CA1123988A - Ambient temperature curable hydroxyl containing polymer/silicon compositions - Google Patents
Ambient temperature curable hydroxyl containing polymer/silicon compositionsInfo
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- CA1123988A CA1123988A CA338,031A CA338031A CA1123988A CA 1123988 A CA1123988 A CA 1123988A CA 338031 A CA338031 A CA 338031A CA 1123988 A CA1123988 A CA 1123988A
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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
-
- 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 aminosilicon compound, said compositions being useful as protective coating compositions.
Ambient temperature curable compositions comprising a hydroxyl containing organic polymer and an aminosilicon compound, said compositions being useful as protective coating compositions.
Description
` 11,931 ~ 23g8!5t This invention relates to novel room temperature curable compositions comprising a hydroxyl containing organic thermoplastic polymer and an aminosillcon 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 temper-ature curable compositions the prior ar~ has had to pre-react the starting organic polymer with ~he organosilane at elevated temperatures. One exception to such methods has been the use of halosilanes whic~ are known to react at room temperature with hydroxy~ containing polymers, howe~er, this procedure has the disadvantage of also ~producing an undesirable acid by-product, e.g. hydrogen chloride, which if not removet m~y have a deleterious effect on the per-fonmance o the cured composition.
It has now been discovered that room temperature curable poLymer compositions can also be easily prepzred at room temperature by ~imply mixlng a hydroxyl containing organic thermoplastic polymer with certain hydrolyzable aminosilicon compounds without also resulting in undesirable by-produc~s.
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 temper-ature curable compositions the prior ar~ has had to pre-react the starting organic polymer with ~he organosilane at elevated temperatures. One exception to such methods has been the use of halosilanes whic~ are known to react at room temperature with hydroxy~ containing polymers, howe~er, this procedure has the disadvantage of also ~producing an undesirable acid by-product, e.g. hydrogen chloride, which if not removet m~y have a deleterious effect on the per-fonmance o the cured composition.
It has now been discovered that room temperature curable poLymer compositions can also be easily prepzred at room temperature by ~imply mixlng a hydroxyl containing organic thermoplastic polymer with certain hydrolyzable aminosilicon compounds without also resulting in undesirable by-produc~s.
2.
~39~8 11, 931 Thus, it is an object of this invention to provide room temperature curable compositions comprising a hydroxyl con~aining organic thermoplastic polymer and a hydrolyzable aminosilicon compound. It is another obJect of this inven-tion to provide cured crosslinked products, e.g. solvent resistant coatings, derived from the curable compositions of this invention. Other objects and advantages of this invention will become 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, 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 hydro-lyzable aminosilicon compound selected from the class consisting of aminosilicon compounds having the formula Rla R2 R2 I ~ t 2 (I) . X3~a-Si-R(NR3)tN-R
- 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 radical selected from the group consisting o~ hydrogen, an alkyl radical having 1 to 4 carbon atoms and a ~ilyl radical of the formula ~la -R-Sl~X3-a;
~ ~ ~ 3 ~ 8 ~ ' wherein R, Rl, and X are the same as deined aboYe; R3 is a divalent alkylene radical having 2 to 4 carbon atoms; a has a value of 0 to 2; t has a value of 0 to 4; and wherein said composition contains about 5 to 50 parts by weight of said hydrolyzable aminosilicon compound (B) per lO0 parts by weight of said organic polymer (A).
Any hydroxyl containing organic thermoplastic polymer having at least two hydroxyl radicals which are directly bonded to non-carboxylic 0 carbon atoms ~ i.e. -C-) can be employed as the organic polymer component of the room temperature (i.e. ambient~ curable compositions of this lnvention. Such ~ypes of hydroxyl containing organic polymers and/or methods for their preparation are well known in the polymer art. Of course it is to be understood that the hydroxyl containing orgaDic thermoplastic polymers 2mployable in this invention include homopolymers, copolymers, terpolymers and the llke and tha~ mixtures of more than one type or class of polymers can be employed if desired.
Llkewise, it is to be understood that the particular proportions of polymer units and molecular weights of the hydroxy containing organic thermoplastic polymer components of this invention are not generally critical to the inven-tion. Iltustrat~ve examples of such hydroxyl containing organic thermoplastic polymers include:
4.
~ 11,931 (a) Hydroxyalkyl acrylate modified vinyl chloride polymers such as the uniformly random hydroxyl-functional copolymers or terpolymers of (i) vinyl chloride;
(ii) hydroxyalkyl acrylate having 2 to 4 carbons in the alkyl 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, me~hacrylic, maleic, fum~ric, 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-functionai copolymers and terpolymers are tescribed in U.S. 3,884,887 and U.S.
~39~8 11, 931 Thus, it is an object of this invention to provide room temperature curable compositions comprising a hydroxyl con~aining organic thermoplastic polymer and a hydrolyzable aminosilicon compound. It is another obJect of this inven-tion to provide cured crosslinked products, e.g. solvent resistant coatings, derived from the curable compositions of this invention. Other objects and advantages of this invention will become 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, 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 hydro-lyzable aminosilicon compound selected from the class consisting of aminosilicon compounds having the formula Rla R2 R2 I ~ t 2 (I) . X3~a-Si-R(NR3)tN-R
- 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 radical selected from the group consisting o~ hydrogen, an alkyl radical having 1 to 4 carbon atoms and a ~ilyl radical of the formula ~la -R-Sl~X3-a;
~ ~ ~ 3 ~ 8 ~ ' wherein R, Rl, and X are the same as deined aboYe; R3 is a divalent alkylene radical having 2 to 4 carbon atoms; a has a value of 0 to 2; t has a value of 0 to 4; and wherein said composition contains about 5 to 50 parts by weight of said hydrolyzable aminosilicon compound (B) per lO0 parts by weight of said organic polymer (A).
Any hydroxyl containing organic thermoplastic polymer having at least two hydroxyl radicals which are directly bonded to non-carboxylic 0 carbon atoms ~ i.e. -C-) can be employed as the organic polymer component of the room temperature (i.e. ambient~ curable compositions of this lnvention. Such ~ypes of hydroxyl containing organic polymers and/or methods for their preparation are well known in the polymer art. Of course it is to be understood that the hydroxyl containing orgaDic thermoplastic polymers 2mployable in this invention include homopolymers, copolymers, terpolymers and the llke and tha~ mixtures of more than one type or class of polymers can be employed if desired.
Llkewise, it is to be understood that the particular proportions of polymer units and molecular weights of the hydroxy containing organic thermoplastic polymer components of this invention are not generally critical to the inven-tion. Iltustrat~ve examples of such hydroxyl containing organic thermoplastic polymers include:
4.
~ 11,931 (a) Hydroxyalkyl acrylate modified vinyl chloride polymers such as the uniformly random hydroxyl-functional copolymers or terpolymers of (i) vinyl chloride;
(ii) hydroxyalkyl acrylate having 2 to 4 carbons in the alkyl 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, me~hacrylic, maleic, fum~ric, 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-functionai copolymers and terpolymers are tescribed in U.S. 3,884,887 and U.S.
3,755,271.
(b) Polyether polyol polymers such as the alkylene 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 combination ~ clude ethylene glycol; diethylene glycol; propylene glycol, 1,5-pentanediol; hexylene glycol; dipropylene giycol; trimethylene glycol; 1,2-cyclohexanediol; 3-cyclo-hexane~ dimethanol and dibromo-derivative thereof;
glycerol; 172,6-hexanetriol; l,l,l-trime~byolethane;
l,l,l-trimethyolpropane; 3-(2~hydroxyethoxy)- and 3-~2-hydroxypropoxy)-1,3-propanediols; 2,4-dimethyl-2-(2-hydroxyethoxy)methylpentanediol-1,5; 1,1,1-tris~2-hydroxyethoxy)methyl~ethane; l,l,l-tris~2-hydroxypropoxy) methyl~propane; pentaerythritol; sorbitol; sucrose; alpha-5.
` ~ ~ 2 ~ 11,931 methyl glucoside; and other such polyhydric compounds consisting of carbon 3 hytrogen and oxygen and having usually not more than about 15 carbon atoms per molecule. Illustra-tive alkylene oxides include ethylene oxi~e, 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. phenoxy 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) Polyhydrox~ containing acrylic polymers such as the copolymers and terpolymers of hydroxyalkyl acrylates having 2 to 4 carbon atoms in the alkyl segments and alkyl acrylates and/or alkyl methacrylates having 1 to ~ carbon atoms in the alkyl segments.
(d) Polyvinyl alcohol polymers such as the hydrolyzed or partially hydrolyzed polymers derived from the ho polymers of vinyl esters o~ saturated fatty acids of 1-6 carbon atoms or the copolymers of said vinyl esters and one or more ethylenically unsaturated monomers such as ~23~3 11, 93~
ethylene, p~-opylene, butylene, acrylonitrile, methacrylo-nitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene, butadiene, and the like.
(e) Polyhydroxy containing polyvinyl acetal polymers such as polyvinylbutyral resins and the like.
(f) Polyester polyol polymers such as the reaction products of polyfunctional organic carboxylic acids and polyhydric alcohols, which reaction products contain at least two 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 ~uch lactones with polyhydric alcohols~
Typical of the polyfunctional organLc carboxylic acids that can be employed in producing polyester polyols useful in this invention are: dicarboxyLic aliphatic acids such as succinic,~adipic, sebacic, aæelaic, 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 aihydrides of any of these various acids can be employed in producing the polyester polyols.
The polyhydric alcoho~s (organic polyols) that can be employed in producing the polyester polyol starting 7.
11,931 3 ~
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; tr~methyolethane; pentaerythritol; propylene ~lycol; 1,2-, 1,3- and 1,4-butylene glycols; l,S-pentanediol;
sorbitol; and the like, incLuding mixtures thereof.
Other polyhydric alcohols that can be employed in producing the polyes~er polyols useful in this invention are the polymeric polyhydric alcohols which include the linear and branched chain polyethers having a plurality of acyclic ether oxygens and at leas~ 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 o the poly(oxyalkylene) polyols include the poly(oxyethylene) glycols prepared by the addition of ethylene oxide to water, ethylene glycol or diethyl~ne glycol; poly(oxypropylene~
glycols prepared by the addition of propylene oxide to water, propylene glycol or dipropylene glycol; mixed 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 ~ 11,931 Illustrative of further polyester polyols are the reaction 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 mLxtures thereof, wi~h any of the following: glycerol; trimethylolpropane, 1,2,6-hexanetriol; pentaerythritol; sorbitol; glycosides such as methyl, ethyl, propyl, butyl and 2-ethyLhexyl arabinoside, xyloside, ~ructoside, glucoside, and rhammoside; sucr^se;
mononuclear polyhydroxybenzenes such as resorcinDl pyro-gallol, phloroglucinol, hydroquinone, 4,6-di tertiary-hutylcatechol, and catechol; polynuclear hydroxyben2enes ("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 containing one to twelve carbon atoms, such compounds being typically illustrated by 2,2-bis(p-hydroxyphenyl)-propane, bis(p-hydroxyphenyl)-methane and the 20 various diphenols and diphenol methanes disclosed in United States Patent Nos. 2,506,486 and 2,744,882, respectively. Another type of polyester polyol is that produced by reaction o~ a polycarboxylic acid and the polyether adducts formed by reaction vf ethylene oxide, propylene oxide or butylene oxide with phenol-formaldehyde condensation products such as the novolaks.
~g) Phenolic resln polymers such as the solid resoles and novolak resins disclosed in U.S~ Patent
(b) Polyether polyol polymers such as the alkylene 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 combination ~ clude ethylene glycol; diethylene glycol; propylene glycol, 1,5-pentanediol; hexylene glycol; dipropylene giycol; trimethylene glycol; 1,2-cyclohexanediol; 3-cyclo-hexane~ dimethanol and dibromo-derivative thereof;
glycerol; 172,6-hexanetriol; l,l,l-trime~byolethane;
l,l,l-trimethyolpropane; 3-(2~hydroxyethoxy)- and 3-~2-hydroxypropoxy)-1,3-propanediols; 2,4-dimethyl-2-(2-hydroxyethoxy)methylpentanediol-1,5; 1,1,1-tris~2-hydroxyethoxy)methyl~ethane; l,l,l-tris~2-hydroxypropoxy) methyl~propane; pentaerythritol; sorbitol; sucrose; alpha-5.
