~
amino-carhoxyl~c aci.d ester of the silane and carboxylate ~ materials employed as seen b~ tQe foll~ing illustration:
.' 11 .
C2H50CCX=CH2 + H2NCC~2~35iCOC2H5~3 _ >
O
2H50Ccx2c~2N~CCH2~3Sicoc2x5~3 .~ Intermediate I
T~e amino-carboxylic acid ester-silane inter-mediate product so formed can t~en be subse~uently amidated ,' 10 with eîther Cl~ a primary amino silicon compound of Formula ':. CII~ ab,ove, C2~ a primar~ organoamine, or C3~ a primary organic polyamine to produce the aminoorganosilicon acylamino com~ounds depicted by Formula CI~ above as seen by the following illustrations (1) Intermediate I + ~2~CcH2)3sicoc2Hs~3 >
' ~ O ~:
~ccH2c~l2~ ccH2~3si~oc2H5)3]2 ~ C2H5H
.~ (2) Intermediate I + ClgH37i~H2 - - ~
O
.. , ~I
. 20 ClgH37NHCCH2CH2NH(CH2)3Si(Oc2Hs)3 + C2H5H
.
(3) Inter,mediate I + H2NC2H4NH2 o ,.,. H2NC2H4~C(CH2)2~1HCcH2)3si(oc2H5)3 + C2H5H ::
,.. ~ ~ "' , The amino-carboxylic acid ester containing silane ~':
c~mpounds employable as t~e starting materials for such ; types o.f processes as depicted above and/or the Michael `;~ addition method for their preparation are well known in ', the art as seen ror example by U.S. Patent 2,929,829 and '~ ma~y be illustrated by the following formula :
' ` ~:., .: 13.
~,~ - , ..... .. .
9 S ~ ~ 123~3 ~a R3 R3 ~ Q O
CIII~ X3_a-bi-R-N~R2N~ tCllC~COR6 wherein R, Rl, R~, R3, Q, X, a and` t are t~e same as defined a~ove and R6 is a ~onovalent ~ydrocar~on radical, prefera~l~ an al~l radical having l to 4 car~on atoms such. as met~Yl, et~.yl, propyl, ~utyl, and t~e like.
~llustrative examples of olefinic carboxylate : compounds which mav ~e employed in such a Michael addition process include thos~of the formula CIV? QCCH~ = CCQ2COOR6 wh~rein O and R6 are t~e same as defined above such as, CH2=CHCOOC2Xs; CH2=CHCOOCH3; CH2=CCCX3~COOCH3;
CH3CH=CHCOOC2Hs; C6HsCH=ChCOOC2Hs; CE300CCH=CXCOOCH3;
and the like.
Illustrative aminosilanes that can ~e employed in such a Michael addition process include tho~of Formula (II~ a~ove such as ;, CCH30) 3siCH2NH2 (C2H50) 3si(cH2) 3P~H2 (CH30)3siCcH2)3L~H2 (cH3o~3si(cH2)3NHcH
CC3x7o?3si(cx2)3~H2 ~`
CCH30C2H402 3sicCH2~ 3NH2 CC2Hso22cx3siccH2~3Na2 (C2HsO~2c2HssiCcH2~3NH2 CC2H50~. 3s i CH2 C~2NH2 CC2H50~ 3sicH2cH2cH ccH3 ~ ~2 CC2HsO~3SiCCH2)4~H2 CE30~3SiCCH2~3NHCCH2~2NH2 (c4H9o)2{cH3)siccx2~3~Hc~3 (CH30)3Si(CH2)3~ C2H4)2NH2 14.
5 8 ~ 12363 (CH30~3Si(CH2)3(NHC2H4)3NH2 (c2H5o)3si(c~2)3(NHc~H4)4NH2 (C2HS0)2C~3si(cH2)4NE~2 (CH30)(CH3)2Si(cH2)4 (CH30)3Si(CH2~3NHc4H9 (C2H50)3Si(CH2)3~HCH3 (c~H5o)3sicH2cH(cH3)NH2 and the like.
The processing conditions of said Michael addition are well known and taught e.g. in U.S.P. 2,929,829 and in this instance, merely involve forming a mixture of about 1 mole of the aminosilicon compound and about one mola of the olefinic carboxylate compound and maintaining the mixture at a te~perature, preferably about room temper-ature, until the aminosilicon compound has added to the double bond of the olefinic carboxate thereby producing the desired Michael addition product.
. As pointed out above the aminoorganosilicon used acylamino compounds/in this invention as shown by Fonmula (I) above can be produced by amidating an amino-carboxylic acid ester containing silane of Formula (III) above with either tl) a primary aminosilane compound of Formula (II) above; ~2) a primary organic amine or (3) a primary organic polyamine.
;. Illustrative primary aminosilane reactants 'L include those of the formula Rl R3 (V) X3_aSi-R(NR2)tMH2 :
~958~ 12363 wherein R, Rl, R2, R3, X, a and t are the same as defined above such as (~30) 3siCH 2NH2 (C2H50)3Si(~2)3NH2 .- (CH30)3Si(~l2)3NH2 (CH30)3Si(C~l2)4NH2 .` (C3H70)3Si(~ H2)3NH2 (CH30C2H40)3si(cH2)3NH2 (C2H50)2CH3Si(CH2)3NH2 ,~ 10 (C2H50)2C2H5Si(Cx2)3NH2 (C2H50)3SiCH2CH2cH(cH3)NH2 (C2X50)3Si(CH2)4NH2 ( CH30) 3Si ( CH2 ) 3~H ( CH2 ) 2NH2 '~
(C:H30)3Si(CH2)3(N~C2H4)2NH2 ' (CH30)3Si(CH2)3(NHC2H4)3N~[2 (C2H50)3Si(CH2)3(NHC2H4)4NH2 (C2HsO)2(CH3)Si(cH2)4NH2 (CH30)~CH3)2Si(cH2)4NH2 ., (C2H50)3SiCH2CH(C~3)NH2 . 20 and the like.
.
,!` Illustrative primary organic amines include those of the formula (VI) R7NH2 wherein R7 :is a monovalent hydrocarbon radical having from .~ 1 to 20 carbon atoms,such as methylamine, ethylamine, propylamine, octylamine, octadecy~amine, eicosylamine, ; phenylamine 7 and the like.
. -16-. . . . .
~ 5~33L 12363 Illustra~ive prim2ry organic polyamines include those of the formula : (VII) R3 . R4(N-R2~b~H2 wherein R2, R3, R4 and R4are the same as defined above, and b has a value of 1 to 4, such as--H2NCH2 CH2NH.2 H~NHcH2cH2]2NH2 H~NHCH2CH2]3NH~
H~NHCH2CH2 ] 4NH2 H~NHcH2cH2cH2]2NH2 H(CH3)NCH2cH2NH2 , . H(C2H~)NCH2cH2NH2 (C4Hg)NC~2CH2CH2NH2 H(C6Hs)NCH2cH2NH2 .,'!, (c~3)2NcH2cH2NH2 (C2H5) 2NCH2CH2NH2 .~ 20 H2NCH2CH2NHCH2CH2cH2~H2 and the like.
Of course, it is obvious that the particularchoice of amidation processes will merely depend upon which type of silane product is desired and that all three of the .~ : above depicted amidation processes can be carried out merely by forming a mixture of a carboalkoxyalkylamino- :
organosilane such as shown in Fon~ula (III) above with any of the amino compounds shown in Formulas (V), (VI)or ~:
(VII) above and maintaining the mixture at a temperature -17- ::
~29581 2363 at which the carboalkoxy group and primary amino group acylamino react to produce the desired aminoorganosilico~ compound.
The relative amounts of the two reactants used as the starting materials for said above amidation processes is not n~rrowly critical. For example, from o~e to ten chemical equivalents of primary amine starting materials of Formulas (V), (VI) or (VII) can be employed for each mole o the carboalkoxyalkylaminosilane of Formula :~ .
III above. However, an excess of such primary amine reactants is not desirable unless the unreacted excess can be readily removed from the reaction mixture or does not interfere with the intended use of the desired silane condensation product. In general, however, when the amino starting material is an aminosilane of Formula (V) above or a primary amine of Formula (VI) abovP or a primary polyamine of Formula ~VII) above that contains only one ; primary amino group it is preferred that the car~oalkoxy- "
alkylaminoorganosilane startir.g material be reacted with :~ a stoichiometric amount (1 mole to 1 mole) of said amino starting materials. On the other hand, when the amino starting material is a primary polyamine of Formula (VII) above that contains two primary ~nino groups it is essential to employ a stoichiometric excess of said polyamine in order to avoid producing bis-silylated compounds containing more than a single acyl~mino group.
Moreover, while it is preferred to prepare the amino-~; organosilicon acylamino compounds used in this invention by .
~ ~Z~S~l 12363 t first forming the amino carboxylic acid ester containing silane intermediate of Formula (III) above and then reac-ting said intermediate with the primary amino starting material it is to be understood that, if desired the bis ` used silylated compounds/in this invention can aLso be prepared in a single step for example, by reacting an olefinic com-pound of Formula (IV) above that contains only one carbo-alkoxy group with a primary aminosilane of Formula (V) above using a mole ratio of 0.5 moles of the carboxylate compound to 1 mole of the ~m;nosilane. It is generally preferred to employ an olefinic carboxylate starting material which contains the same type of alkoxy group as `: the alkoxy radicals of the aminosilane starting material since when different alkoxy groups are involved (e.g. in the reaction of methyl acrylate and a triethoxy containing silane starting material the process can lead to a mixed methoxy-ethoxy silane adduct intermediate andlor an acyl-amino containing mixed methoxy-ethoxy silane product.
The above amidation processes may be carried out over a wide range of temperatures such as from 0C to ; 200C; however, it is generally preferred to employ a temperature in the range of from about 25C to about 150C.
The by-product alcohol may be removed by any conventional method such as by distillation and pressures other than atmospheric pressure may be used to aid in the removal of the alcohol if desired. Of course, it is to be under-stood that the aminoorganosilicon acylamino compounds for this invention can be employed in their crude product form or purified if desired after removal of the alcohol by any : ~LlZ;9581 12~63 a conventional method such as further distillation. Moreover, it is often desirable to employ a catalyst to accelerate th~
condensation reaction (amidation) between the carboalkoxy group and primary amino group of the star~ing materials.
Illustrative catalysts which may be employed for this purpose are the tin catalysts described in U.S. Patent.
2,890,208 as well as other metal catalysts such as those described in U.S. Patent 3,169,945.
: 10 Accordingly, illustrative aminoorganosilicon used acylamino compounds/i~ this invention i~clude such compounds as :' O
1~ .
