Coatings that contain reactive silicon oligomers

A coating comprising the silated reaction product of R.sup.1 (OH).sub.m and OCN(CH.sub.2).sub.t SiR.sup.4 (OR.sup.5).sub.2 and/or R.sup.2 --(SiYX.sub.2).sub.n ; a graft copolymer having an acrylic polymer based backbone and stabilizing arms comprising ethylenically unsaturated monomer, the backbone being insoluble and the arms being soluble in the composition; a melamine crosslinker; and an acrylic polyol; m, n, t, R.sup.1, R.sup.2 R.sup.4, R.sup.5, X and Y being defined in the text.

BACKGROUND OF THE INVENTION 
This invention concerns a composition comprising a silicon component, a 
stable non-aqueous dispersion, a crosslinker and an organic polyol, which 
composition cures to provide mar and etch resistant coatings particularly 
useful as a topcoat in multi-layered coating systems. 
A number of patents disclose silicon-containing curable coatings, all of 
them lacking the particular combination of components that make the 
instant compositions so effective in resistance to mar and etch. 
Representative of such patents is U.S. Pat. No. 4,467,081. 
Basecoat-clearcoat systems have found wide acceptance in the past decade as 
automotive finishes. Continuing effort has been directed to such coating 
systems to improve the overall appearance, the clarity of the topcoat, and 
the resistance to deterioration. Further effort has been directed to the 
development of coating compositions having low volatile organic content 
(VOC). A continuing need exists for coating formulations which provide 
outstanding performance characteristics after application, and 
particularly mar-resistance and resistance to environmental etching. 
Heretofore, mar-resistant coatings were attained by softening the coating, 
which depreciates other performance characteristics. The instant invention 
overcomes this problem. 
SUMMARY OF THE INVENTION 
This invention concerns a coating composition comprising the following 
components in amounts based on total weight of the composition: 
I) from 0 to 50 percent of the reaction product of a polyol of the formula 
EQU R.sup.1 --(OH).sub.m 
with 
EQU R.sup.2 --(SiYX.sub.2).sub.n 
the reaction product having a weight average molecular weight less than 
about 10,000, preferred less than about 3,000; 
II) from 0 to 50 percent of a graft copolymer comprising a backbone of 
acrylic polymer and, grafted thereto, a plurality of substantially linear 
stabilizer arms containing at least about 2 percent of ethylenically 
unsaturated monomer with functionality that reacts with at least one of 
components I, III and V, the backbone being substantially insoluble and 
the stabilizer arms being substantially soluble in the composition; 
III) from 0 to 30, preferred 0 to 20 percent, of an alkylated melamine 
formaldehyde crosslinking agent; 
IV) from 0 to 40, preferred 15 to 20 percent, of an organic polyol polymer 
having a hydroxyl number of about 50 to 200 and a weight average molecular 
weight of about 1,000 to 20,000, wherein the acrylic polymer comprises 
polymerized monomers selected from the group consisting of styrene; alkyl 
methacrylates and alkyl acrylates where the alkyl group has 1 to 12 carbon 
atoms; cycloaliphatic acrylates; cycloaliphatic methacrylates; aryl 
acrylates; aryl methacrylates; acrylamide; methacrylamide; acrylonitrile; 
methacrylonitrile; hydroxyalkyl acrylates and hydroxyalkyl methacrylates 
where the alkyl group has 1 to 4 carbon atoms; and mixtures thereof; 
V) from 0 to 50, preferred 15 to 20 percent, of a silane functional polymer 
which is the reaction product of about 5 to 70 percent by weight of 
ethylenically unsaturated silane-containing monomers selected from the 
group consisting of alkoxysilane monomers, acyloxysilane monomers, and 
mixtures thereof, with about 30 to 95 percent by weight of ethylenically 
unsaturated non-silane containing monomers selected from the group 
consisting of styrene; alkyl acrylate and alkyl methacrylate where the 
alkyl groups have 1 to 12 carbon atoms; cycloaliphatic acrylates; 
cycloaliphatic methacrylates; aryl acrylates; aryl methacrylates; 
acrylamide; methacrylamide; acrylonitrile; methacrylonitrile; hydroxyalkyl 
acrylates and hydroxyalkyl methacrylates where the alkyl group has 1 to 4 
carbon atoms; and mixtures thereof; 