` ~ ~ 2 ~ 11,931 methyl glucoside; and other such polyhydric compounds consisting of carbon 3 hytrogen and oxygen and having usually not more than about 15 carbon atoms per molecule. Illustra-tive alkylene oxides include ethylene oxi~e, 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. phenoxy 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) Polyhydrox~ containing acrylic polymers such as the copolymers and terpolymers of hydroxyalkyl acrylates having 2 to 4 carbon atoms in the alkyl segments and alkyl acrylates and/or alkyl methacrylates having 1 to ~ carbon atoms in the alkyl segments.
(d) Polyvinyl alcohol polymers such as the hydrolyzed or partially hydrolyzed polymers derived from the ho polymers of vinyl esters o~ saturated fatty acids of 1-6 carbon atoms or the copolymers of said vinyl esters and one or more ethylenically unsaturated monomers such as ~23~3 11, 93~
ethylene, p~-opylene, butylene, acrylonitrile, methacrylo-nitrile, vinyl chloride, vinylidene chloride, styrene, alpha-methylstyrene, butadiene, and the like.
(e) Polyhydroxy containing polyvinyl acetal polymers such as polyvinylbutyral resins and the like.
(f) Polyester polyol polymers such as the reaction products of polyfunctional organic carboxylic acids and polyhydric alcohols, which reaction products contain at least two 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 ~uch lactones with polyhydric alcohols~
Typical of the polyfunctional organLc carboxylic acids that can be employed in producing polyester polyols useful in this invention are: dicarboxyLic aliphatic acids such as succinic,~adipic, sebacic, aæelaic, 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 aihydrides of any of these various acids can be employed in producing the polyester polyols.
The polyhydric alcoho~s (organic polyols) that can be employed in producing the polyester polyol starting 7.
11,931 3 ~
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; tr~methyolethane; pentaerythritol; propylene ~lycol; 1,2-, 1,3- and 1,4-butylene glycols; l,S-pentanediol;
sorbitol; and the like, incLuding mixtures thereof.
Other polyhydric alcohols that can be employed in producing the polyes~er polyols useful in this invention are the polymeric polyhydric alcohols which include the linear and branched chain polyethers having a plurality of acyclic ether oxygens and at leas~ 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 o the poly(oxyalkylene) polyols include the poly(oxyethylene) glycols prepared by the addition of ethylene oxide to water, ethylene glycol or diethyl~ne glycol; poly(oxypropylene~
glycols prepared by the addition of propylene oxide to water, propylene glycol or dipropylene glycol; mixed 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 ~ 11,931 Illustrative of further polyester polyols are the reaction 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 mLxtures thereof, wi~h any of the following: glycerol; trimethylolpropane, 1,2,6-hexanetriol; pentaerythritol; sorbitol; glycosides such as methyl, ethyl, propyl, butyl and 2-ethyLhexyl arabinoside, xyloside, ~ructoside, glucoside, and rhammoside; sucr^se;
mononuclear polyhydroxybenzenes such as resorcinDl pyro-gallol, phloroglucinol, hydroquinone, 4,6-di tertiary-hutylcatechol, and catechol; polynuclear hydroxyben2enes ("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 containing one to twelve carbon atoms, such compounds being typically illustrated by 2,2-bis(p-hydroxyphenyl)-propane, bis(p-hydroxyphenyl)-methane and the 20 various diphenols and diphenol methanes disclosed in United States Patent Nos. 2,506,486 and 2,744,882, respectively. Another type of polyester polyol is that produced by reaction o~ a polycarboxylic acid and the polyether adducts formed by reaction vf ethylene oxide, propylene oxide or butylene oxide with phenol-formaldehyde condensation products such as the novolaks.
~g) Phenolic resln 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 cresol, bisphenol-A, para-substituted phenols and the like while formaldehyde 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 hydroxyalkyl acrylate modified vinyl chloride polymers described above having (a) from about 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-ethylenically unsaturated carboxylic acids . 20 as described above and vinyl esters of saturated fatty acids as described above, the preferred polymerizable monomer being vinyl aceta~e, and (c) ~rom 10 to 30 weight percent mer units derived from hydroxyalkyl acrylate as described above, preferably hydroxypropyl acrylate. The most preferred polymer being a ~miformly hydroxyl-functional random terpolymer o~ about 80 weiy~ht percent vinyl chloride mer units, about 5 weight percent vinyl acetate mer units and about 15 weight percent hydroxypropyl acrylate mer units.
10 .
, B~
~ 31 With regard to the aminosilicon compounds and mixtures thereof of Formula I above it is to be understood that each X, R, Rl, R2, R3, a and t may be the same or different in any given aminosilicon compound and mixtures thereof. Moreover, illustrative radicals represented by X above include alkoxy radicals having 1 to 6 carbon~atoms, such as methoxy, ethoxy, propoxy, 2-methoxyethoxy, isopropoxy, hexyloxy and the like, the preferred alkoxy radicals being methoxy, ethoxy and 2-methoxyethoxy. Illustra~ive divalent alkylene radicals represented by R above include methylene, ethylene, propylene, isopropylene, butylene and the like, the preferred divalent alkylene groups being ethylene ~-C2H4-) and propylene (-C3H6-). Illustrative radicals represented by Rl above include alkyl radicals such a.-;
methyl, ethyl, propyl, isopropylJbutyl and the like.
Illustrative radicals represented by R2 above include hydrogen, ~lkyl radicals such as methyl, ethyl~ propyl, isopropyl, butyl and the like, as well as silyl groups of the formula Ra -R-Si~X3-a whexein R, Rl, X and a are the same as defined above. In those amlnosilicon compounds of Formula (I) tnat contain only one silicon atom R2 is preferably hydrogen. Illus-trative divalent alkylene groups represented by R3 above include ethylenel propylene, isopropylen~, butylene, and the like, the preferred divalent alkylene groups being ethylene and propylene. In the more preferred organosilicon compounds a is preferably O and t is preferably 1.
11 .
11, g31 3~
Illustrative aminosilicon compounds that may be employed in this invention include, for example (CH30) 3siCH2NH2 (C2H$0)3Si(CH2)3NH2 ( I;:H30~ 3Si ( CH2 ) 3MH2 ( CH30) 3S i (CH2 ) 3~HCH3 (C3~170)3Si(CH2)3N}~2 (CH30C2H40)35i(CE2)3NH2 (C2H50)2CH3Si(CH2)3~H2 ( C2H50) 2 CzH5 Si ( (~H2 ) 3NH2 (C2HsO)3si (~2)2NH2 (c2H5o)3sicH2cH2cH(cH3)NH2 (C2H50)3si(cH2)4NH2 (CH30)3Si(CH2)3N~(CH2)2NH2 (c4H9o)2(cH3)sitcH2)3NHcH3 ( CH30) 3S~ ) 3N ( C2H5 ) 2 : .
( CH30) 3Si ( CH2 ) 3 (NHC2H4) 2NH2 (CH30) 3Si (~2) 3 (NHC2H4) 3NH2 ~C2H50)3Si(c~H2)3NH(c~2)3si(oc2H5)3 ( CH30) 3Si (CH2 ) 3N~ (CH2 ) 2NE~ ( CH2 ) 3 ( 3 3 (c2H5o)3si(cH2)3~(cH2)3si~oc2H5)3]
(CH2 ) 3Si (OC2H5) 3 ( ( ~3o) 3~ 2 ) 3 ~NH ( cH2) ~ ] 2NE~ si (OCH3)3 (c~30)3Si(CH2)3 ~NH(CH2~2]3~H(CH2)3 (OCH3) 3 (CH30)3Si(CH2)3NH(CH2)2N[(CH2)3Si(OCH3)3]-(CH2)3Si(C~CH3)3 ~CH30~ 3Si ~ CH2 ) 3N ~ 2 ) 3Si (Oc~3) 3 ] (CH2 ) 2N
(cH2)3si(ocH3)3] (CH2)3SilOCH3)3 8~ 31 ~C2H50)3si(cH2)3NH(cH~2NH(c~2)~
Si(OcH3)3 (CH30CzH40)3Si(CH2)3NH(cH2)2 ( 2 3 Si(oc2H4oc~3)3 and the like, as well as mixtures thereof.
The aminosilicon compounds and mixtures of Formula (I) above which can be used as the silicon co~ponent or the compositions of this invention are also well known in the art as are methods for their preparation. Thus, with regard to the aminosilicon compounds and mixtures thereof employable in this invention it is to be understood that while a single type of aminosilicon compound or mixtures of various combinations of different aminosilicon compounds can be used, it is not nece~ssary to form said mixtures by combining individually isolated aminosilicon compounds, although such may be done if desired. For example, it is well known in the ar~ that am~nosilicon compounds such as the polyamino silanes and multiple silylated aminosilicon compounds of Formula (~) above are~normally produced in the form of a mixture consisting essentially of different types of such aminosilicon compounds of Formula I above due to the mann2r in which they are generally prepared. For instance, in the conventional reactions employed to produce polyaminoalkylene silanes or multiple silylated polyaminoalkyl~ne compounds, e.g. by the reaction of an alkylenediamine and a haloaLkyl silane or by the reaction of an aminoalkyleneaminoalkylene silane and a haloalkyl silane~
~ ~ ~3~1 11,931 _~--J~
in addition to the desired product, the crude reaction product can be expected to consist of a mixture of symmetrical and unsymmetrical bis, ~ris and tetrakis silyl compounds, and the like, due to the multiple amino reaction ~ites on the amino starting material. Accordingly, included within the definition of the aminosilicon compounds that can be employed in the composi~ions of this inveation are such crude aminosilicon compound reaction products that contain mor~ than one amino group and/or silyl group as shown by Fonmula (I) above. Indeed, since the more pre-ferred aminosilicon compounds e~ployable in this invention are ~hose containing more than one am no group and/or more than one silyl group it is generally preferred to employ th2 crude reaction product mixture obtained upon producing the type of aminosilicon compound that one wishes to use in the particular composition of this invention desired ~or a particular end result, since such eliminates the time and efort caused by additional procedural s~eps necessary.
in preparing and isolating any particular singular amino-silicon compound prior to its use herein.
Accordingly, the more preferred aminosilicon com-pounds employable in this invention are those o~ Formula (I) above wherein at least one R2 group represents a silyl radical of the for~ula la -R-Si3_a and mixtures thereof, wherein R, Rl and a are the same as defined above, e.g. ~H3O)3Si(CH2)3NH(CH2)2NH(CH2)3 Si(OCH3)3O
14.
3~88 11, 931 Moreover, due to the fact that the present lnver.tion allows for the use of the crude reactiun product mixtures of said preferred aminosilicon compounds produced by either above described conventional procedures thereby rendering it unnecessary to obtain a single species of the desired aminosilicon compound, the more preferred aminosîlicon compound component of this invention is a crude aminosilicon reaction product mixture having an average empirical mole ratio of the following structural units [~ ~x ~A) [~N-R3)tN-] (B) a ~R-Si-X3_a]y (C~
wherein R, Rl, R3, a, and t are the same as defined above, with Rl preferably being a hydrogen radical, t preferably having a value of 1 to 2 and a preferably being 0; while x has a value o O to 6 preferably 1 to 4, ~ has a value of 1 to 6, preferably 2 to 5; the su~ sf x + ~ being a value of 3 to 6, preferably 4 to 5. Of course it is understood that said structural units (A) and (C) are both directly bonded to said structural uni~ thereby satisfying all of the ~ree valences of said structural units (A), (B) and (C).
The most preferred aminosilicon compound employable ln the composition of this inventlon i.s a crude aminosilicon ~3~38 ~l,g3l reaction produce mixture having an average empirical mole ratio of the following structural units [H~x (A) [-N-CH2CH2-N-~ ~B) ~ (CH2)3-Si-(0CH3)3]y (C) wherein x has a value of 0 to 3; ~ has a value of } ~o 4, preferably ? to 4; the sum of x + ~ being 4; said structural units (A) and (C) both being directly bonded ~o said stxuc-tural unit (B) thereby satisfying all of the free valancesof said structural units (A), (B) and (C).