~ccH2cH2~NH(cH2)3si(oc2H5)3)2 O
;' ' (CH3o)3si(cH2)3NH(cH2)2NHccH2cH2N~(cH2)3si(oc2H5~3 , ~, :~ O
i~ 20 NH2cH2~H2NHccH2cH2NH(cH2)3si(oc2H5)3 O
Jl .~ C18H37NHccH2cH2NH(cH2)3si(oc2Hs)3 ': , O
2( 2)2 (cH2)2NHcc~ CH2NH(CH2)3Si(0C2Hs)3 CH ~NHcc(cH3)Hc~2~H(cH2)4si(oc2H5)2cH3 ' ~t EC~H2cH2~-ENH(cH2)4si(cH3)2ocH3]2 fC~H2CH2~{N(C4Hg) (C~I2)3si(ocH3)3]2 -2~-~Z~58~ 12363 .. `
fC(CH3)HCH2~N(CH3) (CH2)3Si(OC2H5)3]2 . O
,:
CCH2C(CH3)H~NH(CX2)3Si(OCH3)3]2 :. O
. 11 '. fccH2c(~ 6H5)H~fNH(cH2)3si(oc2H~)3]
, 10 0 ~CCH2C(COOCH3)H~NX(CX2)3Si(OCH3)3]
: O
. fccH2cH2~NHc(cH3)HcH2si(oc2H5)3~2 O
Eccx2cx2~NHcH2si(ocH3)3]2 ~; O
` 20 ll CCX2CX2~NH(CX2)3Si(OCX3)3~2 O
.,, 1~ .
fCCH2CH2~ ENX(CX2)2NH(CH2)3Si(OCE3)3]2 ~'. O
, Cl8H37NHCCH2CH2NH(C~I2)22~H(CH2)3Si(OC~3)3 O
. 1~ .
!,.i` NH2CH2CH2NHCCH2CH2NH(CX2)2NH(CH2)3Si(ocH3~3 - ~
;
~' ' (CH30)3si(CH2)3~1HCCH2CH2NH(CH2)2NH(CH2)3Si(O~H3~3 : :"
."' ' ~,`
`.;` 11 i`' ~ccH2cH2~-ENH(cH2)2NH(cH2)3si(oc2H5)3]2 ~ .
and the like. The most preferred aminoorganosilicon com~
pounds used in this invention are the bis-silyl compounds.
.
~Z~58~
1~,363 The hydroxyl-containing organic polymer/amino-organosilicon acylamino compositions of this invention are uniformly blended solutions containing about S to about 50 parts by weight, and more preferably about 10 to about 40 parts by weight of the aminoorganosilicon acylamino compound per 100 parts by weight of the organic polymer, and can be prepared by merely mechanically mixing said ingredients together along with other various conventional components that may be included if desired in the room temperature curable compositions. The particular design of mixing equipment and the method and order of the various components is not critical, although it is preferred to add the aminoorganosilicon acylamino compound to a solution of the organic polymer and additional ingredients when employed. In addition since the compositions of this invention are reactive in the presence of water the mixing of the various components should be conducted under substantially anhydrous type conditions, such as closing the equipment so that the ambient atmosphere can be controlled. Moreover, since the compositions of this invention are mildly basic in nature, it is desirable to exclude or control their conta~t with any acidic or potentially acidic environmental components such as S02, C0~, or HCl which may be in the atmosphere. It may also be desirable to dry or dehydrate any additional components which are addled.
12,363 As indicated above the compositions of this invention may also contain additional components so long as they and/or their amounts would not destroy the basic concept of this invention such as alkyl silicates to increase the solids content of the cured composition without increasing the viscosity o the curable composi-tion, fillers, pigments, dyestuffs, diluents, solvents, dispersing agents, dessicants such as molecular sieves, odorants, plasticizers, softeners, elastomeric modifiers, thermal stabilizers, antioxidants, and the like. The particular choice and amount of such additives when employed will of course merely depend on the ultimate end use desired for the compositions of this invention.
The hydroxyl containing organic polymer/amino-organosilicon acylamino compositions o this invention have a wide variety of utility such as in the fields of coatings, laquers, paints, inks, dyes, tints, impregnations, adhesives, caulks, sealants and the likeO Said compositions `
are especiaLly useful as room temperature curable coating compositions which may be applied over a wide variety of substrates, such as metals, plastics, wood, cloth foam, glass, and the like, as well as over primers, by any conventional method such as by spraying, brushing, dipping, flow coating, and the like. Said compositions are particularly useful in all fields of use where cured (crosslinked) protective and/or decorative solvent resistant coatings are desired, such as in the fields of maintenance and marine coatings.
.. ~ . ,, - , . . ,: . . . . . .
~295~ 12,363 While not wishing to be bound by any particular theory of mechanism involved, lt is believed that the aminoorganosilicon acylamino compound reacts with the polymer via transesterification followed by hydrolysis of ~` the silane portion upon exposure to the ambient moisture in the air which then cures (cxosslinks) into a solid film.
The most preferred coating composition of this invention are those consisting essentially of a hydroxy-alkyl acrylate modified vinyl chloride polymer as defined above and an aminoorganosilicon acvlamino compound or mixtures thereof as defined above, said composition containing about 5 to 50 and more preferably about 10 to 40 parts by weight of said silicon compound per L00 parts by weight of said polymer. Said preferred compo-sition may also and more often preferably contains the following additional additives such as an organic solvent in an amount sufficient to dissolve the polymer employed;
about 70 to 100 parts by weight of a pigment per 100 parts by weight of said polymer; 0 to about 70 parts by weight of a filler material per 100 parts by weight of said pol~mer; 0 to about 25 parts by weight of an alkyl sili-cate per 100 parts by weight of said polymer; ~nd based on the total weight of the composition, 0 to about 1 per cent by weight of a dispersing agent for the pigment and 0 to about 3 per cent by weight of a dessicant. The most preferred hydroxyalkyl acrylate modified vinyl ~2~58~ 12,363 ; chloride polymers and aminoorganosilicon acylamino compounds useful ln this invention have already been defined above.
In general a typical coating c:omposition will consist of about lO to 35 per cent by weight of said hydro~yalkyl acrylate m~`dified vinyl chloride polymer based on the total weight of the romposition. Of courqe, it is obviou~
that the particular additives employed are not critical and any suitable sol~ent, pigment, filler, alkyl silicate, dispersing agent and dessicant can be employed. In general, the preferred solvents are methylisobu-tyl ketone,-xylene and mixtures thereof, while the preferred pigment is titanium dioxide and the preferred des3icant is molecular sieves.
.. . .
~L~L295~
12,363 The alkyl silicates are also well known in the art and include unhydrolyzed alkyl and alkoxyalkyl sili-cates and alkyl and alkoxyalkyl silicates hydrolyzed up to about 85 per cent by weight. Alkyl silicates are produced by the reaction of silicon tetrachloride and alcohols and alkoxy alcohols, generally in a reactor equipped with a stirrer, condenser and vat scrubber. The hydrogen chloride by-product is removed by reflux which may be carried out at reduced or atmospheric pressure.
Through this process, the most common products TEOS
ttetraethyl orthosilicate) and Cellosolve (Trademark of the Union Carbide Corporation for monoalkyl ethers of ethylene glycol) silicate are made. Subsequently, these products may be partially hydrolyzed by the addition of water and an acid catalyst. The amount of water added determines the degree of hydrolysis in the ~inal product.
Commercially available products derived from ethanol include the unhydrolyzed TEOS, Condensed Ethyl Silicate ;
(about 7 per cent hydrolysis), Ethyl Silicate 40 (40 per cent hydrolysis con~aining 40% SiO2), and Ethyl Silicate P-18, having an 80 to 85 per cent hydrolysis level.
The following examples illustrate the present invention and are not to be regarded as limitative. All ,,; . ~ , , ~. :
5 8 ~
parts and percentages are by weight unless otherwise specified.
For the sake of brevity in the Examples, the designations in the first column of Table ]: will be used i~ lieu of the complete description given in the second column.
TABLE I
Designation COmPOSitiOn Polymer A A uniformly rand~m hydroxyl-functional terpolymer of 8070 vinyl chloride mer units, 5% vinyl acetate mer units and 15% hydroxypropyl acrylate mer units. Inherent viscosity is 0.3.
Silane A The crude silane reaction produce of Example A below having the formula ~CCH2CH2~NH(CH2)3Si~3]2 wherein each X is individually selected from the class consisting of methoxy and ethoxy radicals Silane B The crude silane reaction product of Example B below having the formula O ,:
Il :
~CCH2CH2 ~ ~NH (CH2 )2NH (CH2 ) 3Si tocH3 ) 3]
Silane C The crude silane reaction product of Example C below having the formula O
~CcH2cH2~H(cH2)3si(oc~I3)3]
Silane D A silane having the formula ,0, [(c2H5o)3si(cH2)3NH(cH2)2cNHcH23-2 Silane E A silane having the formula ~ (CH30) 3Si (CH2 )3NH(CH2 )2CNHCH2 ~2 Nuosperse~ 657 A dispersing agent supplied by :
Tenneco, Inc.
:: :
- ~Z958~ 12363 Example _ About 276.3 grams (1.25 moles) of gamma-aminopropyltriethoxysilane was added to a 500 ml., 3 necked flask equipped with a mechanical stirrer, heating mantle, addition funnel, thermometer and distillation head and receiver protected by a nitrogen by-pass. About 53.8 grams (0.62 moles) of methyl acrylate was then rapidly added via a funnel with stirring and cooling at such a rate that the contents of the flask were maintained below 25C. After addition, the contents of the flask were stirred for about 3 hours at room temperature and then about 0.66 grams (0.2 weight percent~
of dibutyl tin oxide added as catalyst and the reaction mixture heated to about 135C. to 150C with the appearance of refluxing alcohol (methanol and ethanol) in the distilla-tion head. About 16.2 grams (theory 19.8 grams, assuming all the distillate to be methanol) of said alcohol mixture was removed and collected over 2.5 hours to yield about 307.7 grams ~theory 310 grams) of the crude mixed methoxy-ethoxy silane reaction product.
O
X3Si(CH2)3~(~2)2CNH(CH2)3six3 wherein each X is individually selected from the class consisting of methoxy and ethoxy radicals. An amine analysis of said silane product showed 2.01 moles N/kg.
(theory 2.02 moles titratable N/kg.). Gas chromatographic analysis of the elutable materials of said silane product showed it to consist of about 11.39 weight percent of ~ , 9 S 8 1 123~3 alcohol (methanol and ethanol), about 7.25 weight percent of mixed methoxy-ethoxy si;ane X3Si(CH2)3NH2 wherein X is the same as defi.ned above, about 6.27 weight percent of the mixed methoxy-ethoxy silane Michael adduct intermediate X3Si(CH2)3~HCH2CH2coocH3 wherein X is the same as defined above, and about 71.43 weight percent of the acylamino containing n~xed methoxy-ethoxy silane X3Si(CH2)3NH(CH2)2CNH(CH2)3SiX3 wherein X is the same as defined above, while the remainder of said product did not elute.