VI) from 0 to 50 percent of the reaction product of a polyol of the formula 
EQU R.sup.3 --(OH).sub.p 
with an alkoxysilane of the formula 
EQU O.dbd.C.dbd.N--(CH.sub.2).sub.t --SiR.sup.4 (OR.sup.5).sub.2 
wherein: 
R.sup.1 is selected from the group consisting of 
a) C.sub.2 to C.sub.20 alkyl; cycloaliphatic of aromatic rings, each 
optionally substituted with at least one member selected from the group 
consisting of O, N, P and S; 
b) two or more cycloaliphatic or aromatic rings connected to each other 
through a covalent bond, or through an alkylene group of 1 to 5 carbon 
atoms, or through a heteroatom, or fused together to share two or more 
carbon atoms, each optionally substituted with a member selected from the 
group consisting of O, N, P and S; and 
c) linear polyester, branched polyester, linear and branched polyester, 
polyacrylate, polyolefin, polyether, polycarbonate, polyurethane, or 
polyamide, each such group having a weight average molecular weight 
between about 300 and 10,000, preferred less than 3,000; 
R.sup.2 is selected from the group consisting of 
a) C.sub.1 to C.sub.20 alkyl, cycloaliphatic or aromatic rings, each 
optionally substituted with a member selected from the group consisting of 
O, N, P and S; and 
b) two or more cycloaliphatic or aromatic rings connected to each other 
through a covalent bond, or through an alkylene group of 1 to 5 carbon 
atoms, or through a heteroatom, or fused together to share two or more 
carbon atoms, each optionally substituted with a member selected from the 
group consisting of O, N, P and S; 
R.sup.3 is selected from the group consisting of 
a) C.sub.2 to C.sub.20 alkyl, cycloaliphatic or aromatic rings, each 
optionally substituted with a member selected from the group consisting of 
O, N, P and S; 
b) two or more cycloaliphatic or aromatic rings, each connected to each 
other through a covalent bond, or through an alkylene group of 1 to 5 
carbon atoms, or through a heteroatom, or fused together to share two or 
more carbon atoms, each optionally substituted with a member selected from 
the group consisting of O, N, P and S; and 
c) linear polyester, branched polyester, linear and branched polyester, 
polyacrylate, polyolefin, polyether, polycarbonate, polyurethane or 
polyamide each such group having a weight average molecular weight between 
about 300 and 10,000, preferred less than 3,000; 
R.sup.4 is selected from the group consisting of alkyl of 1 to 12 carbon 
atoms, alkoxy containing 1 to 4 carbon atoms; 
R.sup.5 is selected from the group consisting of alkyl of 1 to 12 carbon 
atoms; 
X is independently selected from the group consisting of alkoxy containing 
1 to 20 carbon atoms, acyloxy containing 1 to 20 carbon atoms, phenoxy, 
halogen, amine, amide, urea, imidazole, carbamate, ketoximine, and 
oxazolidinone; 
Y is selected from the group consisting of alkyl of 1 to 12 carbon atoms, 
alkoxy containing 1 to 20 carbon atoms, acyloxy containing 1 to 20 carbon 
atoms, phenoxy, halogen, amine, amide, urea, imidazole, carbamate, and 
oxazolidinone; 
m is a positive integer of 2 or higher, preferred 2 to 30; 
n is a positive integer of 1 or higher, preferred 1 to 3; 
p is a positive integer of 2 or higher, preferred 2 to 30; and 
t is a positive integer of 1 to 8; 
wherein I.noteq.VI and 5 to 75 percent by weight of the composition is one 
or both of components I and VI. Preferred compositions comprise 20 to 60 
percent of I and/or VI and about 10 to 30 percent of V, most preferably 20 
percent of V. 
The compositions of this invention are oligomer-based and thus have a low 
volatile organic content (VOC). Characteristics of the compositions 
include hydroxy-containing, multifunctional structured polyester oligomers 
containing aliphatic and cycloaliphatic rings where the hydroxyls can be 
partly capped with silane functionality using a urethane linkage; 
structured oligomeric polymers containing silicate functionality; 
polymeric micro particles insoluble in the composition; and melamine 
crosslinker. This formulation provides improved scratch, mar and etch 
resistance. The silicates provide decreased viscosity which help lower 
VOC. In addition, the hydrogen bonding provided by the urethane linkages 
help maintain film integrity. The coatings are especially useful in 
automotive clearcoats. 