The hydxoxyl-containing organic polymer-amino-silicon compositions of this invention are unifonmly blended solutions containing about 5 to about S0 parts by weight, and more preferably about 10 to abou~ 40 parts by weight of the aminosilicon compound per 100 parts by weight of the organic polymer, and can be prepared by merely mechani-cally mixing said ingredients together along with other various ronventional components that may be included if desired in the room temperature curable compositions. The particular design of n~xing equipment and the method and order o the various components is not critical, although it is pre~erred to add ehe aminosilicon 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 16.
~;23~B8 11, 931 o the various components should be conducted under substantially anhydrous type conditions, such as closing the equipment so that the ambient atmosphere can be contro~led. Moreover~ since the compositions of this invention are mildly basic in nature, it is desirable to exclude or control their contact with any acidic or potentially acidic environmental components such as S02, C02, or HCl which m~y be in the a~mosphere. I~ may also be desira~le to dry or dehydrate any additional components whic~ are added.
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 o~ the cured composition without increasing the viscosity of the curable composi-tion, filiersS 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 em~loyed will of course merely depend on the ultimate end use desired for the compositions of this invention.
The hydroxyl-containing organic polymer-amino-silicon compositions of this inventioll have a wide variety of utility such as in the fields of coatings, laquers, paints, inks, dyes, tints, impregnations, adhesives, caulks, sealants and the like. Said compositions are 17.
~ ~ ~ 3 ~ ~ ~ 11,931 especially useful as room temperature curable coating compositions which may be applied over a wide variety uf 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 (cro~sLinked) pro~ective and/or decorative solvent resistant coatings are desired, such as in the fields of main~enance and ~rine coatin~sO
For exampLe, the compositions of this invention when kept anhydrous have been found to provide excellent protective and solvent resistant cured coatings for metals merely by air drying the curable coatLng composition at room (a~bient) temperature after it has been applied to the metal. ~ormally, the ambient moisture in the air is sufficient to cure (crossLink) the coating into a dry, hard corrosion and solvent resistant protective film on the metal. The curable composition generally becomes dry very quickly and cured coatings having excellent properties have been achieved within 24 hours ~fter coating the substrate. Of course, it i5 to be understood that the curing may be accelerated, ~f desired, by the employment of elevated temperatures.
18.
~ 11,931 In addition to the surprisingly excellent solvent resistance of the cured compositions of this invention such cured coatings have also been found to have good impact strength, weatherabllity and environ~ental resistance as exhibited by their good stability against salt sprays, and against chalking on exposure to sunlight, as well as their resistance to deteriora~ion, corrosion and blistering upon being immersed in both fresh water and seawater for prolonged periods of time. Of course it is to be under-stood tha~ the ultimate properties of any given roomtemperature curable coating composition will depend upon such obvious factors as the various ingredients employed, their concentrations, the crosslinked density of the final composition, and the like. However, the optimum results desired for any composition is well within the bounds of routine experimentation.
While not wishing to be bound by any particular theory of mechanism involved, it is believed that the aminosilicon compound reacts with the polymer via transesterification followed by hydrolysis of the silane portion. Experiments have indicated that the aminosilicon compound i5 bound to the hydroxyl containing polymer through an Si.-O-C bond via transesterification which then upon exposure to the ambient moisture in the air hydrolyzes and cures (crosslinks) into a solid fil~.
The most preferred coating composition of this invention are those consisting essentially of a hydroxyalkyl 19 .
11,~31 ~ ~ ~ 3 ~ ~ 8 acrylste modified vinyl chloride polymer as defined above and a hydrolyzable aminosilicon 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 100 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 lQ0 par~s by weight of said polymer; 0 to about 25 parts by weight of an alkyl sili-cate per 100 parts ~y weight of said polymer; and 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 weigh~ of a dessicant. The most preerred hydroxyalkyl acrylate modified vinyl chloride polymers and aminosilicon compounds useful in ~his invention have already been defined above. In general a typical coating composition will consist of about 10 to 35 per cent by weight of said hydroxyalkyl acrylate modified vinyl chloride polymer based on the total weight of the composition. Of course, it is obvious that the particular additives employed are not critical and any suitable solvent, pigment, filler, alkyl silicate, dispersing agent and dessicant can be employed~ ~n 2~) o ~ 3~ g3l general, the preferred solvents are methylisobutyl ketone, xylene and mixtures thereof, while the preferred pigment is titanium dioxide and the preferred de~sicant is molecular sieves.
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 e~uipped with a stirrer, condenser and vat scrubber. The hydrogen chloride by-product is removed by re1ux which may be carried out at reduced or atmospheric pressure.
Through this process, the most common products TEOS
(tetraethyl 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 detenmines the degree of hydrolysis in the final 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 containing 40% SiO2), and Ethyl Silicate P-18, having an 80 to as per cent hydrolysis level.
The following examples illustrate the present invention and are not to be regarded as limitative. All 21.
. _ ,.
~ 11,931 parts and percentages are by weight unless otherwise specified .
For the sake of brevity in the ~xamples, the designations in the first column of Table I will be used in lieu of the complete description given in the second column.
TABL~ I
Desi~nation Com~sition o Polymer A A uniformly random hydroxyl-functional terpolymer of 80% vinyl chloride mer units, 5% vinyl acetate mer units and 15% hydroxypropyl ~crylate mer units.
Inherent viscosity is 0.3.
Polymer B A partiaLly hydrolyzed polyvinyl a:Lcohol - terpolymer o 91% vinyl chloride mer units, 3% vinyl aceta~e mer units and 6% vinyl alcohol mer units. Viscosity is 60 cps (20% resin in methyl ethyl ketone). Sold by Union Carbide Corpor-ation under the product designation VAGH.
Polymer C A thermoplastic poLyhydroxyether phenoxy resin polymer having a specific gravity of 1.18 and sold by Union Carbide Corporation under the product designation PKHH.
Polymer D A bisphenol A-formaldehyde phenolic resin containing approximately 16% methylol groups, sold by Union Carbide Corporation under the product designation BK-S~18.
Polymer E A polyhydroxyl containing acrylate poLymer so7d by Rohm & Haas under the product designation Acryloid AT-56.
Polymer F A polyvinyl butyral resin polymer contain-ing 1% vinyl acetate mer units and 20%
vinyl alcohol mer units having an Inherent viscosity of 0.90 and sold by Union Carbide Corporation under the product designation XYE~.
2~o 11, 9~1 TABLE I (cont'd.) Desi~na~ion Composition Nuospers ~ 657 A dispersing agent supplied by Tenneco, Inc.
ES-40 A partially hydrolyzed ethyl poLy-silicate containing 40 percent by weight of SiO2.
TEOS Unhydrolyzed tetraethyl orthosilicate.
Silane A A commercial gxade silane designated as N-beta-(Aminoethyl)-gamma-aminopropyl-trimethoxy-silane sold under the pro-duc~ name A-1120 by Union Carbide Corporation.
Silane B A silane having the formula (c2Hso)3si(cH2)3NH2 Silane C The crude aminosilane reaction product mixture of ~xample A of this application.
Silane D A silane having thP formula (cH3o)~si(cEl2)3NH(~2)~NH2 distilled from Silane A
Silane E A silane having the formula (CH30)3Si(CH2)3NH2 Silane F A silane having the formula (cH3o)3sicH2c~2si(oc~3)3 SiIane G The crude aminosilane reaction pro-duct mixture of Example B of this application.
Silane H The crude aminosilane reaction product mixture of Example C of this appli-cation~
EXAMPLE A
An aminosilicon compound was prepared by reacting 399.8 grams (1.8 moles) of an aminosilane having the forIula (CH30)3Si ~CH2)3NH(cH2)2NH2 (which was distilled from Silane A) with 357.7 grams ~1.8 moles) of a silane having the formulR
23.
~ 3 ~ ~ ~ 11,931 (C~30)3Si(CH2)3Cl at 110C. for an hour. The reaction product was then cooled to room temperature and treated with 108.2 grams (1.8 moles) of ethylene diamine to remove HCl from the reaction product which was then stripped to 175C under vacuum (0.5 mm Hg~ to remove all lites up to the amino-silane starting m2terial. About 650 grams of a cxude aminosilicon reaction product mixture was ob~ained which had an Amine Equivalent of 1.72 grams-nitrogen and consisted essentially of 2 major amount of aminosilicon compounds having the following mole structural unit ratios: :
L H~ ~-N- C2H4- N-~ r~CH2 ) 3S i ( OCH3 ) ~H~ LN-C2H4-N-] ~CX~)3Si(OCH3) and r, ~ 1 r ¦ -N-C2~4-N i ~CH2)3Si(OC~3)3 ~
and a minor amount of unreacted (CH30)3Si(~2)3NH(c~2)2NH2 starting material. As employed in this application the crude reaction product mixture o this Example is desig-nated Silane C.
~e~
An aminosilicon co~pound was prepared by reacting 2443 grams (11.0 moles~ of Silane A (12.6% titratable nitro~
gen~ with 1747 grams t8.8 moles) of a silane having the formula 2~o ~ ~ 3 9 ~ ~ 11,931 (CU30)3si-tcH2)3cl at 110+10~C. for four hours. The reac~ion product was then cooled to room~temperature and treated with 529 grams (8.8 moles) of ethylene diamine at 60C. to remove HCl from the reaction product which was then stripped at 100C./40m~ Hg. to remove the residual ethylene diamine.
About 3576 grams of a crude aminosilicon reaction product mixture was obtained. Gas chrom~tographic ~nalysis of the crude reaction product mixture showed it to consist essentially of about 30 percent by weight of an amuno-silicon compound having the following mole ratio of structural units [ ~3~ E!N- CH2CH2N-~ ~EC'H2 ) 3Si (OCH3)~
about 24 percent by weight of an aminosilicon compound h~ving the following mole ratio of structural units [H ~ [ ~_C2H4-N-~ ~ CH2)3Si(cH3) ~ 3 about 5 percent by weight of an aminQsilicon compound having the following mole ratio of structural units L-N- CH~CH2 -N-~ ~CH2)3Si(OCH3)3~
about 19 percent by weight (CH30)3Si~CH~)3~(~H2)2NH2 and about 5 percent by weight of (CH30)~Si-0-li(OCH3)2 H2N(CH~)2HN(CH2)3 (CH2)3NH(CH2)2 2 the remainder of the reaction product consisting essentially of mix non-eluting polysiloxane polymers. As employed in 25.
, ~ ~ 11,931 this application the crude reaction product mixture of this Example is designa~ed Silane G.
EXAMPLE C
An aminosilicon compound was prepared by repeating Example II on a plant scale. 400 pounds of Silane A was reacted with 286 pounds of (CH30)3Si(CH2~3Cl at about 110C. for about three hours. The reaction product was cooled to about 70C. and ~reated with 130 pounds of ethylene diamine in an agitator for 30 minutes and 183 pounds of hydrochloride by-product ~chloride content 31.7%) was removed from the reaction product.
The reaction product was then stripped at 100C./47~m Hg.
for two hours to rem.~e 6 pounds oX lites. Upon cooling and filtration 590 pounds of a crude aminosilicon reaction product mixture was obtained which consisted of a major amount o aminosilicon compounds having the following mole structural unit ratios:
~H~ EN~ C~H4-N-~ ~CH2 ) 3Si (OCH3) 3]2 1~ ~ E 2H4 N-~ ~LCHZ)3Si(OCH3)3]
and ~ N-C2H~-N~ CH2)3Si(~C~3)J4 and a minor amount (about 15.1 percent by weight) of unreacted Silane A. As employed in this application the crude reaction product mixture of this Example is designated Silane ~1.
26.
~ 3 ~ ~ 11931 A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared having the following total formulation Com ound Parts by Wei~ht p Pol~mer A 25.45 Titanium Dioxide 19.09 Methylisobutyl Ketone 27.57 Xylene 27.57 Nuosperse 657 0.32 ES-40 Varied~
Silane A Varied*
*Parts by weight given in Table II 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 with c~irring and the mixture ground in a pebble mill o~ernight. The amino-silane compound was then added with stirring as was the ethyl silicate when used until a uniform coating com~o-sition was obtained. Each coating composition was then thinned to a No. 4 Ford cup viscosity of 20-25 sec~nds by the addition of a 50/50 weight percent solvent blend of methylisobutyl ketone and xylene. Each coating compositLon was then sprayed onto aluminu 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 ~aving been air dried at room ~emperature for various periods of time was then measured by subjecting each air dried coating to double MEK rubs and the results of this 27.