Example B
About 895 grams (5.0 moles) of ga~ma-amino-propyltrimethoxysilane and about 215.2 grams (2.5 moles) of methyl acrylate were allowed to react, while stirring at room temperature, in a two liter, 3 necked flask having the same experimental set-up as described in Example A.
After the methyl acrylate was consumed, the reaction mixture was heated to 135C at 100-160 mmHg. over 4 hours , .
~lZ~S~
and about 27.3 grams of methanol collected, The reaction mixture was cooled to room temperature and about 2.22 grams (0.2 weight percent) of ~butyl tin oxide catalyst added. The reaction mixture w~s then reheated to 135C at 80 ~Hg. for two hours and an additional 62.9 grams of methanol collected (total methanol collected = 90.2 grams, theory 80 grams) ~o yield about 1017.7 grams (theory 1030 grams) of the crude silane reaction product (CH3)3Si(cH2)3NH(cH2)2cNH(cH2)3si(ocH3)3 An amine analysis of said silane product showed 2.7 moles N/kg. (theory 2.42 moles titratable N/kg.).
Gas chromatographic analysis of the elutable materials of said silane product showed 13.5 weight percent methanol, 11.0 weight percent of gamma-aminopropyltrimethoxysilane, about 16.0 weight percent of the Michael addition intenmediate (CH30)3Si(CH2)3NH(CH2)COOCH3 and a weight percent of the acylamino containing trimethoxysilane O
(CH30)3Si(CH2)3NH(CH2)2CNH(CH2)3Si(OCH3)3 while the remainder of the product did not elute.
"
~9~ 12363 .. . .
Following the same proeedure as described in Example A, about 151.9 grams (0.68 moles) of (CH30)3-Si(CH2)3NH(CH2)~NH2 with an amine analysis of 8.82 moles N/kg. (theory 9.0 moles N/kg) distilled from commercial grade N-bet~-(aminoethyl)-gamma-aminopropyltrimethoxy-silane was allowed to react while stirring and cooling to maintain the temperature at about room temperature with about 28.4 grams (0.33 moles of methyl acrylate).
After one hour amine analysis of the reaction mixture was about 7.27 moles N/kg. (theory 6.49 moles titratable N/kg.). Nuclear magnetic resonance analysis indicated total disappearance o~ acxylate protons, but the retention of the carboxymethoxy methyl group protons while the concentration of -NH-protons and the remainder of the spectrum was consistent with the ~ichael addition adduct structure`.
(CH30~3Si(CH2)3NH(CH2)2NH~CH2)~2COOCH3 ~' The reaction mixture was then heated to 150C for 4 hours, distilling 6~0 grams of methanol. A nuclear magnetic resonance analysis at this point of the experiment ;
indicated greater than 90% methanol formation (or less than 10% carbomethoxy methyl group remaining). The distillation was completed under vacuum producing an additional 6.2 grams of methanol (tota methanol 12.2 grams, theory 10.6 grams) and yielding about 159.7 grams (theory 164.3 grams) of the crude silane reaction product ~ ~ Z ~ 363 (cH3o)3s~ 2)3~ 2)2l~H(cx2)2cNH~(cH2)2NH(cH2)3si(ocH3)3 An amine analysis of said silane product showed 5.89 moles N/kg. (theory 6.02 moles titratable N/kg.). Gas chromatographic analysis of the elutable materials of said silane product showed about 1.0 weight percent methanol, about 9.9 weight percent (CH30)3si(CH2)3NH(CH2)2-NH2, about 4.6 weight percent of the Michael addition intermediate (~H30)3Si(CH2)3~(CH2)2L~H(CH2)2COOCH3, while the remainder of said crude silane product did not elute.
Nuclear magnetic resonance analysis of the crude silane reaction product confirmed the above silane product structure.
EX~MPLES 1-5 A series of hydroxyl containing organic polymer-aminoorganosilicon acJlamino coating compositions were prepared having the following total formulation Compound Parts by Weight Polymer A 25.45 Titanium Dioxide 19.09 Methylisobutyl ~etone27.57 Xylene 27.57 ~uosperse 657 0.32 Molecular Sieves 4A 0.5 Silane* Varied*
*The particular Silane employed as well as the parts by weight of said Silane in the total formulation are given in Table I below.
Each coating composition was prepared by dissolving Polymer A in a solvent blend (50/50 wt. %) of methylisobutyl ketone and xylene followed by the addition of the dispersing agent and titanium dioxide pigment (the molecular sieves ~ 363 3L~Z'9~8~ o being added with said pigment) with stirring and the mixture ground ir. a pebble mill overnight. The silane compound was then added with stirring until a unifor~
coating composition was obtained. Each coating composition was then thinned to a No. 4 Ford cup viscosity of 20-25 seconds by the addition of a 50/50 weight percent solvent blend of methylisobutyl ketone and xylene. Each coating composition so prep~red was then applied by a draw down blade to sand blasted steel panels to give a coating thickness of about 2 mils and the coatings on said panels cured by allowing them to air dry at room temperature.
The solvent resistance of each coating on said panels after having been air dried at room temperature for various ~eriods of time was then measured by subjecting each air dried coating to double MEK rubs and the results of this test are reported in Table I below. Said test involves saturating a gauze cloth with methylethylketone and rubbing the saturated cloth back and forth (or up and down) over the air dried coating until the metal surface of the panel is exposed. For example, a numerical double ~K rub rating of five means that the metal surface of the ;
panel was exposed after the methylethylketone saturated cloth was rubbed back and forth (2 strokes) over the coat-ing a total of five times. Thus the higher the numerical double ~K rub rating obtained for a given coating the more solvent resistant the coating is.
~2~5~ 12363 TABLE I
Silane Ex. (Parts by ~ -Double MEK Rubs -~
No Silane Wt.)24 hours 48 hours ~ 10 Days 18 Day~
1 A 5.09 5 - 11 - 14 2 B 5.09 100+ - 100+ - 100+
3 C 5.09 ~00+
~z95~ 12363 methyl glucoside; and other such polyhydric ccmpounds consisting of carbon, hydrogen and oxygen and having usually not more than about 15 carbon atoms per molecule. Illustra-tive alkylene oxides include ethylene oxide, propylene oxide, butylene oxide as well as various mixtures of such oxides. Also included among the polyether polyol polymers useful herein are poly(hydroxyethers) derived from diphenols and epichlorohydrin, e.g. phenvxy resins, as well as those polymers commonly referred to in the art as polymer/poly-ether polyols which may be produced by polymerizing one ormore ethylenically unsaturated monomers dissolved or dispersed in any of the above described alkylene oxide adduct polyols. Illustrative of such unsaturated monomers which may be employed individually or in combination include - ethylene, propylene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene, butadiene, and the like.
~ c) Polyhydroxy containing ac~ylic polymers such as the copolymers and terpolymers of hydroxyalkyl acrylates having 2 to 4 carbon atoms in the alkyl segments and alkyl acrylates andtor alkyl methacrylates having 1 to 6 carbon atoms in the aLkyl segments.
(d) Polyvinyl alcohol polymers such as the hydrolyzed or partially hydrolyzed polymers derived from the homopolymers of vinyl esters of saturated fatty acids of 1-6 carbon atoms or the copolymers of said vinyl esters and one or more ethylenically unsaturated monomers such as 6.
- , ... ..
i.. ; , - ~295~1 123~3 . ~
ethylene, propylene, butylene, acrylonitrile, methacrylo-~- ni~rile, vinyl chloride, vinylidene chlo~ide, styrene, alpha-methylstyrene, butadiene, and the like.
(e) Polyhydroxy containinO polyvinyl acetal polymers such as polyvinylbutyral resins and the like.
(f) Polyester polyol polymers such as the reaction products of polyfuncti.onal organic carboxylic ~` acids and polyhydric alcohols, which reaction products contain at least tWQ hydroxyl groups (as alcoholic OH) per molecule, and cyclic ester polymers containing at least two hydroxyl groups per molecule prepared from epsilon capro-lactone or other lactones and the copolymers of such lactones with polyhydric alcohols.
Typical of the polyfunctional organic carboxylic ; acids that can be employed in producing polyester polyols useful in this invention are: dicarboxylic aliphatic acids such as succinic, adipic, sebacic, azelaic, glutaric, pimelic, malonic and suberic acids; and dicarboxylic aromatic acids such as phthalic acid, terephthalic acid, isophthalic acid and the like. Other polycarboxylic acids that can be employed are the "dimer acids" such as the dimer of linoleic acid. Hydroxyl-containing monocarboxylic acids (such as ricinoleic acid) can also be used. Alternatively, the a~hydrides of any of these various acids can be employed in producing the polyester polyols.
The polyhydric alcohols (organic polyols) that can be employed in producing the polyester polyol starting 7.
~ 1 Z 9 5 8 1 12363 material useful in this invention include the monomeric polyhydric alcohols such as, for example, glycerol; 1,2,6~
hexanetriol; ethylene glycol; diethylene glycol; trimethylol propane; trimethyolethane; pentaerythritol; propylene glycol; 1,2-, 1,3- and 1,4-butylene glycols; 1,5-pentanediol;
sorbitol; and the like, including mixtures thereo.
Other polyhydric alcohols that can be employed in producing the polyester polyols useful in this invention are the polymeric polyhydric alcohols which include the linear and branched chain polyethers having a plurality of acycl~c ether oxygens and at least two alcoholic hydroxyl radicals.
Illustrative of such polyether polyols are the poly(oxyalkylene) polyols containing one or more chains of connected oxyalkylene radicals which are prepared by the reaction of one or more alkylene oxides with acyclic and alicyclic polyols. Examples of the poly(oxyalkylene) polyols include the poly(oxyethylene) glycols prepared by the addition of ethylene oxide to water, ethylene glycol or diethylene glycol; poly(oxypropylene) glycols prepared by the addition of propylene oxide to water, propylene glycol or dipropylene glycol; m~xed oxy-ethylene-oxypropylene polyglycols prepared in a similar manner utilizing a mixture of ethylene oxide or a sequential addition of ethylene oxide and propylene oxide; and the poly(oxybutylene) glycols and copolymers such as poly(oxy-ethylene-oxybutylene) glycols and poly(oxypropylene-oxy-butylene) glycols. Included in the term "poly(oxybutylene) glycols" are polymers of 1,2-butyleneoxide and 2,3-butyleneoxide.
8 . -i .. . ..