DETAILS OF THE INVENTION 
Component (I) 
This is a representative reaction mechanism for preparing an exemplary 
Component I of the composition. Synthesis of the hybrid silane-silicate 
component: 
##STR1## 
Preferred representatives of Component I are selected from the group 
consisting of the reaction product of at least one organic polyol; and a 
silicon-containing material comprising at least one silicon-containing 
substance essentially free of alkali metal ions, having atoms bonded 
directly to Si, all of said atoms being independently selected from the 
group consisting of C, O, N and halogen, said silicon-containing substance 
having moieties directly bonded to Si of which at least two are easily 
displaceable by reaction with alcohol or water; wherein said reaction 
product is homogeneous and contains residual moieties from the 
silicon-containing material which are directly bonded to Si and are easily 
displaceable by reaction with alcohol or water, and can also contain 
residual hydroxyl moieties from the organic polyol; said reaction product 
being self-curable to a continuous film by reaction of residual moieties 
from the organosilicon-containing material directly bonded to Si, with 
moisture and/or residual hydroxyl moieties from the organic polyol. 
The silicon-containing substance required in the silicon-containing 
material is defined as follows. An organosilicon-containing substance 
useful in the invention is essentially free of alkali metal ions which 
distinguish it from generally known inorganic silicates such as alkali 
metal silicates including, for example, sodium orthosilicate. 
Preferred organic polyol reactants for forming Component I are selected 
from (a) simple diols, triols, and higher hydroxyl alcohols, (b) 
polymer-based polyacrylate, polyester, polyether, polyamide, polyurethane, 
polycarbonate, polyhydrocarbon polyols, typically having a hydroxyl 
equivalent weight of about 30 to 1000, preferably from 50 to 500. 
The simple diols, triols, and higher hydroxyl alcohols are generally known, 
examples of which include 2,3-dimethyl-2,3-butanediol (pinacol), 
2,2-dimethyl-1-1,3-propanediol (neopentyl glycol), 
2-ethyl-2-methyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 
1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 
1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 
4,4'-isopropylidenedicyclohexanol, 
4,8-bis(hydroxyethyl)tricyclo[5.2.1.0]decane, 
1,3,5-tris(hydroxyethyl)cyanuric acid (theic acid), 
1,1,1-tris(hydroxymethyl)ethane, glycerol, pentaerythritol, sorbitol, 
sucrose and the like. 
Linear and branched polyacrylic polyols include but are not limited to the 
polymers comprising polymerized monomers selected from the group 
consisting of styrene; alpha-methylstyrene; alkyl methacrylates; alkyl 
acrylates where the alkyl group has 1 to 12 carbon atoms; cycloaliphatic 
acrylates; cycloaliphatic methacrylates; aryl acrylates, aryl 
methacrylates; acrylamide; methacrylamide; acrylonitrile; 
methacrylonitrile; hydroxyalkyl acrylates and hydroxyalkyl methacrylate 
where the alkyl group has 1 to 4 carbon atoms; and mixtures thereof. 
Throughout this disclosure, "alkyl groups" include cyclic alkyl groups 
within that term. 
Linear and branched polyester polyols useful in the preparation of I are 
known and prepared by conventional methods using simple diols, triols, and 
higher hydroxyl alcohols known in the art, including but not limited to 
the previously described simple diols, triols and higher hydroxyl alcohols 
with polycarboxylic acids. Examples of suitable polycarboxylic acids 
include but are not limited to hexahydro-4-methylphthalic acid; 
tetrahydrophthalic acid; phthalic acid; isophthalic acid; terephthalic 
acid; trimellitic acid; adipic acid; azelaic acid; sebasic acid; succinic 
acid; maleic acid; glutaric acid; malonic acid; pimelic acid; suberic 
acid; fumaric acid; itaconic acid; and the like. Anhydrides of the above 
acids, where they exist can also be employed and are encompassed by the 
term "polycarboxylic acids". In addition, multifunctional monomers which 
contain both hydroxyl and carboxyl functionalities, or their derivatives 
are also useful. Such monomers include but are not limited to lactones 
such as caprolactone; butyrolactone; valerolactone; propiolactone, and 
hydroxyacids such as hydroxy caproic acid; dimethylolpropionic acid and 
the like. 