~ 398~ 11931 test are reported in Table II 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 MEK rub rating of five means that the metal surface of the panel was exposed after the methylethylketone saturated cloth was rubbed back and ~orth (2 strokes) over the coating a ~otal of five times. Thus the higher the numerical double MEK
rub rating obtained for a given coating the more solvent resistant the coating is.
The solvent resistance of each coating on said panels after having been air dried at room temperature for various periods of time was also measured by a solvent extraction test and the results of said tests are reported in Table II below. Said test involves measuring ~he difference in weight of the air dried coated panel before and after immersing the coated panel in boi~ing methyl-ethy~ketone for 18 hours in order to obtain the weight ~0 percent of eoating extracted from the test panel. Thus the lower the weight percent of coa~ing that is extrzcted for a given coating, the more solvent resistant the coating 28.
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29 .
9 ~ ~ 11931 The above results of T~BLE II de~onstrate thatthe hydroxyl containing polymer-aminosilane compositions of this invention can be empLoyed as room temperature crosslinkable coating composi~ions to provide very good solvent resistant coatings; that the solYent resistance of said coatings increases with time and levels off; that there is a direct correlation between the solvent extraction test and MEK rub test, as the MEK rub rating increases the percen~ extractables decreases; and that no ethyl siLicate is necessary to obtain excellent solven~ resistant coatings ~Examples 17 and 18)~ while coatings obtained from formu-lations having little or no amino silane (Examples 1 and 16) have little if any solvent resistance.
A hydroxyl containing organic polymer~amino-silicon coating composition having ~he following total formulation .
ComPound ~ Parts by Wei~
Polymer A 25.45 Titanium Dioxide 19.09 Methylisobutylketone 27.57 Xylene 27.57 Nuosperse 657 0.32 ES-40 6.36 Silane A 6.4 : . was prepared and thinned to a spray viscosity in the same manner as described in Examples 1-18, The coating compa-sition was then sprsyed on to a series of zinc rich prlmed steel panels to glve a top coating of about 2 mals and the top coatings on said panels cured by allowing them to air dry at room temperature for two weeks. The cured top coated steel panels were then ested for resistance against 3~, ~L~88 11931 salt spray, synthetic seawater immersion and fresh water immersian and exhibited excellent results. The cured top coating of the panels tested exhibited no been deterioration after (a) having/subjected to a salt spray for lOOO hours, (b) after having been immerse~ in syn-thetic seawater for lOOO hours, ~nd ~c) after having been immersed in fresh water for 1000 hours. Said top coated steel panels were also tested ~or adhesion of the top-coating to the pr~mer by a cross-hatch adhesion test with Scotch tape after having undergone the above three envir~
onmental tests. The only adhesion failure observed in each instance was cohesive failure of the primer ~o the steel.
EX~MPLES ~0-23 A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared in the same manner as described in Examples 1-18 having the following total formulations.
~ Parts By Weight --Compound Example Example Example Example 21 22 _ 23 Polymer A 25.45 25.45 25.4525.45 Titanium Dioxide19.09 1~.09 19.0919.09 Methylisobutyl Ketone 27.57 27.57 27.5727.57 Xylene 27.57 27.57 27.5727.57 Nuosperse 657 0.32 0.32 0.320.32 ~S-40 8 - - -Silane A - 8 - 4 Silane B 8 - - -Silane C - - 8 3~.
8~ 1931 Each coating composition was then appLied ~o sand blasted steel panels by a draw down bLade to give a coating thick-ness of about 1-1/2 to 2 mlls thick 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 periods of time was then measured by subjecting each air dried coating to double acetone rubs and the results of this test are reported in Tabl~e III below. Said test is the same as the double MEK rub test given in Exa~ples 1-18 save for the fact that acetone was used as the solvent instead of methylethylketone.
TAB~E III
Example ~ -Double Acetone Xubs~
No. 1 Day 3 Days 1 Week 2 Weeks 1 Month 8 - 100+ - -22 100~
23 3 - 2~ 35 ~Double acetone rubs were stopped after reaching 100.
In addition the cured coating composition of Example 23 after having been cured by air drying at room temperature for 24 hours exhibited an i~pact strength of grea~er than 160 inch pounds, both direct and reverse, on a Dart Impact Tester, while the same coating without the aminosilane had an impact strength of less than about 20 inch pounds.
._ A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared in the same 32.
~ 3 ~ 11931 manner as described in Examples 1 18 having the following total formulation _ _ Compound Parts By Weig~t Polymer A 25.0 Titanium Dioxide 19.0 Methylisobutyl Ketone 28~0 Xylene 28~0 Silane* ~,o *The particular silane employed in each composition is given in TABLE IV below, Each coating composition was then applied to sand blasted steel panels by a draw-down blade to give a coating of about 2 mils thick and the coa~ings on said panels cured by allowing them to air dry at room tempera-ture. The solvent resistance of each coating ater having been air dried at room temperature for various periods of time was then measured by the same double acetone rub test desc:ribed in Examples 20-23 and ~he results of said test are given in Table IV below.
TAsLE IV
Exa~ple 5ilane ~ Double Acetone Rubs -- -No. . Used ~ 5 Days2 Weeks 6 Ueeks 24 Silane C 100+ - - -Si}ane A 25 69 100~ ~ -26 Sila~e D 16 45 100~ - -27 Silane E 20 23 100+ - -28 Silane B 5 24 29 100~
29 Silane F 9 5 8 - 16 ~Double acetone rubs were stopped a~ter reachin~ 100. r A hydroxyl containing organic polymer-aminosilicon coating composition was prapared in the same manner as described in Examples 24-29 having the following total formulation.
~ ~ 3 ~ ~ ~ 11931 __Co~ound _~ Parts by Wei~
Polymer A 25.0 Titanium Dioxide 19.0 Methylisobutyl Ketone 28.0 Xylene 28.0 ES-40 12.0 Silsne A 12.0 The composition so prepared was coated onto a sand blasted steel panel and tested for solvent resistance in the same manner as described in Examples ~4-29. The results of the double acetone rub test are given in Table V below.
TABLE V
Example Double Acetone Rubs No.~ 2 Weeks 16 100+
+Double ~cetone rubs were stopped after reaching 100.
A hydroxyl containing organic polymer-aminosilicon coating composition having the follo~ing tot~l formulation Compound _arts by Wei~_t Polymer A 24 Titanium Dioxide 18 Methylisobutyl Ketone 26 Xylene 26 Nuosperse 657 0.3 Silane A 4.8 was prepared and thinned to a spray viscosity in the same manner as described in Examples 1-18. The coating composi-tion was then sprayed onto a sand blasted steel panel to give a coating thickness of about 1~5 mils and the coating cured by allowing it to air dry at room te~perature for 24 hours. Said cured coating exhibi~ed an impact strength of about lZ4 inch pounds, bo~h direct and reverse, on a Dart Impact Tester~ while a similar cured coating without 34.
~39~38 ll, 931 the aminosilane compound failed below 28 inch pounds on both tests. o A hydroxyl con~aining organic polymer-amino^
silicon coating composition having the following total ormu1ation.
Compound _ Parts By Wei~ht Polymer A 30.7 Titanium Dioxide 23.0 Methylisobutyl Ketone 23.0 Xylene 23.0 Nuosperse 657 0.3 Silane G 6.14 was prepared a~d thinned to a spray viscosity in the same m~nner as described in Examples 1-18. The coating composition was then sprayed on to a series of four diferent primed steel panels to give a top coating of about 2-3 mils over the various primed steel panels.
The top coatings on said panels were then cured by allowing them to air dry at room temperature for two weeks.
The cured topcoated steel panels were then ~ested for res~stance against blistering a~d corrosion by subjecting two top coated panels from each primed panel ca~egory to (1) a 5% salt water ~pray test for 1000 hours, (2) to synthetic seawater immersion for 1000 hours and (3) to fresh water immersion or 1000 hours. No corrosion or bListering was observed for any o the top coated panels so tested~
~ 3 ~ ~ 8 A series o~ hydroxyl containing organic polymer-aminosilicon coating compositions were prepared in the same manner as described in Examples lW18 having the following total formulation.
ComPound _ _Parts_b~ Wei~ht Polymer ~ 20 Titanium Dioxide 14 Methylisobutyl Ketone 32.85 Xylene 32.85 Nuosperse 657 0.3 5ilane G Varied *Parts by weight given in Table VI below.
Each coating co~position so prepared was then applied to a series of aluminum panels by a draw down blade 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 cured coating on said panels after having been air dried at room ~ temperature for various periods of time was measured by subjecting each air dried coating to the same double MEX
rub test described in Examples l-L8 and the results of said test are given in Table VI below.
TABLE VI
E~le Silane G - Double ~ER Rubs - -No. (Parts by wt,) 24 hrs. 48 hrs. 72 hrs. 1 Week 33 4 10~
34 3 ~0 ~0 59 90 + Double MEK rubs stopped after reaching 100.
36.
1193:L
~ 2 ~
EXAMPLFS 36 and 37 A series of hydroxyl containing polymer-amino-silicon coating compositions were prepared in the same manner as described in Examples 1-18 (the molecular sieves being added with the titanium dioxide pigment) having the following total ormu1ations Parts By Weight _ Compound_ _ _ Example 36 Polymer A 25.45 25.45 Titanium Dioxide 19.09 19.09 Methylisobutyl Ketone27.57 27.32 Xylene 27.57 27.32 Molecular Sieves 4A - 0.5 Nuosperse 657 0O3 0.3 Silane H Varied~ Varied~
~Parts by weight gLven in Table VII below.
Each coating composition so prepared was then applied to a series of aluminum panels by a draw do~
blade to give a coating thicknesc 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 c:ured coating on said panels were then measured by subJecting esch cured coating to the same double MEK rub test described in Examples 1-18, both before and after said cured coatings had undergone various hydrolytic stability tests. The results of said double MEK rub tests are given in Table VII below.
~23~
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A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared having the following total formulations.
~ Parts By Weight ~
Compou~d _ _ Example 38 Ex =~le 39 ExamPle 40 _~E~ L
Polymer C - 17~5 - -Poly~er D 38.5 - - -Pol~me~ E - - 66 Polymer F - ^ - 9.1 Titanium Dioxide 23 12.5 8 6.3 Xylene - - 23 ~ethyl Ethyl Keto~e 38.5 - - -Cellosolve Acetate - 57 -. -Toluene ~ 13 - -Butyl Alcohol - - 3 17.7 Isopropyl Alcohol - - - 66.9 ÆS-40 6 ~ 8 Silane C 6 2 8 4 Each polyol was dissolved in the solvent or solvent blend employed and ~itanium dioxide added while mixing with a high speed disperser until a Hegman fineness of grind of 6 to 8 was obtained. The ethyl silicate if used was then added followed by the aminosilane with stirring until a uniform coating composition was obtained. Each coating composition was then applied to sand blasted steel panels with a draw down blade to give a coating thickness of about 2 ~ils. The coatings on said panels were then cured by allowing them to air dry at room temperature and the solvent resistance of each cured coating after having been air dried at room temperature for various periods of time measured by the same double acetone rub test described in Examples 20 to 23. I'he results of said test are reported in the following table.
3g.