3L~ Z 9 S 8 ~ 12363 , Illustrative of further polyester polyols are the re-~ction products of any of the aforesaid polycarboxylic acids and the polyhydric alcohols prepared by the reaction of one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, with any of the following: glycerol; trimethylolpropane9 1,2,6-he~anetriol; pentaerythritol; sorbitol; glycosides such as methyl, ethyl, propyl, butyl cmd 2-ethyLhexyl arabinoside, xyloside, fructoside, glucoside, and rhammoside; sucrose;
mononuclear polyhydroxybenzenes such as resorcinoL, pyro-- gallol, phloroglucinol, hydroquinone, 4,6-di-tertiary-butylcatechol, and catechol; polynuclear hydroxybenæenes ("polynuclear" designating at least two benzene nuclei) such as the di-, tri- and tetraphenylol compounds in which two to four hydroxybenzene groups are attached either ~ directly by means of single bonds or through an aliphatic ; hydrocarbon radical containinO one to twelve carbon atoms, such compounds being typically illustrated by 2,2-bis(p-hydroxyphenyl)-propane, bis(p-hydroxyphenyl)-methane and the various diphenols and diphenol methanes disclosed in United States Patent ~os. 2,506,486 and 2,744,882, respectively. Another type of polyester polyol is that produced by reaction of a polycarboxylic acid and the polyether adducts formed by reaction of ethylene oxide, propylene oxide or butylene oxide with phenol-formaldehyde condensation products such as the novolaks.
` 1~2~581 12363 (g) Phenolic resin polymers such as the solid resoles and novolak resins disclosed in U.S. Patent 4,116,921 and British Patent 1,417,437. The phenol of the resin can be unsubstituted phenol or substituted such as c~esol, bi-phenol-A, para-substituted phenols and the like while for-maldehyde or a material that generates formaldehyde in situ is the aldehyde employed in making phenol resins. The preferred phenolic resins are resoles produced by reacting formaldehyde with bisphenol-A at elevated temperatures in the presence of a base-catalyst and having a neutralized pH
of about 3 to 8.
The preferred hydroxyl containing organic thermo-plastic polymer components of this invention are the hydro-xylalkyl acrylate modified vinyl chloride polymers described above having (a) from abou~ 50 to 85 weight percent vinyl chloride derived mer units; (b) from 0 to 10 weight percent mer units derived from a polymerizable monomer selected from the class consisting of alkyl esters of alpha, beta-ethyleni- `~
cally unsaturated carboxylic acids as described above and vinyl esters of saturated fatty acids as described above, the preferred polymerizable monomer being vinyl acetate, and (c) from 10 to 30 weight percent mer units derived from hydroxy-alkyl acrylate as described above, preferably hydroxypropyl acrylate. The most preferred polymer being a uniformly hydroxyl-functional random terpolymer of about 80 weight percent vinyl chloride mer units, about 5 weight percent vinyl acetate mer units and about 15 weight percent hydroxypropyl acrylate mer units. ~
:
.
~- `'' .
~z9~ 12363 , .
~ ith regard to the aminoorganosilicon acylamino compounds and m~xtures thereof of Formula I a~ove it is to be understood tXat each X, R, Rl, R2, R3, R4, a, t and x may ~e the same or different in any given silicon compound and mixtures thereof. ~oreover, îllustrat;ve radicals represented by X above inclucle alkoxy radicals ~aving 1 ~o 6 carDon atoms, such as methoxy, ethoxy, propoxy, 2-methoxyethoxy, isopropoxy, Qexyloxy and the like, the pre~erred alkoxy radîcal being methoxy. Illustrative divalent alkylene radicals represented ~y R a~ove include - methylene, ethylene, propylene, isopropylene, butylene and the like, the preferred divalent alkylene groups ~eing eth~lene C-C2H4-~ and propylene C-C3H6-~. Illustrative radicals represented ~y Rl above include alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl and the ~.
like. Illustrative divalent alkylene radicals represented by R2 above include ethylene, ~ropylene, isopropylene, butylene, and the lîke, the preferred divalent alkylene groups being ethylene and propylene. Illustrative radicals represented ~y R3 above include hydrogen, phenyl and alkyl radicals having from 1 to 20 carbon atoms suc~ as methyl, ethvl, propyl, octyl, octadecyl, eicosyl and the like.
Preferably R3 is hydrogen. Illustrative radicals repre-- sented by R4 above include hydrogen, phenyl, alkyl radicals having from l to 20 carbon atoms such as methvl, ethyl, propyl, octyl, octadecyl, eicosyl, and the like as well as silyl groups of the formula '' Ra -R-Si.-X3_a 1 1 . :
- ~2958~ 12363 wherein R, Rl, X and a are the same as defined above.
; Preferably R4 represents a silyl group. Illustrative radicals represented by Q above include hydrogen, phenyl, alkyl radicals having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl and the like, as well as ~ster radicals of the formula Il~
-C-o-R5 wherein R5 represents an alkyl radical having from 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, and the like. Preferably Q is hydrogen. In the more preferred aminoorganosilicon acylamino compounds of this invention a is preferably 0.
. For instance, the aminoorganosilicon acylamino compounds can be prepared by following simple processing procedures involving the use of Michael addition products as the starting materials. For example, aminosilane compounds of the formula Rl R3 la (II) X3-a-Si-R-N-(R2N)tH -wherein X, R, Rl, R2, R3, a and t are the same as defined i above can be reacted with an olefinic carboxylate ester by ` the Michael addition method to form the corresponding . . . . . .
~ 1~29~8~ 12~
amino-carhoxyl~c aci.d ester of the silane and carboxylate ~ materials employed as seen b~ tQe foll~ing illustration:
.' 11 .
C2H50CCX=CH2 + H2NCC~2~35iCOC2H5~3 _ >
O
2H50Ccx2c~2N~CCH2~3Sicoc2x5~3 .~ Intermediate I
T~e amino-carboxylic acid ester-silane inter-mediate product so formed can t~en be subse~uently amidated ,' 10 with eîther Cl~ a primary amino silicon compound of Formula ':. CII~ ab,ove, C2~ a primar~ organoamine, or C3~ a primary organic polyamine to produce the aminoorganosilicon acylamino com~ounds depicted by Formula CI~ above as seen by the following illustrations (1) Intermediate I + ~2~CcH2)3sicoc2Hs~3 >
' ~ O ~:
~ccH2c~l2~ ccH2~3si~oc2H5)3]2 ~ C2H5H
.~ (2) Intermediate I + ClgH37i~H2 - - ~
O
.. , ~I
. 20 ClgH37NHCCH2CH2NH(CH2)3Si(Oc2Hs)3 + C2H5H
.
(3) Inter,mediate I + H2NC2H4NH2 o ,.,. H2NC2H4~C(CH2)2~1HCcH2)3si(oc2H5)3 + C2H5H ::
,.. ~ ~ "' , The amino-carboxylic acid ester containing silane ~':
c~mpounds employable as t~e starting materials for such ; types o.f processes as depicted above and/or the Michael `;~ addition method for their preparation are well known in ', the art as seen ror example by U.S. Patent 2,929,829 and '~ ma~y be illustrated by the following formula :
' ` ~:., .: 13.
~,~ - , ..... .. .
9 S ~ ~ 123~3 ~a R3 R3 ~ Q O
CIII~ X3_a-bi-R-N~R2N~ tCllC~COR6 wherein R, Rl, R~, R3, Q, X, a and` t are t~e same as defined a~ove and R6 is a ~onovalent ~ydrocar~on radical, prefera~l~ an al~l radical having l to 4 car~on atoms such. as met~Yl, et~.yl, propyl, ~utyl, and t~e like.
~llustrative examples of olefinic carboxylate : compounds which mav ~e employed in such a Michael addition process include thos~of the formula CIV? QCCH~ = CCQ2COOR6 wh~rein O and R6 are t~e same as defined above such as, CH2=CHCOOC2Xs; CH2=CHCOOCH3; CH2=CCCX3~COOCH3;
CH3CH=CHCOOC2Hs; C6HsCH=ChCOOC2Hs; CE300CCH=CXCOOCH3;
and the like.
Illustrative aminosilanes that can ~e employed in such a Michael addition process include tho~of Formula (II~ a~ove such as ;, CCH30) 3siCH2NH2 (C2H50) 3si(cH2) 3P~H2 (CH30)3siCcH2)3L~H2 (cH3o~3si(cH2)3NHcH
CC3x7o?3si(cx2)3~H2 ~`
CCH30C2H402 3sicCH2~ 3NH2 CC2Hso22cx3siccH2~3Na2 (C2HsO~2c2HssiCcH2~3NH2 CC2H50~. 3s i CH2 C~2NH2 CC2H50~ 3sicH2cH2cH ccH3 ~ ~2 CC2HsO~3SiCCH2)4~H2 CE30~3SiCCH2~3NHCCH2~2NH2 (c4H9o)2{cH3)siccx2~3~Hc~3 (CH30)3Si(CH2)3~ C2H4)2NH2 14.
5 8 ~ 12363 (CH30~3Si(CH2)3(NHC2H4)3NH2 (c2H5o)3si(c~2)3(NHc~H4)4NH2 (C2HS0)2C~3si(cH2)4NE~2 (CH30)(CH3)2Si(cH2)4 (CH30)3Si(CH2~3NHc4H9 (C2H50)3Si(CH2)3~HCH3 (c~H5o)3sicH2cH(cH3)NH2 and the like.
The processing conditions of said Michael addition are well known and taught e.g. in U.S.P. 2,929,829 and in this instance, merely involve forming a mixture of about 1 mole of the aminosilicon compound and about one mola of the olefinic carboxylate compound and maintaining the mixture at a te~perature, preferably about room temper-ature, until the aminosilicon compound has added to the double bond of the olefinic carboxate thereby producing the desired Michael addition product.
. As pointed out above the aminoorganosilicon used acylamino compounds/in this invention as shown by Fonmula (I) above can be produced by amidating an amino-carboxylic acid ester containing silane of Formula (III) above with either tl) a primary aminosilane compound of Formula (II) above; ~2) a primary organic amine or (3) a primary organic polyamine.
;. Illustrative primary aminosilane reactants 'L include those of the formula Rl R3 (V) X3_aSi-R(NR2)tMH2 :
~958~ 12363 wherein R, Rl, R2, R3, X, a and t are the same as defined above such as (~30) 3siCH 2NH2 (C2H50)3Si(~2)3NH2 .- (CH30)3Si(~l2)3NH2 (CH30)3Si(C~l2)4NH2 .` (C3H70)3Si(~ H2)3NH2 (CH30C2H40)3si(cH2)3NH2 (C2H50)2CH3Si(CH2)3NH2 ,~ 10 (C2H50)2C2H5Si(Cx2)3NH2 (C2H50)3SiCH2CH2cH(cH3)NH2 (C2X50)3Si(CH2)4NH2 ( CH30) 3Si ( CH2 ) 3~H ( CH2 ) 2NH2 '~
(C:H30)3Si(CH2)3(N~C2H4)2NH2 ' (CH30)3Si(CH2)3(NHC2H4)3N~[2 (C2H50)3Si(CH2)3(NHC2H4)4NH2 (C2HsO)2(CH3)Si(cH2)4NH2 (CH30)~CH3)2Si(cH2)4NH2 ., (C2H50)3SiCH2CH(C~3)NH2 . 20 and the like.
.