Preferred linear and branched polyester polyols are prepared using simple 
diols, triols, and higher hydroxyl alcohols known in the art including but 
not limited to the previously described simple diols, triols and higher 
hydroxyl alcohols with anhydrides known in the art including but not 
limited to the previously described anhydrides such as 
hexahydromethylphthalic anhydride giving the corresponding polycarboxylic 
acids, which are then reacted with alkylene oxides, preferably with the 
glycidyl esters of organic acids such as commercial Cardura-E.RTM.. By 
this method, the resulting polyester polyol can predominantly contain 
secondary hydroxyl groups. 
Linear and branched polyether polyols useful in the preparation of I are 
known and prepared by conventional methods, typically by the ring-opening 
polymerization of cyclic ethers and/or acetals known in the art including 
but not limited to epoxides, oxetanes, furanes and higher cyclic ethers, 
optionally also using simple diols, triols, and higher hydroxyl alcohols 
known in the art including but not limited to the previously described 
simple diols, triols and higher hydroxyl alcohols in order to introduce 
the hydroxyl end groups and to control polymer molecular weight and 
topology. Examples of polyether polyols include the generally known 
poly(tetramethylene oxide) diols, e.g., commercial Terathane.RTM., 
prepared by polymerization of tetrahydrofuran in the presence of cationic 
catalysts. The useful polyether polyols also include the poly(propylene 
oxide) diols prepared by cationic or anionic polymerization or 
copolymerization of propylene oxide. The simple diols, triols, and higher 
hydroxyl alcohols can be used as initiators/telogens to make controlled 
linear and branched structures. 
Linear and branched amide-containing polyols are known and prepared by 
analogous processes described for preparation of the polyester polyols 
from any of the above described diacids and diols and/or higher hydroxyl 
alcohols or lactones, but using in addition certain amount of diamines 
and/or higher amines and/or aminoalcohols. 
Linear and branched polycarbonate polyols useful in the preparation of I 
are known and prepared by conventional methods using simple diols, triols, 
and higher hydroxyl alcohols including but not limited to the previously 
described simple diols, triols, and higher hydroxyl alcohols with 
carbonates. Aliphatic polycarbonate polyols can also be prepared from 
1,3-dioxan-2-ones. Conventional methods for the preparation of the 
aliphatic polycarbonate polyols include transesterification of simple 
diols, triols, and higher hydroxyl alcohols with lower dialkyl carbonates, 
dioxolanones, or diphenyl carbonate in the presence of catalysts such as 
alkali metal, tin, and titanium compounds. 
Linear and branched polyurethane polyols useful in the preparation of I are 
known and prepared by conventional methods using simple diols, triols, and 
higher hydroxyl alcohols including but not limited to the previously 
described simple diols, triols, and higher hydroxyl alcohols, polyester 
polyols, amide-containing polyols, polycarbonate polyols, polyhydrocarbone 
polyols with organic polyisocyanates. The organic polyisocyanate can be 
reacted with the polyol either directly to form the polyurethane polyol or 
by the prepolymer method wherein the polyol and polyisocyanate are reacted 
in relative proportion to first produce an isocyanate-terminated 
prepolymer with subsequent reaction of the prepolymer with the same or 
different additional polyol to form the polyurethane polyol. The 
polyisocyanate which is reacted with the polyol can be any organic 
polyisocyanate. The polyisocyanate can be aromatic, aliphatic, 
cycloaliphatic, or heterocyclic and can be substituted or unsubstituted. 
Many such organic polyisocyanates are known, examples of which include: 
toluene diisocyanate isomers, diphenylmethane diisocyanate isomers, 
biphenyl diisocyanate, tetramethylene-1,4-diisocyanate, 
hexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexane 
diisocyanate isomers, hexahydrotoluene diisocyanate isomers and mixtures 
thereof. 