T LE VlII
Example -- Double Aceto~e Rubs--~~~~~~
No. 24 Hours 4 DaYs1 Week2 Weeks 1 MDnth 38 - 12 1~ 14 15 39 26 62 76 - 100+
41 86 70 73 - 100+
Double acetone rubs stopped after reaching 100, E~AMPLES 42 to 49 A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared having the following total formuLations - -- Parts By Weight -- -CoIpound _ E~.42 Ex,43 Ex.44 Ex.45 Ex,46 Ex.47 Ex.48 Ex~49 Polymer A 25.45 25,45 25.45 25.45 25.45 25045 25,45 25.45 Titanium Dioxide 19.09 19~09 19,09 19.09 19.09 19~09 l.9.09 19.09 Methylisobutyl 27.57 27.57 27.57 27,57 27.57 27,57 27.57 27.57 Ketone Xyle~e 27.57 ~7.57 27.57 ~7.57 27.57 27.57 27,57 27.57 Nuosperse 657 0.32 0.32 0,32 0.32 0.32 0~32 0.32 0.32 M~lecular Sieves - - 0.5 0.5 2.55 2.55 2.55 2.55 Methanol - 2 - 2 - ~ - 2 Distilled Water 1.2 1.2 1~2 1,2 1.2 1.2 1.2 1,2 Silane H 5.08 5.08 5.08 5.08 5,0 5,0 5,0 5.0 Each composition was prepared by dissolving the solvent in the solvent blend followed by addition of the titanium dioxide, molecular sieves and Nuosperse 657 while mixing in a high spee~ disperer until a finely ground mixture was obtained. The water, methanol and silane~ in that order, were then stirred into the composition until a uniform coating composition was obtained. Each coating composition was then applied to sand blasted steel panels with a draw down blade to give a coating thickness of about 2 mils. The coatings on said panels were then curèd by allowing them to air dry at room temperature and the solvent resistance of each cured coa~ing after having been 40.
air dried at ~ario~s periods of time measured by the same double MEK rub test described in Examples 1-18.
The results of said test are given in the following tzble.
TABLE IX
- Double MEK Rubs Example No. 24 Hours 8 Days ~3 22 100+
44 12 ~0+
47 25 100~
4~ 50 100+
~Double MEK rubs stopped a~ter reaching 100.
EXAMPLES 50 and 51 A series of hydroxyl containing pol~mer-amino-silicon coating compositions were prepared in the same manner as described in E~amples 36 and 37 having the following total formulations.
- Parts by Weight ComPound _ _ Exam~le 50 Polyol A 25.45 25.45 Titanium Dioxide 19.09 19.09 Methylisobutyl Ketone~ 27.57 27.32 Xylene 27.57 27.32 Nuosperse 657 0.3 ~3 Molecular Sieves 4A ~ 0.5 Silane A 1.28 1.28 Each coating composition so prepared was then applied to alllm1num panels by a draw down blade to give a coating of about 2 mils and the coatings on said paneLs cured by allowing th~m to ai.r dry at room temperature.
The solvent resistance of each cured coating on said panels was then measured after having been air dried at 41.
~2~t~
various periods of time by the same double MEX rub test described in Examples 1-18. The results of said test are given in the following table.
-- TABLE X
Example ~ Double MEK Rubs - -_ No. 1 Week 2 Weeks 3 Weeks _ Month 2 Months 23 47 ~0 100 51 38 73 100+ ~00~ 100 +Double MEK rubs stopped after reaching lOO.
Various ~odifications 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 claLms.
42.
The preferred hydroxyl containing organic thermo-plastic polymer components of this invention are the hydroxyalkyl acrylate modified vinyl chloride polymers described above having (a) from about 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-ethylenically unsaturated carboxylic acids . 20 as described above and vinyl esters of saturated fatty acids as described above, the preferred polymerizable monomer being vinyl aceta~e, and (c) ~rom 10 to 30 weight percent mer units derived from hydroxyalkyl acrylate as described above, preferably hydroxypropyl acrylate. The most preferred polymer being a ~miformly hydroxyl-functional random terpolymer o~ about 80 weiy~ht percent vinyl chloride mer units, about 5 weight percent vinyl acetate mer units and about 15 weight percent hydroxypropyl acrylate mer units.
10 .
, B~
~ 31 With regard to the aminosilicon compounds and mixtures thereof of Formula I above it is to be understood that each X, R, Rl, R2, R3, a and t may be the same or different in any given aminosilicon compound and mixtures thereof. Moreover, illustrative radicals represented by X above include alkoxy radicals having 1 to 6 carbon~atoms, such as methoxy, ethoxy, propoxy, 2-methoxyethoxy, isopropoxy, hexyloxy and the like, the preferred alkoxy radicals being methoxy, ethoxy and 2-methoxyethoxy. Illustra~ive divalent alkylene radicals represented by R above include methylene, ethylene, propylene, isopropylene, butylene and the like, the preferred divalent alkylene groups being ethylene ~-C2H4-) and propylene (-C3H6-). Illustrative radicals represented by Rl above include alkyl radicals such a.-;
methyl, ethyl, propyl, isopropylJbutyl and the like.
Illustrative radicals represented by R2 above include hydrogen, ~lkyl radicals such as methyl, ethyl~ propyl, isopropyl, butyl and the like, as well as silyl groups of the formula Ra -R-Si~X3-a whexein R, Rl, X and a are the same as defined above. In those amlnosilicon compounds of Formula (I) tnat contain only one silicon atom R2 is preferably hydrogen. Illus-trative divalent alkylene groups represented by R3 above include ethylenel propylene, isopropylen~, butylene, and the like, the preferred divalent alkylene groups being ethylene and propylene. In the more preferred organosilicon compounds a is preferably O and t is preferably 1.
11 .
11, g31 3~
Illustrative aminosilicon compounds that may be employed in this invention include, for example (CH30) 3siCH2NH2 (C2H$0)3Si(CH2)3NH2 ( I;:H30~ 3Si ( CH2 ) 3MH2 ( CH30) 3S i (CH2 ) 3~HCH3 (C3~170)3Si(CH2)3N}~2 (CH30C2H40)35i(CE2)3NH2 (C2H50)2CH3Si(CH2)3~H2 ( C2H50) 2 CzH5 Si ( (~H2 ) 3NH2 (C2HsO)3si (~2)2NH2 (c2H5o)3sicH2cH2cH(cH3)NH2 (C2H50)3si(cH2)4NH2 (CH30)3Si(CH2)3N~(CH2)2NH2 (c4H9o)2(cH3)sitcH2)3NHcH3 ( CH30) 3S~ ) 3N ( C2H5 ) 2 : .
( CH30) 3Si ( CH2 ) 3 (NHC2H4) 2NH2 (CH30) 3Si (~2) 3 (NHC2H4) 3NH2 ~C2H50)3Si(c~H2)3NH(c~2)3si(oc2H5)3 ( CH30) 3Si (CH2 ) 3N~ (CH2 ) 2NE~ ( CH2 ) 3 ( 3 3 (c2H5o)3si(cH2)3~(cH2)3si~oc2H5)3]
(CH2 ) 3Si (OC2H5) 3 ( ( ~3o) 3~ 2 ) 3 ~NH ( cH2) ~ ] 2NE~ si (OCH3)3 (c~30)3Si(CH2)3 ~NH(CH2~2]3~H(CH2)3 (OCH3) 3 (CH30)3Si(CH2)3NH(CH2)2N[(CH2)3Si(OCH3)3]-(CH2)3Si(C~CH3)3 ~CH30~ 3Si ~ CH2 ) 3N ~ 2 ) 3Si (Oc~3) 3 ] (CH2 ) 2N
(cH2)3si(ocH3)3] (CH2)3SilOCH3)3 8~ 31 ~C2H50)3si(cH2)3NH(cH~2NH(c~2)~
Si(OcH3)3 (CH30CzH40)3Si(CH2)3NH(cH2)2 ( 2 3 Si(oc2H4oc~3)3 and the like, as well as mixtures thereof.
The aminosilicon compounds and mixtures of Formula (I) above which can be used as the silicon co~ponent or the compositions of this invention are also well known in the art as are methods for their preparation. Thus, with regard to the aminosilicon compounds and mixtures thereof employable in this invention it is to be understood that while a single type of aminosilicon compound or mixtures of various combinations of different aminosilicon compounds can be used, it is not nece~ssary to form said mixtures by combining individually isolated aminosilicon compounds, although such may be done if desired. For example, it is well known in the ar~ that am~nosilicon compounds such as the polyamino silanes and multiple silylated aminosilicon compounds of Formula (~) above are~normally produced in the form of a mixture consisting essentially of different types of such aminosilicon compounds of Formula I above due to the mann2r in which they are generally prepared. For instance, in the conventional reactions employed to produce polyaminoalkylene silanes or multiple silylated polyaminoalkyl~ne compounds, e.g. by the reaction of an alkylenediamine and a haloaLkyl silane or by the reaction of an aminoalkyleneaminoalkylene silane and a haloalkyl silane~
~ ~ ~3~1 11,931 _~--J~
in addition to the desired product, the crude reaction product can be expected to consist of a mixture of symmetrical and unsymmetrical bis, ~ris and tetrakis silyl compounds, and the like, due to the multiple amino reaction ~ites on the amino starting material. Accordingly, included within the definition of the aminosilicon compounds that can be employed in the composi~ions of this inveation are such crude aminosilicon compound reaction products that contain mor~ than one amino group and/or silyl group as shown by Fonmula (I) above. Indeed, since the more pre-ferred aminosilicon compounds e~ployable in this invention are ~hose containing more than one am no group and/or more than one silyl group it is generally preferred to employ th2 crude reaction product mixture obtained upon producing the type of aminosilicon compound that one wishes to use in the particular composition of this invention desired ~or a particular end result, since such eliminates the time and efort caused by additional procedural s~eps necessary.
in preparing and isolating any particular singular amino-silicon compound prior to its use herein.
Accordingly, the more preferred aminosilicon com-pounds employable in this invention are those o~ Formula (I) above wherein at least one R2 group represents a silyl radical of the for~ula la -R-Si3_a and mixtures thereof, wherein R, Rl and a are the same as defined above, e.g. ~H3O)3Si(CH2)3NH(CH2)2NH(CH2)3 Si(OCH3)3O
14.
3~88 11, 931 Moreover, due to the fact that the present lnver.tion allows for the use of the crude reactiun product mixtures of said preferred aminosilicon compounds produced by either above described conventional procedures thereby rendering it unnecessary to obtain a single species of the desired aminosilicon compound, the more preferred aminosîlicon compound component of this invention is a crude aminosilicon reaction product mixture having an average empirical mole ratio of the following structural units [~ ~x ~A) [~N-R3)tN-] (B) a ~R-Si-X3_a]y (C~
wherein R, Rl, R3, a, and t are the same as defined above, with Rl preferably being a hydrogen radical, t preferably having a value of 1 to 2 and a preferably being 0; while x has a value o O to 6 preferably 1 to 4, ~ has a value of 1 to 6, preferably 2 to 5; the su~ sf x + ~ being a value of 3 to 6, preferably 4 to 5. Of course it is understood that said structural units (A) and (C) are both directly bonded to said structural uni~ thereby satisfying all of the ~ree valences of said structural units (A), (B) and (C).
The most preferred aminosilicon compound employable ln the composition of this inventlon i.s a crude aminosilicon ~3~38 ~l,g3l reaction produce mixture having an average empirical mole ratio of the following structural units [H~x (A) [-N-CH2CH2-N-~ ~B) ~ (CH2)3-Si-(0CH3)3]y (C) wherein x has a value of 0 to 3; ~ has a value of } ~o 4, preferably ? to 4; the sum of x + ~ being 4; said structural units (A) and (C) both being directly bonded ~o said stxuc-tural unit (B) thereby satisfying all of the free valancesof said structural units (A), (B) and (C).
The hydxoxyl-containing organic polymer-amino-silicon compositions of this invention are unifonmly blended solutions containing about 5 to about S0 parts by weight, and more preferably about 10 to abou~ 40 parts by weight of the aminosilicon compound per 100 parts by weight of the organic polymer, and can be prepared by merely mechani-cally mixing said ingredients together along with other various ronventional components that may be included if desired in the room temperature curable compositions. The particular design of n~xing equipment and the method and order o the various components is not critical, although it is pre~erred to add ehe aminosilicon 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 16.
~;23~B8 11, 931 o the various components should be conducted under substantially anhydrous type conditions, such as closing the equipment so that the ambient atmosphere can be contro~led. Moreover~ since the compositions of this invention are mildly basic in nature, it is desirable to exclude or control their contact with any acidic or potentially acidic environmental components such as S02, C02, or HCl which m~y be in the a~mosphere. I~ may also be desira~le to dry or dehydrate any additional components whic~ are added.
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 o~ the cured composition without increasing the viscosity of the curable composi-tion, filiersS 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 em~loyed will of course merely depend on the ultimate end use desired for the compositions of this invention.
The hydroxyl-containing organic polymer-amino-silicon compositions of this inventioll have a wide variety of utility such as in the fields of coatings, laquers, paints, inks, dyes, tints, impregnations, adhesives, caulks, sealants and the like. Said compositions are 17.