,!` Illustrative primary organic amines include those of the formula (VI) R7NH2 wherein R7 :is a monovalent hydrocarbon radical having from .~ 1 to 20 carbon atoms,such as methylamine, ethylamine, propylamine, octylamine, octadecy~amine, eicosylamine, ; phenylamine 7 and the like.
. -16-. . . . .
~ 5~33L 12363 Illustra~ive prim2ry organic polyamines include those of the formula : (VII) R3 . R4(N-R2~b~H2 wherein R2, R3, R4 and R4are the same as defined above, and b has a value of 1 to 4, such as--H2NCH2 CH2NH.2 H~NHcH2cH2]2NH2 H~NHCH2CH2]3NH~
H~NHCH2CH2 ] 4NH2 H~NHcH2cH2cH2]2NH2 H(CH3)NCH2cH2NH2 , . H(C2H~)NCH2cH2NH2 (C4Hg)NC~2CH2CH2NH2 H(C6Hs)NCH2cH2NH2 .,'!, (c~3)2NcH2cH2NH2 (C2H5) 2NCH2CH2NH2 .~ 20 H2NCH2CH2NHCH2CH2cH2~H2 and the like.
Of course, it is obvious that the particularchoice of amidation processes will merely depend upon which type of silane product is desired and that all three of the .~ : above depicted amidation processes can be carried out merely by forming a mixture of a carboalkoxyalkylamino- :
organosilane such as shown in Fon~ula (III) above with any of the amino compounds shown in Formulas (V), (VI)or ~:
(VII) above and maintaining the mixture at a temperature -17- ::
~29581 2363 at which the carboalkoxy group and primary amino group acylamino react to produce the desired aminoorganosilico~ compound.
The relative amounts of the two reactants used as the starting materials for said above amidation processes is not n~rrowly critical. For example, from o~e to ten chemical equivalents of primary amine starting materials of Formulas (V), (VI) or (VII) can be employed for each mole o the carboalkoxyalkylaminosilane of Formula :~ .
III above. However, an excess of such primary amine reactants is not desirable unless the unreacted excess can be readily removed from the reaction mixture or does not interfere with the intended use of the desired silane condensation product. In general, however, when the amino starting material is an aminosilane of Formula (V) above or a primary amine of Formula (VI) abovP or a primary polyamine of Formula ~VII) above that contains only one ; primary amino group it is preferred that the car~oalkoxy- "
alkylaminoorganosilane startir.g material be reacted with :~ a stoichiometric amount (1 mole to 1 mole) of said amino starting materials. On the other hand, when the amino starting material is a primary polyamine of Formula (VII) above that contains two primary ~nino groups it is essential to employ a stoichiometric excess of said polyamine in order to avoid producing bis-silylated compounds containing more than a single acyl~mino group.
Moreover, while it is preferred to prepare the amino-~; organosilicon acylamino compounds used in this invention by .
~ ~Z~S~l 12363 t first forming the amino carboxylic acid ester containing silane intermediate of Formula (III) above and then reac-ting said intermediate with the primary amino starting material it is to be understood that, if desired the bis ` used silylated compounds/in this invention can aLso be prepared in a single step for example, by reacting an olefinic com-pound of Formula (IV) above that contains only one carbo-alkoxy group with a primary aminosilane of Formula (V) above using a mole ratio of 0.5 moles of the carboxylate compound to 1 mole of the ~m;nosilane. It is generally preferred to employ an olefinic carboxylate starting material which contains the same type of alkoxy group as `: the alkoxy radicals of the aminosilane starting material since when different alkoxy groups are involved (e.g. in the reaction of methyl acrylate and a triethoxy containing silane starting material the process can lead to a mixed methoxy-ethoxy silane adduct intermediate andlor an acyl-amino containing mixed methoxy-ethoxy silane product.
The above amidation processes may be carried out over a wide range of temperatures such as from 0C to ; 200C; however, it is generally preferred to employ a temperature in the range of from about 25C to about 150C.
The by-product alcohol may be removed by any conventional method such as by distillation and pressures other than atmospheric pressure may be used to aid in the removal of the alcohol if desired. Of course, it is to be under-stood that the aminoorganosilicon acylamino compounds for this invention can be employed in their crude product form or purified if desired after removal of the alcohol by any : ~LlZ;9581 12~63 a conventional method such as further distillation. Moreover, it is often desirable to employ a catalyst to accelerate th~
condensation reaction (amidation) between the carboalkoxy group and primary amino group of the star~ing materials.
Illustrative catalysts which may be employed for this purpose are the tin catalysts described in U.S. Patent.
2,890,208 as well as other metal catalysts such as those described in U.S. Patent 3,169,945.
: 10 Accordingly, illustrative aminoorganosilicon used acylamino compounds/i~ this invention i~clude such compounds as :' O
1~ .
~ccH2cH2~NH(cH2)3si(oc2H5)3)2 O
;' ' (CH3o)3si(cH2)3NH(cH2)2NHccH2cH2N~(cH2)3si(oc2H5~3 , ~, :~ O
i~ 20 NH2cH2~H2NHccH2cH2NH(cH2)3si(oc2H5)3 O
Jl .~ C18H37NHccH2cH2NH(cH2)3si(oc2Hs)3 ': , O
2( 2)2 (cH2)2NHcc~ CH2NH(CH2)3Si(0C2Hs)3 CH ~NHcc(cH3)Hc~2~H(cH2)4si(oc2H5)2cH3 ' ~t EC~H2cH2~-ENH(cH2)4si(cH3)2ocH3]2 fC~H2CH2~{N(C4Hg) (C~I2)3si(ocH3)3]2 -2~-~Z~58~ 12363 .. `
fC(CH3)HCH2~N(CH3) (CH2)3Si(OC2H5)3]2 . O
,:
CCH2C(CH3)H~NH(CX2)3Si(OCH3)3]2 :. O
. 11 '. fccH2c(~ 6H5)H~fNH(cH2)3si(oc2H~)3]
, 10 0 ~CCH2C(COOCH3)H~NX(CX2)3Si(OCH3)3]
: O
. fccH2cH2~NHc(cH3)HcH2si(oc2H5)3~2 O
Eccx2cx2~NHcH2si(ocH3)3]2 ~; O
` 20 ll CCX2CX2~NH(CX2)3Si(OCX3)3~2 O
.,, 1~ .
fCCH2CH2~ ENX(CX2)2NH(CH2)3Si(OCE3)3]2 ~'. O
, Cl8H37NHCCH2CH2NH(C~I2)22~H(CH2)3Si(OC~3)3 O
. 1~ .
!,.i` NH2CH2CH2NHCCH2CH2NH(CX2)2NH(CH2)3Si(ocH3~3 - ~
;
~' ' (CH30)3si(CH2)3~1HCCH2CH2NH(CH2)2NH(CH2)3Si(O~H3~3 : :"
."' ' ~,`
`.;` 11 i`' ~ccH2cH2~-ENH(cH2)2NH(cH2)3si(oc2H5)3]2 ~ .
and the like. The most preferred aminoorganosilicon com~
pounds used in this invention are the bis-silyl compounds.
.
~Z~58~
1~,363 The hydroxyl-containing organic polymer/amino-organosilicon acylamino compositions of this invention are uniformly blended solutions containing about S to about 50 parts by weight, and more preferably about 10 to about 40 parts by weight of the aminoorganosilicon acylamino compound per 100 parts by weight of the organic polymer, and can be prepared by merely mechanically mixing said ingredients together along with other various conventional components that may be included if desired in the room temperature curable compositions. The particular design of mixing equipment and the method and order of the various components is not critical, although it is preferred to add the aminoorganosilicon acylamino compound to a solution of the organic polymer and additional ingredients when employed. In addition since the compositions of this invention are reactive in the presence of water the mixing of the various components should be conducted under substantially anhydrous type conditions, such as closing the equipment so that the ambient atmosphere can be controlled. Moreover, since the compositions of this invention are mildly basic in nature, it is desirable to exclude or control their conta~t with any acidic or potentially acidic environmental components such as S02, C0~, or HCl which may be in the atmosphere. It may also be desirable to dry or dehydrate any additional components which are addled.
12,363 As indicated above the compositions of this invention may also contain additional components so long as they and/or their amounts would not destroy the basic concept of this invention such as alkyl silicates to increase the solids content of the cured composition without increasing the viscosity o the curable composi-tion, fillers, pigments, dyestuffs, diluents, solvents, dispersing agents, dessicants such as molecular sieves, odorants, plasticizers, softeners, elastomeric modifiers, thermal stabilizers, antioxidants, and the like. The particular choice and amount of such additives when employed will of course merely depend on the ultimate end use desired for the compositions of this invention.
The hydroxyl containing organic polymer/amino-organosilicon acylamino compositions o this invention have a wide variety of utility such as in the fields of coatings, laquers, paints, inks, dyes, tints, impregnations, adhesives, caulks, sealants and the likeO Said compositions `
are especiaLly useful as room temperature curable coating compositions which may be applied over a wide variety of substrates, such as metals, plastics, wood, cloth foam, glass, and the like, as well as over primers, by any conventional method such as by spraying, brushing, dipping, flow coating, and the like. Said compositions are particularly useful in all fields of use where cured (crosslinked) protective and/or decorative solvent resistant coatings are desired, such as in the fields of maintenance and marine coatings.
.. ~ . ,, - , . . ,: . . . . . .
~295~ 12,363 While not wishing to be bound by any particular theory of mechanism involved, lt is believed that the aminoorganosilicon acylamino compound reacts with the polymer via transesterification followed by hydrolysis of ~` the silane portion upon exposure to the ambient moisture in the air which then cures (cxosslinks) into a solid film.
The most preferred coating composition of this invention are those consisting essentially of a hydroxy-alkyl acrylate modified vinyl chloride polymer as defined above and an aminoorganosilicon acvlamino compound or mixtures thereof as defined above, said composition containing about 5 to 50 and more preferably about 10 to 40 parts by weight of said silicon compound per L00 parts by weight of said polymer. Said preferred compo-sition may also and more often preferably contains the following additional additives such as an organic solvent in an amount sufficient to dissolve the polymer employed;
about 70 to 100 parts by weight of a pigment per 100 parts by weight of said polymer; 0 to about 70 parts by weight of a filler material per 100 parts by weight of said pol~mer; 0 to about 25 parts by weight of an alkyl sili-cate per 100 parts by weight of said polymer; ~nd based on the total weight of the composition, 0 to about 1 per cent by weight of a dispersing agent for the pigment and 0 to about 3 per cent by weight of a dessicant. The most preferred hydroxyalkyl acrylate modified vinyl ~2~58~ 12,363 ; chloride polymers and aminoorganosilicon acylamino compounds useful ln this invention have already been defined above.
In general a typical coating c:omposition will consist of about lO to 35 per cent by weight of said hydro~yalkyl acrylate m~`dified vinyl chloride polymer based on the total weight of the romposition. Of courqe, it is obviou~
that the particular additives employed are not critical and any suitable sol~ent, pigment, filler, alkyl silicate, dispersing agent and dessicant can be employed. In general, the preferred solvents are methylisobu-tyl ketone,-xylene and mixtures thereof, while the preferred pigment is titanium dioxide and the preferred des3icant is molecular sieves.