Polyhydrocarbone polyols useful in the preparation of I are known and 
prepared by conventional methods using olefins such as isoprene, 
butadiene, styrene usually polymerized in the presence of multifunctional 
anionic initiators, followed by hydroxylation with epoxides or in the 
presence of multifunctional cationic initiators for monomers like 
isobutylene, styrene followed by hydroxylation of olefin terminal groups. 
Many such polyhydrocarbone polyols are known and commercially available, 
an example of which is Shell's Kraton Liquid.RTM. Polymers. 
Preferred silicon-containing reactants for forming I are selected from at 
least one silicon-containing substance essentially free of alkali metal 
ions, having atoms bonded directly to Si, all said atoms being selected 
from the group consisting of C, O, N, and/or halogen, said 
silicon-containing substance having at least two moieties directly bonded 
to Si which are easily displaceable by reaction with water and/or alcohol. 
Examples of moieties directly bonded to Si which are displaceable by 
reaction with alcohol or water include but are not limited to --OR 
(alkoxy, aryloxy), --O(O)CR (acyloxy), --NH(O)CR (amide), --NH(O)COR 
(carbamate), --NH(O)CNHR (urea), --ON.dbd.CR.sup.2 (ketoximine), 
--NR.sup.2 (amine), --X (halogen). 
The preferred silicon-containing reactants useful in preparing I are 
selected from (a) simple monosilanes, R.sup.2 --SiYX.sub.2, (b) 
multisilanes, R.sup.2 --(SiYX.sub.2).sub.n containing at least two 
reactive silane groups preferably two or three having a silicon equivalent 
weight of about 30 to 600, preferably from 50 to 400. 
The simple monosilanes R.sup.2 --SiYX.sub.2 include structures where 
R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.20 
linear or branched alkyl, cycloaliphatic or aromatic rings, each 
optionally substituted with a member selected from the group consisting of 
O, N, P and S; alkoxy containing 1 to 20 carbon atoms, acyloxy containing 
1 to 20 carbon atoms, phenoxy, halogen, amine, amide, urea, imidazole, 
carbamate, ketoximine and oxazolidinone; X is selected from the group 
consisting of alkoxy containing 1 to 20 carbon atoms, acyloxy containing 1 
to 20 carbon atoms, phenoxy, halogen, amine, amide, urea, imidazole, 
carbamate, ketoximine and oxazolidinone; Y is selected from the group 
consisting of alkyl of 1 to 12 carbon atoms, alkoxy containing 1 to 20 
carbon atoms, acyloxy containing 1 to 20 carbon atoms, phenoxy, halogen, 
amine, amide, urea, imidazole, carbamate, ketoximine and oxazolidinone. 
Examples of the monosilanes include but are not limited to the following 
alkoxysilanes: tetramethoxysilane, tetraethoxysilane, teterapropoxysilane, 
methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, 
ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, 
propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, 
isobutyltrimethoxysilane, isobutyltriethoxysilane, 
isobutyltripropxysilane, octyltrimethoxysilane, octyltriethoxysilane, 
octyltripropoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, 
isooctyltripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 
vinyltripropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 
phenyltripropoxysilane. 
Examples of silicon-containing reactants other than the above alkoxysilanes 
include the analogous silanes in which the alkoxysilane groups are 
replaced by the following groups which are also displaceable by reaction 
with alcohol or water: acetoxy, phenoxy, chloro, methylethylketoximine, 
acetamide, carbamate, amine, imidazole, urea, and oxazolidinone. 