~ ~ ~ 3 ~ ~ ~ 11,931 especially useful as room temperature curable coating compositions which may be applied over a wide variety uf 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 (cro~sLinked) pro~ective and/or decorative solvent resistant coatings are desired, such as in the fields of main~enance and ~rine coatin~sO
For exampLe, the compositions of this invention when kept anhydrous have been found to provide excellent protective and solvent resistant cured coatings for metals merely by air drying the curable coatLng composition at room (a~bient) temperature after it has been applied to the metal. ~ormally, the ambient moisture in the air is sufficient to cure (crossLink) the coating into a dry, hard corrosion and solvent resistant protective film on the metal. The curable composition generally becomes dry very quickly and cured coatings having excellent properties have been achieved within 24 hours ~fter coating the substrate. Of course, it i5 to be understood that the curing may be accelerated, ~f desired, by the employment of elevated temperatures.
18.
~ 11,931 In addition to the surprisingly excellent solvent resistance of the cured compositions of this invention such cured coatings have also been found to have good impact strength, weatherabllity and environ~ental resistance as exhibited by their good stability against salt sprays, and against chalking on exposure to sunlight, as well as their resistance to deteriora~ion, corrosion and blistering upon being immersed in both fresh water and seawater for prolonged periods of time. Of course it is to be under-stood tha~ the ultimate properties of any given roomtemperature curable coating composition will depend upon such obvious factors as the various ingredients employed, their concentrations, the crosslinked density of the final composition, and the like. However, the optimum results desired for any composition is well within the bounds of routine experimentation.
While not wishing to be bound by any particular theory of mechanism involved, it is believed that the aminosilicon compound reacts with the polymer via transesterification followed by hydrolysis of the silane portion. Experiments have indicated that the aminosilicon compound i5 bound to the hydroxyl containing polymer through an Si.-O-C bond via transesterification which then upon exposure to the ambient moisture in the air hydrolyzes and cures (crosslinks) into a solid fil~.
The most preferred coating composition of this invention are those consisting essentially of a hydroxyalkyl 19 .
11,~31 ~ ~ ~ 3 ~ ~ 8 acrylste modified vinyl chloride polymer as defined above and a hydrolyzable aminosilicon 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 100 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 lQ0 par~s by weight of said polymer; 0 to about 25 parts by weight of an alkyl sili-cate per 100 parts ~y weight of said polymer; and 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 weigh~ of a dessicant. The most preerred hydroxyalkyl acrylate modified vinyl chloride polymers and aminosilicon compounds useful in ~his invention have already been defined above. In general a typical coating composition will consist of about 10 to 35 per cent by weight of said hydroxyalkyl acrylate modified vinyl chloride polymer based on the total weight of the composition. Of course, it is obvious that the particular additives employed are not critical and any suitable solvent, pigment, filler, alkyl silicate, dispersing agent and dessicant can be employed~ ~n 2~) o ~ 3~ g3l general, the preferred solvents are methylisobutyl ketone, xylene and mixtures thereof, while the preferred pigment is titanium dioxide and the preferred de~sicant is molecular sieves.
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 e~uipped with a stirrer, condenser and vat scrubber. The hydrogen chloride by-product is removed by re1ux which may be carried out at reduced or atmospheric pressure.
Through this process, the most common products TEOS
(tetraethyl 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 detenmines the degree of hydrolysis in the final 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 containing 40% SiO2), and Ethyl Silicate P-18, having an 80 to as per cent hydrolysis level.
The following examples illustrate the present invention and are not to be regarded as limitative. All 21.
. _ ,.
~ 11,931 parts and percentages are by weight unless otherwise specified .
For the sake of brevity in the ~xamples, the designations in the first column of Table I will be used in lieu of the complete description given in the second column.
TABL~ I
Desi~nation Com~sition o Polymer A A uniformly random hydroxyl-functional terpolymer of 80% vinyl chloride mer units, 5% vinyl acetate mer units and 15% hydroxypropyl ~crylate mer units.
Inherent viscosity is 0.3.
Polymer B A partiaLly hydrolyzed polyvinyl a:Lcohol - terpolymer o 91% vinyl chloride mer units, 3% vinyl aceta~e mer units and 6% vinyl alcohol mer units. Viscosity is 60 cps (20% resin in methyl ethyl ketone). Sold by Union Carbide Corpor-ation under the product designation VAGH.
Polymer C A thermoplastic poLyhydroxyether phenoxy resin polymer having a specific gravity of 1.18 and sold by Union Carbide Corporation under the product designation PKHH.
Polymer D A bisphenol A-formaldehyde phenolic resin containing approximately 16% methylol groups, sold by Union Carbide Corporation under the product designation BK-S~18.
Polymer E A polyhydroxyl containing acrylate poLymer so7d by Rohm & Haas under the product designation Acryloid AT-56.
Polymer F A polyvinyl butyral resin polymer contain-ing 1% vinyl acetate mer units and 20%
vinyl alcohol mer units having an Inherent viscosity of 0.90 and sold by Union Carbide Corporation under the product designation XYE~.
2~o 11, 9~1 TABLE I (cont'd.) Desi~na~ion Composition Nuospers ~ 657 A dispersing agent supplied by Tenneco, Inc.
ES-40 A partially hydrolyzed ethyl poLy-silicate containing 40 percent by weight of SiO2.
TEOS Unhydrolyzed tetraethyl orthosilicate.
Silane A A commercial gxade silane designated as N-beta-(Aminoethyl)-gamma-aminopropyl-trimethoxy-silane sold under the pro-duc~ name A-1120 by Union Carbide Corporation.
Silane B A silane having the formula (c2Hso)3si(cH2)3NH2 Silane C The crude aminosilane reaction product mixture of ~xample A of this application.
Silane D A silane having thP formula (cH3o)~si(cEl2)3NH(~2)~NH2 distilled from Silane A
Silane E A silane having the formula (CH30)3Si(CH2)3NH2 Silane F A silane having the formula (cH3o)3sicH2c~2si(oc~3)3 SiIane G The crude aminosilane reaction pro-duct mixture of Example B of this application.
Silane H The crude aminosilane reaction product mixture of Example C of this appli-cation~
EXAMPLE A
An aminosilicon compound was prepared by reacting 399.8 grams (1.8 moles) of an aminosilane having the forIula (CH30)3Si ~CH2)3NH(cH2)2NH2 (which was distilled from Silane A) with 357.7 grams ~1.8 moles) of a silane having the formulR
23.
~ 3 ~ ~ ~ 11,931 (C~30)3Si(CH2)3Cl at 110C. for an hour. The reaction product was then cooled to room temperature and treated with 108.2 grams (1.8 moles) of ethylene diamine to remove HCl from the reaction product which was then stripped to 175C under vacuum (0.5 mm Hg~ to remove all lites up to the amino-silane starting m2terial. About 650 grams of a cxude aminosilicon reaction product mixture was ob~ained which had an Amine Equivalent of 1.72 grams-nitrogen and consisted essentially of 2 major amount of aminosilicon compounds having the following mole structural unit ratios: :
L H~ ~-N- C2H4- N-~ r~CH2 ) 3S i ( OCH3 ) ~H~ LN-C2H4-N-] ~CX~)3Si(OCH3) and r, ~ 1 r ¦ -N-C2~4-N i ~CH2)3Si(OC~3)3 ~
and a minor amount of unreacted (CH30)3Si(~2)3NH(c~2)2NH2 starting material. As employed in this application the crude reaction product mixture o this Example is desig-nated Silane C.
~e~
An aminosilicon co~pound was prepared by reacting 2443 grams (11.0 moles~ of Silane A (12.6% titratable nitro~
gen~ with 1747 grams t8.8 moles) of a silane having the formula 2~o ~ ~ 3 9 ~ ~ 11,931 (CU30)3si-tcH2)3cl at 110+10~C. for four hours. The reac~ion product was then cooled to room~temperature and treated with 529 grams (8.8 moles) of ethylene diamine at 60C. to remove HCl from the reaction product which was then stripped at 100C./40m~ Hg. to remove the residual ethylene diamine.
About 3576 grams of a crude aminosilicon reaction product mixture was obtained. Gas chrom~tographic ~nalysis of the crude reaction product mixture showed it to consist essentially of about 30 percent by weight of an amuno-silicon compound having the following mole ratio of structural units [ ~3~ E!N- CH2CH2N-~ ~EC'H2 ) 3Si (OCH3)~
about 24 percent by weight of an aminosilicon compound h~ving the following mole ratio of structural units [H ~ [ ~_C2H4-N-~ ~ CH2)3Si(cH3) ~ 3 about 5 percent by weight of an aminQsilicon compound having the following mole ratio of structural units L-N- CH~CH2 -N-~ ~CH2)3Si(OCH3)3~
about 19 percent by weight (CH30)3Si~CH~)3~(~H2)2NH2 and about 5 percent by weight of (CH30)~Si-0-li(OCH3)2 H2N(CH~)2HN(CH2)3 (CH2)3NH(CH2)2 2 the remainder of the reaction product consisting essentially of mix non-eluting polysiloxane polymers. As employed in 25.
, ~ ~ 11,931 this application the crude reaction product mixture of this Example is designa~ed Silane G.
EXAMPLE C
An aminosilicon compound was prepared by repeating Example II on a plant scale. 400 pounds of Silane A was reacted with 286 pounds of (CH30)3Si(CH2~3Cl at about 110C. for about three hours. The reaction product was cooled to about 70C. and ~reated with 130 pounds of ethylene diamine in an agitator for 30 minutes and 183 pounds of hydrochloride by-product ~chloride content 31.7%) was removed from the reaction product.
The reaction product was then stripped at 100C./47~m Hg.
for two hours to rem.~e 6 pounds oX lites. Upon cooling and filtration 590 pounds of a crude aminosilicon reaction product mixture was obtained which consisted of a major amount o aminosilicon compounds having the following mole structural unit ratios:
~H~ EN~ C~H4-N-~ ~CH2 ) 3Si (OCH3) 3]2 1~ ~ E 2H4 N-~ ~LCHZ)3Si(OCH3)3]
and ~ N-C2H~-N~ CH2)3Si(~C~3)J4 and a minor amount (about 15.1 percent by weight) of unreacted Silane A. As employed in this application the crude reaction product mixture of this Example is designated Silane ~1.
26.
~ 3 ~ ~ 11931 A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared having the following total formulation Com ound Parts by Wei~ht p Pol~mer A 25.45 Titanium Dioxide 19.09 Methylisobutyl Ketone 27.57 Xylene 27.57 Nuosperse 657 0.32 ES-40 Varied~
Silane A Varied*
*Parts by weight given in Table II 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 with c~irring and the mixture ground in a pebble mill o~ernight. The amino-silane compound was then added with stirring as was the ethyl silicate when used until a uniform coating com~o-sition was obtained. Each coating composition was then thinned to a No. 4 Ford cup viscosity of 20-25 sec~nds by the addition of a 50/50 weight percent solvent blend of methylisobutyl ketone and xylene. Each coating compositLon was then sprayed onto aluminu 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 ~aving been air dried at room ~emperature for various periods of time was then measured by subjecting each air dried coating to double MEK rubs and the results of this 27.
~ 398~ 11931 test are reported in Table II 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 MEK rub rating of five means that the metal surface of the panel was exposed after the methylethylketone saturated cloth was rubbed back and ~orth (2 strokes) over the coating a ~otal of five times. Thus the higher the numerical double MEK
rub rating obtained for a given coating the more solvent resistant the coating is.
The solvent resistance of each coating on said panels after having been air dried at room temperature for various periods of time was also measured by a solvent extraction test and the results of said tests are reported in Table II below. Said test involves measuring ~he difference in weight of the air dried coated panel before and after immersing the coated panel in boi~ing methyl-ethy~ketone for 18 hours in order to obtain the weight ~0 percent of eoating extracted from the test panel. Thus the lower the weight percent of coa~ing that is extrzcted for a given coating, the more solvent resistant the coating 28.
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a~ a O C~ ~ 0 o r~ O ~ ~ ~ d" ~ ~ ~ ~ C~
. O
cn o u~ ~ u~ ~1 _I a~ ,~ ~ ~ ~ I~ ~o O ~ ~ ~ O~
o 0 ~ a~ ~ ~ ~ ~D cr~ C~ ~ I` ~ `* . . -o ~ ~ o ~ ~ 5~ o c~
Z ~
~ _~~ 0 q~ ~
, ~o a e~ _ C~
~¢~ Oo~D~_l`D~O~
~ ~ O ~ ~ oo co ~o ~ ~o ~ ~ ~ ~ C~l ~ ~ ~ O O ~0 !C
s~ Y
.