.. . .
~L~L295~
12,363 The alkyl silicates are also well known in the art and include unhydrolyzed alkyl and alkoxyalkyl sili-cates and alkyl and alkoxyalkyl silicates hydrolyzed up to about 85 per cent by weight. Alkyl silicates are produced by the reaction of silicon tetrachloride and alcohols and alkoxy alcohols, generally in a reactor equipped with a stirrer, condenser and vat scrubber. The hydrogen chloride by-product is removed by reflux which may be carried out at reduced or atmospheric pressure.
Through this process, the most common products TEOS
ttetraethyl orthosilicate) and Cellosolve (Trademark of the Union Carbide Corporation for monoalkyl ethers of ethylene glycol) silicate are made. Subsequently, these products may be partially hydrolyzed by the addition of water and an acid catalyst. The amount of water added determines the degree of hydrolysis in the ~inal product.
Commercially available products derived from ethanol include the unhydrolyzed TEOS, Condensed Ethyl Silicate ;
(about 7 per cent hydrolysis), Ethyl Silicate 40 (40 per cent hydrolysis con~aining 40% SiO2), and Ethyl Silicate P-18, having an 80 to 85 per cent hydrolysis level.
The following examples illustrate the present invention and are not to be regarded as limitative. All ,,; . ~ , , ~. :
5 8 ~
parts and percentages are by weight unless otherwise specified.
For the sake of brevity in the Examples, the designations in the first column of Table ]: will be used i~ lieu of the complete description given in the second column.
TABLE I
Designation COmPOSitiOn Polymer A A uniformly rand~m hydroxyl-functional terpolymer of 8070 vinyl chloride mer units, 5% vinyl acetate mer units and 15% hydroxypropyl acrylate mer units. Inherent viscosity is 0.3.
Silane A The crude silane reaction produce of Example A below having the formula ~CCH2CH2~NH(CH2)3Si~3]2 wherein each X is individually selected from the class consisting of methoxy and ethoxy radicals Silane B The crude silane reaction product of Example B below having the formula O ,:
Il :
~CCH2CH2 ~ ~NH (CH2 )2NH (CH2 ) 3Si tocH3 ) 3]
Silane C The crude silane reaction product of Example C below having the formula O
~CcH2cH2~H(cH2)3si(oc~I3)3]
Silane D A silane having the formula ,0, [(c2H5o)3si(cH2)3NH(cH2)2cNHcH23-2 Silane E A silane having the formula ~ (CH30) 3Si (CH2 )3NH(CH2 )2CNHCH2 ~2 Nuosperse~ 657 A dispersing agent supplied by :
Tenneco, Inc.
:: :
- ~Z958~ 12363 Example _ About 276.3 grams (1.25 moles) of gamma-aminopropyltriethoxysilane was added to a 500 ml., 3 necked flask equipped with a mechanical stirrer, heating mantle, addition funnel, thermometer and distillation head and receiver protected by a nitrogen by-pass. About 53.8 grams (0.62 moles) of methyl acrylate was then rapidly added via a funnel with stirring and cooling at such a rate that the contents of the flask were maintained below 25C. After addition, the contents of the flask were stirred for about 3 hours at room temperature and then about 0.66 grams (0.2 weight percent~
of dibutyl tin oxide added as catalyst and the reaction mixture heated to about 135C. to 150C with the appearance of refluxing alcohol (methanol and ethanol) in the distilla-tion head. About 16.2 grams (theory 19.8 grams, assuming all the distillate to be methanol) of said alcohol mixture was removed and collected over 2.5 hours to yield about 307.7 grams ~theory 310 grams) of the crude mixed methoxy-ethoxy silane reaction product.
O
X3Si(CH2)3~(~2)2CNH(CH2)3six3 wherein each X is individually selected from the class consisting of methoxy and ethoxy radicals. An amine analysis of said silane product showed 2.01 moles N/kg.
(theory 2.02 moles titratable N/kg.). Gas chromatographic analysis of the elutable materials of said silane product showed it to consist of about 11.39 weight percent of ~ , 9 S 8 1 123~3 alcohol (methanol and ethanol), about 7.25 weight percent of mixed methoxy-ethoxy si;ane X3Si(CH2)3NH2 wherein X is the same as defi.ned above, about 6.27 weight percent of the mixed methoxy-ethoxy silane Michael adduct intermediate X3Si(CH2)3~HCH2CH2coocH3 wherein X is the same as defined above, and about 71.43 weight percent of the acylamino containing n~xed methoxy-ethoxy silane X3Si(CH2)3NH(CH2)2CNH(CH2)3SiX3 wherein X is the same as defined above, while the remainder of said product did not elute.
Example B
About 895 grams (5.0 moles) of ga~ma-amino-propyltrimethoxysilane and about 215.2 grams (2.5 moles) of methyl acrylate were allowed to react, while stirring at room temperature, in a two liter, 3 necked flask having the same experimental set-up as described in Example A.
After the methyl acrylate was consumed, the reaction mixture was heated to 135C at 100-160 mmHg. over 4 hours , .
~lZ~S~
and about 27.3 grams of methanol collected, The reaction mixture was cooled to room temperature and about 2.22 grams (0.2 weight percent) of ~butyl tin oxide catalyst added. The reaction mixture w~s then reheated to 135C at 80 ~Hg. for two hours and an additional 62.9 grams of methanol collected (total methanol collected = 90.2 grams, theory 80 grams) ~o yield about 1017.7 grams (theory 1030 grams) of the crude silane reaction product (CH3)3Si(cH2)3NH(cH2)2cNH(cH2)3si(ocH3)3 An amine analysis of said silane product showed 2.7 moles N/kg. (theory 2.42 moles titratable N/kg.).
Gas chromatographic analysis of the elutable materials of said silane product showed 13.5 weight percent methanol, 11.0 weight percent of gamma-aminopropyltrimethoxysilane, about 16.0 weight percent of the Michael addition intenmediate (CH30)3Si(CH2)3NH(CH2)COOCH3 and a weight percent of the acylamino containing trimethoxysilane O
(CH30)3Si(CH2)3NH(CH2)2CNH(CH2)3Si(OCH3)3 while the remainder of the product did not elute.
"
~9~ 12363 .. . .
Following the same proeedure as described in Example A, about 151.9 grams (0.68 moles) of (CH30)3-Si(CH2)3NH(CH2)~NH2 with an amine analysis of 8.82 moles N/kg. (theory 9.0 moles N/kg) distilled from commercial grade N-bet~-(aminoethyl)-gamma-aminopropyltrimethoxy-silane was allowed to react while stirring and cooling to maintain the temperature at about room temperature with about 28.4 grams (0.33 moles of methyl acrylate).
After one hour amine analysis of the reaction mixture was about 7.27 moles N/kg. (theory 6.49 moles titratable N/kg.). Nuclear magnetic resonance analysis indicated total disappearance o~ acxylate protons, but the retention of the carboxymethoxy methyl group protons while the concentration of -NH-protons and the remainder of the spectrum was consistent with the ~ichael addition adduct structure`.
(CH30~3Si(CH2)3NH(CH2)2NH~CH2)~2COOCH3 ~' The reaction mixture was then heated to 150C for 4 hours, distilling 6~0 grams of methanol. A nuclear magnetic resonance analysis at this point of the experiment ;
indicated greater than 90% methanol formation (or less than 10% carbomethoxy methyl group remaining). The distillation was completed under vacuum producing an additional 6.2 grams of methanol (tota methanol 12.2 grams, theory 10.6 grams) and yielding about 159.7 grams (theory 164.3 grams) of the crude silane reaction product ~ ~ Z ~ 363 (cH3o)3s~ 2)3~ 2)2l~H(cx2)2cNH~(cH2)2NH(cH2)3si(ocH3)3 An amine analysis of said silane product showed 5.89 moles N/kg. (theory 6.02 moles titratable N/kg.). Gas chromatographic analysis of the elutable materials of said silane product showed about 1.0 weight percent methanol, about 9.9 weight percent (CH30)3si(CH2)3NH(CH2)2-NH2, about 4.6 weight percent of the Michael addition intermediate (~H30)3Si(CH2)3~(CH2)2L~H(CH2)2COOCH3, while the remainder of said crude silane product did not elute.
Nuclear magnetic resonance analysis of the crude silane reaction product confirmed the above silane product structure.
EX~MPLES 1-5 A series of hydroxyl containing organic polymer-aminoorganosilicon acJlamino coating compositions were prepared having the following total formulation Compound Parts by Weight Polymer A 25.45 Titanium Dioxide 19.09 Methylisobutyl ~etone27.57 Xylene 27.57 ~uosperse 657 0.32 Molecular Sieves 4A 0.5 Silane* Varied*
*The particular Silane employed as well as the parts by weight of said Silane in the total formulation are given in Table I below.
Each coating composition was prepared by dissolving Polymer A in a solvent blend (50/50 wt. %) of methylisobutyl ketone and xylene followed by the addition of the dispersing agent and titanium dioxide pigment (the molecular sieves ~ 363 3L~Z'9~8~ o being added with said pigment) with stirring and the mixture ground ir. a pebble mill overnight. The silane compound was then added with stirring until a unifor~
coating composition was obtained. Each coating composition was then thinned to a No. 4 Ford cup viscosity of 20-25 seconds by the addition of a 50/50 weight percent solvent blend of methylisobutyl ketone and xylene. Each coating composition so prep~red was then applied by a draw down blade to sand blasted steel panels to give a coating thickness of about 2 mils and the coatings on said panels cured by allowing them to air dry at room temperature.
The solvent resistance of each coating on said panels after having been air dried at room temperature for various ~eriods of time was then measured by subjecting each air dried coating to double MEK rubs and the results of this test are reported in Table I below. Said test involves saturating a gauze cloth with methylethylketone and rubbing the saturated cloth back and forth (or up and down) over the air dried coating until the metal surface of the panel is exposed. For example, a numerical double ~K rub rating of five means that the metal surface of the ;
panel was exposed after the methylethylketone saturated cloth was rubbed back and forth (2 strokes) over the coat-ing a total of five times. Thus the higher the numerical double ~K rub rating obtained for a given coating the more solvent resistant the coating is.
~2~5~ 12363 TABLE I
Silane Ex. (Parts by ~ -Double MEK Rubs -~
No Silane Wt.)24 hours 48 hours ~ 10 Days 18 Day~
1 A 5.09 5 - 11 - 14 2 B 5.09 100+ - 100+ - 100+
3 C 5.09 ~00+
4 D 5.09 3 - 7 - 8 E 7.64 11 16 - 33 -+ Double MEK rubs stopped after reaching 100 The above results of Table I show that better solvent resistent coatings were obtained using silanes ~:
encompassed by this invention (i.e. Silanes A, B and C) then that obtained by the use of si~lilar silanes (Silanes D
and E) not encompassed by thls invention.