29 .
9 ~ ~ 11931 The above results of T~BLE II de~onstrate thatthe hydroxyl containing polymer-aminosilane compositions of this invention can be empLoyed as room temperature crosslinkable coating composi~ions to provide very good solvent resistant coatings; that the solYent resistance of said coatings increases with time and levels off; that there is a direct correlation between the solvent extraction test and MEK rub test, as the MEK rub rating increases the percen~ extractables decreases; and that no ethyl siLicate is necessary to obtain excellent solven~ resistant coatings ~Examples 17 and 18)~ while coatings obtained from formu-lations having little or no amino silane (Examples 1 and 16) have little if any solvent resistance.
A hydroxyl containing organic polymer~amino-silicon coating composition having ~he following total formulation .
ComPound ~ Parts by Wei~
Polymer A 25.45 Titanium Dioxide 19.09 Methylisobutylketone 27.57 Xylene 27.57 Nuosperse 657 0.32 ES-40 6.36 Silane A 6.4 : . was prepared and thinned to a spray viscosity in the same manner as described in Examples 1-18, The coating compa-sition was then sprsyed on to a series of zinc rich prlmed steel panels to glve a top coating of about 2 mals and the top coatings on said panels cured by allowing them to air dry at room temperature for two weeks. The cured top coated steel panels were then ested for resistance against 3~, ~L~88 11931 salt spray, synthetic seawater immersion and fresh water immersian and exhibited excellent results. The cured top coating of the panels tested exhibited no been deterioration after (a) having/subjected to a salt spray for lOOO hours, (b) after having been immerse~ in syn-thetic seawater for lOOO hours, ~nd ~c) after having been immersed in fresh water for 1000 hours. Said top coated steel panels were also tested ~or adhesion of the top-coating to the pr~mer by a cross-hatch adhesion test with Scotch tape after having undergone the above three envir~
onmental tests. The only adhesion failure observed in each instance was cohesive failure of the primer ~o the steel.
EX~MPLES ~0-23 A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared in the same manner as described in Examples 1-18 having the following total formulations.
~ Parts By Weight --Compound Example Example Example Example 21 22 _ 23 Polymer A 25.45 25.45 25.4525.45 Titanium Dioxide19.09 1~.09 19.0919.09 Methylisobutyl Ketone 27.57 27.57 27.5727.57 Xylene 27.57 27.57 27.5727.57 Nuosperse 657 0.32 0.32 0.320.32 ~S-40 8 - - -Silane A - 8 - 4 Silane B 8 - - -Silane C - - 8 3~.
8~ 1931 Each coating composition was then appLied ~o sand blasted steel panels by a draw down bLade to give a coating thick-ness of about 1-1/2 to 2 mlls thick 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 periods of time was then measured by subjecting each air dried coating to double acetone rubs and the results of this test are reported in Tabl~e III below. Said test is the same as the double MEK rub test given in Exa~ples 1-18 save for the fact that acetone was used as the solvent instead of methylethylketone.
TAB~E III
Example ~ -Double Acetone Xubs~
No. 1 Day 3 Days 1 Week 2 Weeks 1 Month 8 - 100+ - -22 100~
23 3 - 2~ 35 ~Double acetone rubs were stopped after reaching 100.
In addition the cured coating composition of Example 23 after having been cured by air drying at room temperature for 24 hours exhibited an i~pact strength of grea~er than 160 inch pounds, both direct and reverse, on a Dart Impact Tester, while the same coating without the aminosilane had an impact strength of less than about 20 inch pounds.
._ A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared in the same 32.
~ 3 ~ 11931 manner as described in Examples 1 18 having the following total formulation _ _ Compound Parts By Weig~t Polymer A 25.0 Titanium Dioxide 19.0 Methylisobutyl Ketone 28~0 Xylene 28~0 Silane* ~,o *The particular silane employed in each composition is given in TABLE IV below, Each coating composition was then applied to sand blasted steel panels by a draw-down blade to give a coating of about 2 mils thick and the coa~ings on said panels cured by allowing them to air dry at room tempera-ture. The solvent resistance of each coating ater having been air dried at room temperature for various periods of time was then measured by the same double acetone rub test desc:ribed in Examples 20-23 and ~he results of said test are given in Table IV below.
TAsLE IV
Exa~ple 5ilane ~ Double Acetone Rubs -- -No. . Used ~ 5 Days2 Weeks 6 Ueeks 24 Silane C 100+ - - -Si}ane A 25 69 100~ ~ -26 Sila~e D 16 45 100~ - -27 Silane E 20 23 100+ - -28 Silane B 5 24 29 100~
29 Silane F 9 5 8 - 16 ~Double acetone rubs were stopped a~ter reachin~ 100. r A hydroxyl containing organic polymer-aminosilicon coating composition was prapared in the same manner as described in Examples 24-29 having the following total formulation.
~ ~ 3 ~ ~ ~ 11931 __Co~ound _~ Parts by Wei~
Polymer A 25.0 Titanium Dioxide 19.0 Methylisobutyl Ketone 28.0 Xylene 28.0 ES-40 12.0 Silsne A 12.0 The composition so prepared was coated onto a sand blasted steel panel and tested for solvent resistance in the same manner as described in Examples ~4-29. The results of the double acetone rub test are given in Table V below.
TABLE V
Example Double Acetone Rubs No.~ 2 Weeks 16 100+
+Double ~cetone rubs were stopped after reaching 100.
A hydroxyl containing organic polymer-aminosilicon coating composition having the follo~ing tot~l formulation Compound _arts by Wei~_t Polymer A 24 Titanium Dioxide 18 Methylisobutyl Ketone 26 Xylene 26 Nuosperse 657 0.3 Silane A 4.8 was prepared and thinned to a spray viscosity in the same manner as described in Examples 1-18. The coating composi-tion was then sprayed onto a sand blasted steel panel to give a coating thickness of about 1~5 mils and the coating cured by allowing it to air dry at room te~perature for 24 hours. Said cured coating exhibi~ed an impact strength of about lZ4 inch pounds, bo~h direct and reverse, on a Dart Impact Tester~ while a similar cured coating without 34.
~39~38 ll, 931 the aminosilane compound failed below 28 inch pounds on both tests. o A hydroxyl con~aining organic polymer-amino^
silicon coating composition having the following total ormu1ation.
Compound _ Parts By Wei~ht Polymer A 30.7 Titanium Dioxide 23.0 Methylisobutyl Ketone 23.0 Xylene 23.0 Nuosperse 657 0.3 Silane G 6.14 was prepared a~d thinned to a spray viscosity in the same m~nner as described in Examples 1-18. The coating composition was then sprayed on to a series of four diferent primed steel panels to give a top coating of about 2-3 mils over the various primed steel panels.
The top coatings on said panels were then cured by allowing them to air dry at room temperature for two weeks.
The cured topcoated steel panels were then ~ested for res~stance against blistering a~d corrosion by subjecting two top coated panels from each primed panel ca~egory to (1) a 5% salt water ~pray test for 1000 hours, (2) to synthetic seawater immersion for 1000 hours and (3) to fresh water immersion or 1000 hours. No corrosion or bListering was observed for any o the top coated panels so tested~
~ 3 ~ ~ 8 A series o~ hydroxyl containing organic polymer-aminosilicon coating compositions were prepared in the same manner as described in Examples lW18 having the following total formulation.
ComPound _ _Parts_b~ Wei~ht Polymer ~ 20 Titanium Dioxide 14 Methylisobutyl Ketone 32.85 Xylene 32.85 Nuosperse 657 0.3 5ilane G Varied *Parts by weight given in Table VI below.
Each coating co~position so prepared was then applied to a series of aluminum panels by a draw down blade 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 cured coating on said panels after having been air dried at room ~ temperature for various periods of time was measured by subjecting each air dried coating to the same double MEX
rub test described in Examples l-L8 and the results of said test are given in Table VI below.
TABLE VI
E~le Silane G - Double ~ER Rubs - -No. (Parts by wt,) 24 hrs. 48 hrs. 72 hrs. 1 Week 33 4 10~
34 3 ~0 ~0 59 90 + Double MEK rubs stopped after reaching 100.
36.
1193:L
~ 2 ~
EXAMPLFS 36 and 37 A series of hydroxyl containing polymer-amino-silicon coating compositions were prepared in the same manner as described in Examples 1-18 (the molecular sieves being added with the titanium dioxide pigment) having the following total ormu1ations Parts By Weight _ Compound_ _ _ Example 36 Polymer A 25.45 25.45 Titanium Dioxide 19.09 19.09 Methylisobutyl Ketone27.57 27.32 Xylene 27.57 27.32 Molecular Sieves 4A - 0.5 Nuosperse 657 0O3 0.3 Silane H Varied~ Varied~
~Parts by weight gLven in Table VII below.
Each coating composition so prepared was then applied to a series of aluminum panels by a draw do~
blade to give a coating thicknesc 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 c:ured coating on said panels were then measured by subJecting esch cured coating to the same double MEK rub test described in Examples 1-18, both before and after said cured coatings had undergone various hydrolytic stability tests. The results of said double MEK rub tests are given in Table VII below.
~23~
~o ~ o o ~ _, o o o ,,~ ~ ,~
.
~o ~
~o ~C ~
~D ~n -I cr~ ~ o~ oO o~ 0 ~o ~ I ~ ~D00~
~3 ~0 u~o ~1~
C~
~ O
3 ~
cl L ~ + I + I
~1 I1~ 0 ~ 1:~ 0 0 0 0 t~
io C!~ C:) O O ~ '`' ~ I
I
~; I
O ~;
~ ~ 0 0 ~ 00 0 0 ~ ~ C
Z~ ~ ~
X + ~e 38 .
rL~ 3~ ~ 4:
A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared having the following total formulations.
~ Parts By Weight ~
Compou~d _ _ Example 38 Ex =~le 39 ExamPle 40 _~E~ L
Polymer C - 17~5 - -Poly~er D 38.5 - - -Pol~me~ E - - 66 Polymer F - ^ - 9.1 Titanium Dioxide 23 12.5 8 6.3 Xylene - - 23 ~ethyl Ethyl Keto~e 38.5 - - -Cellosolve Acetate - 57 -. -Toluene ~ 13 - -Butyl Alcohol - - 3 17.7 Isopropyl Alcohol - - - 66.9 ÆS-40 6 ~ 8 Silane C 6 2 8 4 Each polyol was dissolved in the solvent or solvent blend employed and ~itanium dioxide added while mixing with a high speed disperser until a Hegman fineness of grind of 6 to 8 was obtained. The ethyl silicate if used was then added followed by the aminosilane with stirring until a uniform coating composition was obtained. Each coating composition was then applied to sand blasted steel panels with a draw down blade to give a coating thickness of about 2 ~ils. The coatings on said panels were then cured by allowing them to air dry at room temperature and the solvent resistance of each cured coating after having been air dried at room temperature for various periods of time measured by the same double acetone rub test described in Examples 20 to 23. I'he results of said test are reported in the following table.
3g.
T LE VlII
Example -- Double Aceto~e Rubs--~~~~~~
No. 24 Hours 4 DaYs1 Week2 Weeks 1 MDnth 38 - 12 1~ 14 15 39 26 62 76 - 100+
41 86 70 73 - 100+
Double acetone rubs stopped after reaching 100, E~AMPLES 42 to 49 A series of hydroxyl containing organic polymer-aminosilicon coating compositions were prepared having the following total formuLations - -- Parts By Weight -- -CoIpound _ E~.42 Ex,43 Ex.44 Ex.45 Ex,46 Ex.47 Ex.48 Ex~49 Polymer A 25.45 25,45 25.45 25.45 25.45 25045 25,45 25.45 Titanium Dioxide 19.09 19~09 19,09 19.09 19.09 19~09 l.9.09 19.09 Methylisobutyl 27.57 27.57 27.57 27,57 27.57 27,57 27.57 27.57 Ketone Xyle~e 27.57 ~7.57 27.57 ~7.57 27.57 27.57 27,57 27.57 Nuosperse 657 0.32 0.32 0,32 0.32 0.32 0~32 0.32 0.32 M~lecular Sieves - - 0.5 0.5 2.55 2.55 2.55 2.55 Methanol - 2 - 2 - ~ - 2 Distilled Water 1.2 1.2 1~2 1,2 1.2 1.2 1.2 1,2 Silane H 5.08 5.08 5.08 5.08 5,0 5,0 5,0 5.0 Each composition was prepared by dissolving the solvent in the solvent blend followed by addition of the titanium dioxide, molecular sieves and Nuosperse 657 while mixing in a high spee~ disperer until a finely ground mixture was obtained. The water, methanol and silane~ in that order, were then stirred into the composition until a uniform coating composition was obtained. Each coating composition was then applied to sand blasted steel panels with a draw down blade to give a coating thickness of about 2 mils. The coatings on said panels were then curèd by allowing them to air dry at room temperature and the solvent resistance of each cured coa~ing after having been 40.
air dried at ~ario~s periods of time measured by the same double MEK rub test described in Examples 1-18.
The results of said test are given in the following tzble.
TABLE IX
- Double MEK Rubs Example No. 24 Hours 8 Days ~3 22 100+
44 12 ~0+
47 25 100~
4~ 50 100+
~Double MEK rubs stopped a~ter reaching 100.
EXAMPLES 50 and 51 A series of hydroxyl containing pol~mer-amino-silicon coating compositions were prepared in the same manner as described in E~amples 36 and 37 having the following total formulations.
- Parts by Weight ComPound _ _ Exam~le 50 Polyol A 25.45 25.45 Titanium Dioxide 19.09 19.09 Methylisobutyl Ketone~ 27.57 27.32 Xylene 27.57 27.32 Nuosperse 657 0.3 ~3 Molecular Sieves 4A ~ 0.5 Silane A 1.28 1.28 Each coating composition so prepared was then applied to alllm1num panels by a draw down blade to give a coating of about 2 mils and the coatings on said paneLs cured by allowing th~m to ai.r dry at room temperature.
The solvent resistance of each cured coating on said panels was then measured after having been air dried at 41.
~2~t~
various periods of time by the same double MEX rub test described in Examples 1-18. The results of said test are given in the following table.
-- TABLE X
Example ~ Double MEK Rubs - -_ No. 1 Week 2 Weeks 3 Weeks _ Month 2 Months 23 47 ~0 100 51 38 73 100+ ~00~ 100 +Double MEK rubs stopped after reaching lOO.
Various ~odifications 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 claLms.
42.
Claims (41)
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 hydro-lyzable aminosilicon compound selected from the class consisting of aminosilicon compounds having the average 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; Rl is hydrogen or an alkyl radical having 1 to 4 carbon atoms, R2 is a radical selected from the group consisting of hydrogen, an alkyl radical having 1 to 4 carbon atoms and a silyl radical of the formula wherein R, Rl, and X are the same as defined above; and wherein R3 is a divalent alkylene radical having 2 to 4 carbon atoms; a has a value of 0 to 2 and t has a value of 0 to 4; and wherein said composition contains about 5 to 50 parts by weight of said hydrolyzable aminosilicon compound (B) per 100 parts by weight of said organic polymer (A).
43.
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 radical selected from the group consisting of hydrogen, an alkyl radical having 1 to 4 carbon atoms and a silyl radical of the formula wherein R, Rl, and X are the same as defined above; and wherein R3 is a divalent alkylene radical having 2 to 4 carbon atoms; a has a value of 0 to 2 and t has a value of 0 to 4; and wherein said composition contains about 5 to 50 parts by weight of said hydrolyzable aminosilicon compound (B) per 100 parts by weight of said organic polymer (A).
43.
2. A composition as defined in claim 1 wherein X is an alkoxy radical selected from the group consisting of methoxy, ethoxy and 2-methoxyethoxy, wherein R and R3 are divalent alkylene radicals selected from the group consisting of ethylene and propylene, and wherein a is 0.
3. A composition as defined in claim 2 wherein t is 0.
4. A composition as defined in claim 2 wherein t is 1.
5. A composition as defined in claim 4, wherein R is a propylene radical and R3 is an ethylene radical.
6. A composition as defined in claim 5 wherein each R2 is individually selected from the group consisting of hydrogen, and a silyl radical of the formula -(CH2)3Si-X3
7. A composition as defined in claim 6 wherein X is a methoxy radical.
8. A composition as defined in claim 7 wherein the aminosilicon compound is a mixture of said aminosilicon compounds.
9. A composition as defined in claim 3, wherein X is an ethoxy radical, R is a propylene radical and each R2 is individually selected from the group consisting of hydrogen and a silyl radical of the formula -(CH2)3Si(OC2H5)3
10. A composition as defined in claim 1 wherein the organic thermoplastic polymer is selected from the class consisting of a hydroxylalkyl acrylate modified vinyl chloride polymer, a polyether polyol polymer, a 44.
11,931 polyhydroxy containing acrylate polymer, a polyvinyl alcohol polymer, a polyhydroxy containing polyvinyl scetal polymer, a polyester polyol polymer, a phenolic resin polymer, and mixtures thereof.
11,931 polyhydroxy containing acrylate polymer, a polyvinyl alcohol polymer, a polyhydroxy containing polyvinyl scetal polymer, a polyester polyol polymer, a phenolic resin polymer, and mixtures thereof.
11. A composition as defined in claim 10, wherein X is an alkoxy radical selected from the group consisting of methoxy, ethoxy, and 2-methoxyethoxy, wherein R and R3 are divalent alkylene radicals selected from the group consisting of ethylene and propylene, wherein a is 0, t is 1 and wherein each R2 is individually selec-ted from the group consisting of hydrogen and a silyl radical of the formula -RSiX3
12. A composition as defined in claim 11, wherein the organic thermoplastic polymer is a hydroxy-alkyl acrylate modified vinyl chloride polymer.
13. A composition as defined in claim 11, wherein the organic thermoplastic polymer is a polyether polyol polymer.
14. A composition as defined in claim 11, wherein the organic thermoplastic polymer is a polyhydroxy containing polyvinyl acetal polymer.
15. A composition as defined in claim 11 wherein the organic thermoplastic polymer is a polyhydroxy containing acrylate polymer.
16. A composition as defined in claim 11, wherein the organic thermoplastic polymer is a polyvinyl alcohol polymer.
45.
11,931
45.
11,931
17. A composition as defined in claim 11, wherein the organic thermoplastic polymer is a polyester polyol polymer.
18. A composition as defined in claim 11, wherein the organic thermop}astic polymer is a phenolic resin polymer.
19. A composition as defined in claim 11, wherein R is a propylene radical, R3 is an ethylene radical, X is methoxy and wherein the aminosilicon compound is a mixture of said aminosilicon compounds.
20. A compositian as defined in claim l, wherein said composition contains about 10 to about 40 parts by weight of said hydrolyzable aminosilicon compound (B) per 100 parts by weight of said organic polymer (A).
21. A composition as defined in claim 1 wherein an alkylsilicate is present as an additional ingredient.
22. A composition as defined in claim 21, wherein the alkyl silicate is tetraethyl orthosilicate.
23. A composition as defined in claim 10 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 46.
11,931 said pigment and 0 to about 3 percent by weight of a dessicant material,
11,931 said pigment and 0 to about 3 percent by weight of a dessicant material,
24. A composition as defined in claim 23, wherein X is an alkoxy radical selected from the group consisting of methoxy, ethoxy and 2-methoxyethoxy, wherein R and R3 are divalent alkylene radicals selected from the group consisting of ethylene and propylene, wherein a is 0, t is 1 and wherein each R2 is individually selected from the group consisting of hydrogen and a silyl radical of the formula -RSiX3.
25. A composition as defined in claim 24, wherein the organic thermoplastic polymer is a hydroxy-alkyl acrylate modified vinyl chloride polymer.
26. A composition as defined in claim 24, wherein the organic thermoplastic polymer is a polyether polyol polymer.
27. A composition as defined in claim 26, wherein the polyether polyol polymer is a phenoxy resin.
28. A composition as defined in claim 24, wherein the organic thermoplastic polymer is a polyhydroxy con-taining polyvinyl acetal polymer.
29. A composition as defined in claim 28 wherein the polyhydroxy containing polyvinyl acetal polymer is a polyvinylbutyral resin.
30. A composition as defined in claim 24, wherein the organic thermoplastic polymer is a polyhydroxy containing acrylate polymer.
47.
11,931
47.
11,931
31. A composition as defined in claim 24, wherein the organic thermoplastic polymer is a polyvinyl alcohol polymer.
32. A composition as defined in claim 24, wherein the organic thermoplastic polymer is a polyester polyol polymer.
33. A composition as defined in claim 24, wherein the organic thermoplastic polymer is a phenolic resin polymer.
34. A composition as defined in claim 25, wherein R is a propylene radical, R3 is an ethylene radical, X is methoxy and wherein the aminosilicon compound is a mixture of said aminosilicon compounds.
35. A composition as defined in claim 23, wherein said composition contains about 10 to about 40 parts by weight of said hydrolyzable aminosilicon compound (B) per 100 parts by weight of said organic po}ymer (A).
36. A composition as defined in claim 23, wherein the pigment is titanium dioxide.
37. A composition as defined in claim 25, 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.
48.
11,931
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.
48.
11,931
38. A composition as defined in claim 37, wherein the organic polymer is a hydroxy-functional random terpolymer 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.
39. A composition as defined in claim 38, wherein said composition contains about 10 to about 40 parts by weight of said hydrolyzable aminosilicon compound (B) per 100 parts by weight of said organic polymer (A).
40. A composition as defined in claim 39, wherein the pigment is titanium dioxide,
41. The crosslinked polymer product obtained upon crosslinking the composition of claim 1.
49.
49.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US961,473 | 1978-11-16 | ||
| US05/961,473 US4243767A (en) | 1978-11-16 | 1978-11-16 | Ambient temperature curable hydroxyl containing polymer/silicon compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1123988A true CA1123988A (en) | 1982-05-18 |
Family
ID=25504513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA338,031A Expired CA1123988A (en) | 1978-11-16 | 1979-10-19 | Ambient temperature curable hydroxyl containing polymer/silicon compositions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4243767A (en) |
| EP (1) | EP0011782B1 (en) |
| JP (1) | JPS5917136B2 (en) |
| AU (1) | AU526613B2 (en) |
| CA (1) | CA1123988A (en) |
| DE (1) | DE2965827D1 (en) |
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| JPS5721410A (en) * | 1980-07-11 | 1982-02-04 | Kanegafuchi Chem Ind Co Ltd | Silyl group-containing vinyl resin and its production |
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| DE3220866A1 (en) * | 1982-06-03 | 1983-12-08 | Dynamit Nobel Ag, 5210 Troisdorf | CROSSLINKABLE RESIN MIXTURES |
| JPS5971377A (en) * | 1982-10-15 | 1984-04-23 | Kanegafuchi Chem Ind Co Ltd | Adhesive composition |
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| 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 |
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| 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 |
| 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 |
| US4468492A (en) * | 1983-07-15 | 1984-08-28 | Ppg Industries, Inc. | Polymeric organo functional silanes as reactive modifying materials |
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-
1978
- 1978-11-16 US US05/961,473 patent/US4243767A/en not_active Expired - Lifetime
-
1979
- 1979-10-15 AU AU51784/79A patent/AU526613B2/en not_active Ceased
- 1979-10-19 CA CA338,031A patent/CA1123988A/en not_active Expired
- 1979-11-13 JP JP54146146A patent/JPS5917136B2/en not_active Expired
- 1979-11-15 EP EP79104523A patent/EP0011782B1/en not_active Expired
- 1979-11-15 DE DE7979104523T patent/DE2965827D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU5178479A (en) | 1980-05-22 |
| JPS5917136B2 (en) | 1984-04-19 |
| JPS5571752A (en) | 1980-05-30 |
| EP0011782B1 (en) | 1983-07-06 |
| US4243767A (en) | 1981-01-06 |
| AU526613B2 (en) | 1983-01-20 |
| EP0011782A1 (en) | 1980-06-11 |
| DE2965827D1 (en) | 1983-08-11 |
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