Various modifications and variations of this invention will be obvious to a worker skilled in the art and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the appended claims.
encompassed by this invention (i.e. Silanes A, B and C) then that obtained by the use of si~lilar silanes (Silanes D
and E) not encompassed by thls invention.
Various modifications and variations of this invention will be obvious to a worker skilled in the art and it is to be understood that such modifications and variations are to be included within the purview of this application and the spirit and scope of the appended claims.
Claims (43)
1. A substantially anhydrous, acid-free, room temperature curable composition which comprises (A) an organic thermoplastic polymer containing at least two hydroxyl radicals which are directly bonded to non-carboxylic carbon atoms of said polymer; and (B) a hydrolyzable aminoorganosilicon acylamino compound having the formula and mixtures thereof, wherein:
X is an alkoxy radical having 1 to 6 carbon atoms; R is a divalent alkylene radical having 1 to 4 carbon atoms; R1 is hydrogen or an alkyl radical having 1 to 4 carbon atoms; R2 is a divalent alkylene radical having 2 to 4 carbon atoms; R3 is a radical selected from the group consisting of hydrogen, an alkyl radical having 1 to 20 carbon atoms or a phenyl radical; R4 is a radical selected from the group consisting of an alkyl radical having 1 to 20 carbon atoms, a phenyl radical or a silyl radical of the formula:
wherein X, R and R1 are the same as defined above;
Q is a radical selected from the group consisting of hydrogen, an alkyl radical of 1 to 4 carbon atoms, a phenyl radical or an ester radical of the formula -COOR5 wherein R5 is an alkyl radical having 1 to 4 carbon atoms; and wherein a has a value of 0 to 2 and t and x each have a value of 0 to 4, with the proviso that when x is at least 1, R4 can also be hydrogen; and wherein said composition contains about 5 to 50 parts by weight of said hydrolyzable silicon compound (B) per 100 parts by weight of said organic polymer (A).
X is an alkoxy radical having 1 to 6 carbon atoms; R is a divalent alkylene radical having 1 to 4 carbon atoms; R1 is hydrogen or an alkyl radical having 1 to 4 carbon atoms; R2 is a divalent alkylene radical having 2 to 4 carbon atoms; R3 is a radical selected from the group consisting of hydrogen, an alkyl radical having 1 to 20 carbon atoms or a phenyl radical; R4 is a radical selected from the group consisting of an alkyl radical having 1 to 20 carbon atoms, a phenyl radical or a silyl radical of the formula:
wherein X, R and R1 are the same as defined above;
Q is a radical selected from the group consisting of hydrogen, an alkyl radical of 1 to 4 carbon atoms, a phenyl radical or an ester radical of the formula -COOR5 wherein R5 is an alkyl radical having 1 to 4 carbon atoms; and wherein a has a value of 0 to 2 and t and x each have a value of 0 to 4, with the proviso that when x is at least 1, R4 can also be hydrogen; and wherein said composition contains about 5 to 50 parts by weight of said hydrolyzable silicon compound (B) per 100 parts by weight of said organic polymer (A).
2. A composition as defined in claim 1, wherein R3 is hydrogen; Q is hydrogen; t is 0 or 1;
x is 0 and R4 is an alkyl radical.
x is 0 and R4 is an alkyl radical.
3. A composition as defined in claim 1, wherein R3 is hydrogen; Q is hydrogen; ? is 0 or 1; ? is 1 and R4 is hydrogen or an alkyl radical.
4. A composition as defined in claim 1, wherein R3 is hydrogen; Q is hydrogen; ? is 0 or 1;
? is 0 and R4 is a silyl radical of the formula wherein R, R1 and X and ? are the same as defined above.
? is 0 and R4 is a silyl radical of the formula wherein R, R1 and X and ? are the same as defined above.
5. A composition as defined in claim 4 wherein ? is 0; ? is 0; R is -CH2CH2CH2-; and X is an alkoxy radical selected from the group consisting of methoxy, ethoxy and 2-methoxyethoxy radicals.
6. A composition as defined in claim 5, wherein X is a methoxy radical.
7. A composition as defined in claim 5, wherein X is an ethoxy radical.
8. A composition as defined in claim 1, wherein R3 is hydrogen; Q is hydrogen; ? is 0 or 1;
? is 1 and R4 is a silyl radical of the formula wherein R, R1 and X and ? are the same as defined above.
? is 1 and R4 is a silyl radical of the formula wherein R, R1 and X and ? are the same as defined above.
9. A composition as defined in claim 8, wherein ? is 0; ? is 1; R is -CH2CH2CH2-; R2 is -CH2CH2- and X is an alkoxy radical selected from the group consisting of methoxy, ethoxy and 2-methoxyethoxy radicals.
10. A composition as defined in claim 9, wherein X is a methoxy radical.
11. A composition as defined in claim 9, wherein X is an ethoxy radical.
12. A composition as defined in claim 1 wherein the organic thermoplastic polymer is selected from the class consisting of a hydroxyalkyl acrylate modified vinyl chloride polymer, a polyether polyol polymer, a polyhydroxy containing acrylate polymer, a polyvinyl alcohol polymer, a polyhydroxy containing polyvinyl acetal polymer, a polyester polyol polymer, a phenolic resin polymer, and mixtures thereof.
13. A composition as defined in claim 12, wherein X is an alkoxy radical selected from the group consisting of methoxy, ethoxy, and 2-methoxyethoxy wherein R and R2 are divalent alkylene radicals selected from the group consisting of ethylene and propylene, wherein R3 and Q are hydrogen, wherein ? is 0, wherein ? is 0 or 1, wherein ? is 0 or 1 and wherein R4 is a silyl radical of the formula -R-Si-X3 wherein R and X are the same as defined above.
14. A composition as defined in claim 13, wherein the organic thermoplastic polymer is a hydroxy-alkyl acrylate modified vinyl chloride polymer.
15. A composition as defined in claim 13, wherein the organic thermoplastic polymer is a polyether polyol polymer.
16. A composition as defined in claim 13, wherein the organic thermoplastic polymer is a poly-hydroxy containing polyvinyl acetal polymer.
17. A composition as defined in claim 13, wherein the organic thermoplastic polymer is a poly-hydroxy containing acrylate polymer.
18. A composition as defined in claim 13, wherein the organic thermoplastic polymer is a polyvinyl alcohol polymer.
19. A composition as defined in claim 13, wherein the organic thermoplastic polymer is a polyester polyol polymer.
20. A composition as defined in claim 13, wherein the organic thermoplastic polymer is a phenolic resin polymer.
21. A composition as defined in claim 13, wherein X is methoxy, R is a propylene radical and R2 is an ethylene radical.
22. A composition as defined in claim 1, wherein said composition contains about 10 to about 40 parts by weight of said hydrolyzable aminoorganosilicon acylamino compound (B) per 100 parts by weight of said organic polymer (A).
23. A composition as defined in claim 1 wherein an alkylsilicate is present as an additional ingredient.
24. A composition as defined in claim 23, wherein the alkyl silicate is tetraethyl orthosilicate.
25. A composition as defined in claim 12, which also contains an organic solvent in an amount sufficient to dissolve the organic polymer employed;
about 70 to 100 parts by weight of a pigment per 100 parts by weight of said organic polymer; 0 to about 70 parts by weight of a filler material per 100 parts by weight of said organic polymer; 0 to about 25 parts by weight of an alkyl silicate; and based on the total weight of the composition 0 to about 1 percent by weight of a dispersing agent for said pigment and 0 to about 3 percent by weight of a dessicant material.
about 70 to 100 parts by weight of a pigment per 100 parts by weight of said organic polymer; 0 to about 70 parts by weight of a filler material per 100 parts by weight of said organic polymer; 0 to about 25 parts by weight of an alkyl silicate; and based on the total weight of the composition 0 to about 1 percent by weight of a dispersing agent for said pigment and 0 to about 3 percent by weight of a dessicant material.
26. A composition as defined in claim 25 wherein X is an alkoxy radical selected from the group consisting of methoxy, ethoxy and 2-methoxyethoxy, wherein R and R2 are divalent alkylene radicals selected from the group consisting of ethylene and propylene, wherein R3 and Q are hydrogen, wherein ? is 0, wherein ? is 0 or 1, wherein ? is 0 or 1 and wherein R4 is a silyl radical of the formula -RSiX3 wherein R and X are the same as defined above.
27. A composition as defined in claim 26, wherein the organic thermoplastic polymer is a hydroxy-alkyl acrylate modified vinyl chloride polymer.
28. A composition as defined in claim 26, wherein the organic thermoplastic polymer is a polyether polyol polymer.
29. A composition as defined in claim 28, wherein the polyether polyol polymer is a phenoxy resin.
30. A composition as defined in claim 26, wherein the organic thermoplastic polymer is a polyhydroxy containing polyvinyl acetal polymer.
31. A composition as defined in claim 30, wherein the polyhydroxy containing polyvinyl acetal polymer is a polyvinylbutyral resin.
32. A composition as defined in claim 26, wherein the organic thermoplastic polymer is a polyhydroxy containing acrylate polymer.
33. A composition as defined in claim 26, wherein the organic thermoplastic polymer is a polyvinyl alcohol polymer.
34. A composition as defined in claim 26, wherein the organic thermoplastic polymer is a polyester polyol polymer.
35. A composition as defined in claim 26, wherein the organic thermoplastic polymer is a phenolic resin polymer.
36. A composition as defined in claim 27, wherein R is a propylene radical R2 is an ethylene radical, and X is methoxy.
37. A composition as defined in claim 25, wherein said composition contains about 10 to about 40 parts by weight of said hydrolyzable aminoorganosilicon acylamino compound (B) per 100 parts by weight of said organic polymer (A).
38. A composition as defined in claim 25, wherein the pigment is titanium dioxide.
39. A composition as defined in claim 27, wherein the organic polymer contains (a) from about 50 to about 85 weight percent of vinyl chloride derived mer units, (b) from about 0 to 10 weight percent mer units derived from a polymerizable monomer selected from the class consisting of alkyl esters of alpha, beta-ethyl-enically unsaturated carboxylic acids and vinyl esters of saturated fatty acids, and (c) from 10 to 30 percent mer units derived from hydroxyalkyl acrylate.
40. A composition as defined in claim 39, wherein the organic polymer is a hydroxy-functional random ter-polymer containing about 80 weight percent vinyl chloride mer units, about 5 weight percent vinyl acetate mer units and about 15 weight percent hydroxypropyl acrylate mer units.
41. A composition as defined in claim 40, wherein said composition contains about 10 to about 40 parts by weight of said hydrolyzable aminoorganosilicon acylamino compound (B) per 100 parts by weight of said organic polymer (A).
42. A composition as defined in claim 41 wherein the pigment is titanium dioxide.
43. The crosslinked polymer product obtained upon crosslinking the composition of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US974,614 | 1978-12-29 | ||
| US05/974,614 US4284548A (en) | 1978-12-29 | 1978-12-29 | Ambient temperature curable hydroxyl containing polymer/silicon compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129581A true CA1129581A (en) | 1982-08-10 |
Family
ID=25522257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA338,026A Expired CA1129581A (en) | 1978-12-29 | 1979-10-19 | Ambient temperature curable hydroxyl containing polymer |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4284548A (en) |
| EP (1) | EP0012835B1 (en) |
| JP (1) | JPS5917137B2 (en) |
| AU (1) | AU526631B2 (en) |
| CA (1) | CA1129581A (en) |
| DE (1) | DE2963273D1 (en) |
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|---|---|---|---|---|
| US4239539A (en) * | 1979-06-25 | 1980-12-16 | Union Carbide Corporation | Aminosilane modified zinc-rich coating compositions |
| US4491650A (en) * | 1982-05-05 | 1985-01-01 | Essex Specialty Products, Inc. | Acrylic resin having pendant silane groups thereon, and methods of making and using the same |
| JPS5971377A (en) * | 1982-10-15 | 1984-04-23 | Kanegafuchi Chem Ind Co Ltd | Adhesive composition |
| US4495247A (en) * | 1983-06-30 | 1985-01-22 | E. I. Du Pont De Nemours And Company | Primer coating composition of a fluorocarbon polymer and an amino alkyl alkoxy silane |
| US4490501A (en) * | 1983-06-30 | 1984-12-25 | E. I. Du Pont De Nemours And Company | Coating composition of a fluorocarbon polymer and a polyamine curing agent |
| US4487878A (en) * | 1983-06-30 | 1984-12-11 | E. I. Du Pont De Nemours And Company | Coating composition of a solution fluorocarbon polymer, a dispersed fluorocarbon polymer and a polyamine curing agent |
| US4495248A (en) * | 1983-06-30 | 1985-01-22 | E. I. Dupont De Nemours And Company | Coating composition of a fluorocarbon polymer and a polyamine curing agent |
| US4506054A (en) * | 1983-06-30 | 1985-03-19 | Vasta Joseph A | Coating composition of a solution fluorocarbon polymer, a dispersed fluorocarbon polymer and a polyamine curing agent |
| US4468492A (en) * | 1983-07-15 | 1984-08-28 | Ppg Industries, Inc. | Polymeric organo functional silanes as reactive modifying materials |
| US4668716A (en) * | 1983-09-30 | 1987-05-26 | Union Carbide Corporation | Novel fatty ethenoid acylaminoorganosilicon compounds and their use as a coupling agent |
| US4584138A (en) * | 1983-09-30 | 1986-04-22 | Union Carbide Corporation | Novel fatty ethenoid acylaminoorganosilicon compounds and their use as a coupling agent |
| US4548842A (en) * | 1983-12-20 | 1985-10-22 | Union Carbide Corporation | Fatty ethenoid acylaminoorganosilicon compounds and their use in compositions for coating glass |
| US4659756A (en) * | 1983-12-20 | 1987-04-21 | Union Carbide Corporation | Fatty ethenoid acylaminoorganosilicon compounds and their use in compositions for coating glass |
| GB8510690D0 (en) * | 1985-04-26 | 1985-06-05 | Bostik Ltd | Moisture curable sealants |
| US6316520B1 (en) | 1995-04-19 | 2001-11-13 | Capitol Specialty Plastics, Inc. | Monolithic polymer composition having a releasing material |
| US6177183B1 (en) | 1995-04-19 | 2001-01-23 | Capitol Specialty Plastics, Inc. | Monolithic composition having an activation material |
| US6221446B1 (en) | 1995-04-19 | 2001-04-24 | Capitol Specialty Plastics, Inc | Modified polymers having controlled transmission rates |
| US6486231B1 (en) | 1995-04-19 | 2002-11-26 | Csp Technologies, Inc. | Co-continuous interconnecting channel morphology composition |
| USRE40941E1 (en) * | 1995-04-19 | 2009-10-20 | Csp Technologies, Inc. | Monolithic polymer composition having a releasing material |
| US6214255B1 (en) | 1995-04-19 | 2001-04-10 | Capitol Specialty Plastics, Inc. | Desiccant entrained polymer |
| US5911937A (en) * | 1995-04-19 | 1999-06-15 | Capitol Specialty Plastics, Inc. | Desiccant entrained polymer |
| US6124006A (en) * | 1995-04-19 | 2000-09-26 | Capitol Specialty Plastics, Inc. | Modified polymers having controlled transmission rates |
| US6080350A (en) * | 1995-04-19 | 2000-06-27 | Capitol Specialty Plastics, Inc. | Dessicant entrained polymer |
| US6174952B1 (en) | 1995-04-19 | 2001-01-16 | Capitol Specialty Plastics, Inc. | Monolithic polymer composition having a water absorption material |
| US6194079B1 (en) | 1995-04-19 | 2001-02-27 | Capitol Specialty Plastics, Inc. | Monolithic polymer composition having an absorbing material |
| US6130263A (en) * | 1995-04-19 | 2000-10-10 | Capitol Specialty Plastics, Inc. | Desiccant entrained polymer |
| US6460271B2 (en) | 1995-04-19 | 2002-10-08 | Csp Technologies, Inc. | Insert having interconnecting channel morphology for aldehyde absorption |
| KR19990022348A (en) * | 1995-06-05 | 1999-03-25 | 미리암 디. 메코너헤이 | Coating Composition Containing Silane Functional Group |
| US6632805B1 (en) | 1996-05-07 | 2003-10-14 | Emory University | Methods for using water-stabilized organosilanes |
| US5959014A (en) * | 1996-05-07 | 1999-09-28 | Emory University | Water-stabilized organosilane compounds and methods for using the same |
| US6465532B1 (en) | 1997-03-05 | 2002-10-15 | Csp Tecnologies, Inc. | Co-continuous interconnecting channel morphology polymer having controlled gas transmission rate through the polymer |
| US5954869A (en) | 1997-05-07 | 1999-09-21 | Bioshield Technologies, Inc. | Water-stabilized organosilane compounds and methods for using the same |
| DE19725501C1 (en) * | 1997-06-17 | 1998-12-10 | Huels Silicone Gmbh | Alkoxy crosslinking RTVl silicone rubber mixtures |
| US6762172B1 (en) | 1997-07-17 | 2004-07-13 | Nova Biogenetics, Inc. | Water-stabilized organosilane compounds and methods for using the same |
| US6113815A (en) * | 1997-07-18 | 2000-09-05 | Bioshield Technologies, Inc. | Ether-stabilized organosilane compositions and methods for using the same |
| EP0940456B1 (en) * | 1998-03-03 | 2003-11-26 | Shin-Etsu Chemical Co., Ltd. | Water resistant ink compositions |
| JP3470624B2 (en) * | 1998-12-16 | 2003-11-25 | 信越化学工業株式会社 | Water resistant ink composition |
| US6696002B1 (en) | 2000-03-29 | 2004-02-24 | Capitol Security Plastics, Inc. | Co-continuous interconnecting channel morphology polymer having modified surface properties |
| JP2007321122A (en) * | 2006-06-05 | 2007-12-13 | Shin Etsu Chem Co Ltd | Room temperature-curable organopolysiloxane composition |
| US8349066B2 (en) * | 2006-09-21 | 2013-01-08 | Ppg Industries Ohio, Inc. | Low temperature, moisture curable coating compositions and related methods |
| WO2008036721A1 (en) * | 2006-09-21 | 2008-03-27 | Ppg Industries Ohio, Inc. | Low temperature, moisture curable coating compositions and related methods |
| US20080075871A1 (en) * | 2006-09-21 | 2008-03-27 | Ppg Industries Ohio, Inc. | Low temperature, moisture curable coating compositions and related methods |
| US9458451B2 (en) | 2007-06-21 | 2016-10-04 | Gen-Probe Incorporated | Multi-channel optical measurement instrument |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3252825A (en) * | 1959-09-14 | 1966-05-24 | Owens Corning Fiberglass Corp | Process of coating glass fibers with hydrolyzed condensation product of amino silane and copolymerizable monomer |
| DE1424635A1 (en) * | 1961-07-28 | 1969-12-11 | Kienzle Apparate Gmbh | Collection device for booking machines |
| US3247281A (en) * | 1961-09-27 | 1966-04-19 | Union Carbide Corp | Water repellent compositions containing water soluble aminosilanes and aminosilicones as curing catalysts and process for treating substrates therewith |
| US3252278A (en) * | 1962-08-22 | 1966-05-24 | Owens Corning Fiberglass Corp | Elastomeric-glass fiber products and process |
| US3408420A (en) * | 1964-04-30 | 1968-10-29 | Du Pont | Silane-modified olefinic copolymers |
| US3981851A (en) * | 1972-01-10 | 1976-09-21 | Dow Corning Corporation | Primer compositions |
| GB1485263A (en) * | 1973-07-17 | 1977-09-08 | Dow Corning Ltd | Method for preparing crosslinkable polymers |
| US3907974A (en) * | 1973-11-08 | 1975-09-23 | Dennison Mfg Co | Curable decorating systems for glass or metal containers |
| JPS609070B2 (en) * | 1974-08-21 | 1985-03-07 | 日本原子力研究所 | Manufacturing method of thermosetting resin composition |
| NL7700131A (en) | 1976-02-21 | 1977-08-23 | Pfersee Chem Fab | PROCESS FOR TREATING TEXTILES WITH POLYMERS OF ACRYLIC AND METHACRYLIC ESTERS. |
| DE2712688C3 (en) * | 1977-03-23 | 1979-10-04 | Dynamit Nobel Ag, 5210 Troisdorf | Solvent-free molding compound based on polyvinyl chloride |
-
1978
- 1978-12-29 US US05/974,614 patent/US4284548A/en not_active Expired - Lifetime
-
1979
- 1979-10-15 AU AU51787/79A patent/AU526631B2/en not_active Ceased
- 1979-10-19 CA CA338,026A patent/CA1129581A/en not_active Expired
- 1979-11-13 JP JP54146147A patent/JPS5917137B2/en not_active Expired
- 1979-11-15 EP EP79104524A patent/EP0012835B1/en not_active Expired
- 1979-11-15 DE DE7979104524T patent/DE2963273D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5917137B2 (en) | 1984-04-19 |
| US4284548A (en) | 1981-08-18 |
| EP0012835B1 (en) | 1982-06-30 |
| EP0012835A3 (en) | 1980-07-23 |
| DE2963273D1 (en) | 1982-08-19 |
| EP0012835A2 (en) | 1980-07-09 |
| AU526631B2 (en) | 1983-01-20 |
| AU5178779A (en) | 1980-07-03 |
| JPS5592764A (en) | 1980-07-14 |
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