Multisilanes R.sup.2 --(SiYX.sub.2).sub.n containing at least two reactive 
silane groups are known and typically prepared by methods based on the 
hydrosilylation of dienes, trienes or higher polyolefins with the 
corresponding hydrosilanes. The hydrosilylation can be accomplished either 
using free-radical initiators or various other catalysts, including 
transition metals. The multifunctional silanes R.sup.2 
--(SiYX.sub.2).sub.n include structures where R.sup.2 is selected from the 
group consisting of C.sub.2 to C.sub.20 linear branched alkyl, 
cycloaliphatic or aromatic rings, each optionally substituted with a 
member selected from the group consisting of O, N, P and S; two or more 
cycloaliphatic or aromatic rings, connected to each other through a 
covalent bond, or through an alkylene group of 1 to 5 carbon atoms, each 
optionally substituted with a member selected from the group consisting of 
O, N, P, and S; alkoxy containing 1 to 20 carbon atoms, acyloxy containing 
1 to 20 carbon atoms, phenoxy, halogen, amine, amide, urea, imidazole, 
carbamate, ketoximine and oxazolidinone; X is selected from the group 
consisting of alkoxy containing 1 to 20 carbon atoms, acyloxy containing 1 
to 20 carbon atoms, phenoxy, halogen, amine, amide, urea, imidazole, 
carbamate, ketoximine and oxazolidinone; Y is selected from the group 
consisting of alkyl of 1 to 12 carbon atoms, alkoxy containing 1 to 20 
carbon atoms, acyloxy containing 1 to 20 carbon atoms, phenoxy, halogen, 
amine, amide, urea, imidazole, carbamate, ketoximine and oxazolidinone. 
Examples of multifunctional silanes include but are not limited to 
1,2-bis(trimethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, 
1,8-bis(trimethoxysilyl)octane, 1,4-bis(trimethoxysilylethyl)benzene, 
bis(3-trimethoxysilylpropyl)amine, 
bis(3-trimethoxysilylpropyl)ethylenediamine, bis(trimethoxysilyl) 
derivatives of the following polyolefins: limonene and other terpines, 
4-vinyl-1-cyclohexene, 5-vinyl-2-norbornene, norbornadiene, 
dicyclopentadiene, 1,5,9-cyclododecatriene, tris(trimethoxysilyl) 
derivatives of higher polyolefins such as 1,2,4-trivinylcyclohexane and 
the like. Examples of the substituted multifunctional silanes include but 
are not limited to bis and tris(trimethoxysilane) derivatives of 
polyunsaturated polyesters of the corresponding acids: trimellitic acid, 
cyclohexane dicarboxylic acids, 10-undecenoic acid, vinylacetic acid; and 
bis and tris(trimethoxysilane) derivatives of polyunsaturated polyethers 
of the corresponding polyols: 1,4-cyclohexanedimethanol, 
4,4'-isopropylidenedicyclohexanol. 
The reactive monosilanes and multisilanes usually contain variable levels 
of their corresponding hydrolysis and condensation products from the 
reaction with water which can be added purposely or adventitiously 
introduced from ambient moisture or with other components, particularly 
polyols. The hydrolysis/condensation processes introduce the stable 
--Si--O--Si-- linkages, and increase silane average molecular weight, 
functionality and product I viscosity. 
Optionally, the reactive silanes R.sup.2 --(SiYX.sub.2).sub.n can contain 
an organofunctional group attached to Si not directly but through R.sup.2. 
Examples of functional groups include amino, epoxy, mercapto, isocyanate, 
ureido, phosphate, olefin (vinyl, allyl, acrylate) and the like. The 
organofunctional silanes are known, examples of which include but are not 
limited to 3-aminopropyltrimethoxysilane, 
3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 
3-isocyanopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 
diethylphosphatoethyltriethoxysilane, vinyltrimethoxysilane, 
allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and the 
corresponding analogs of the above where the trimethoxysilane group is 
replaced by various combinations of methyldialkoxysilane groups as defined 
by --SiYX.sub.2. Although the incorporation of some organofunctional 
silanes can be desirable for some properties, their level should be 
minimized or avoided because the organofunctional silanes are 
significantly more expensive than non-organofunctional silanes. 
An objective of this invention is to replace organosilanes (Si--C) by silyl 
ethers (SiO--C). The organofunctional silanes have reactive silane groups 
attached through a very hydrolytically stable Si--C bond, but they are 
more expensive and structurally limited, due to the demanding nature of 
the direct and hydrosilylation synthetic processes. In contrast, the silyl 
ethers have a less hydrolytically stable C--O--Si linkage, but are less 
expensive and available in many variations through a convenient exchange 
process involving polyol hydroxyl group and the silane exchangeable 
groups. Furthermore, the C--O--Si stability can be dramatically increased 
by a few orders of magnitude via steric and hydrophobic factors, which are 
virtually unexplored in heterogeneous polymeric systems. Another objective 
of this invention is to develop stable unconventional polymeric silyl 
ethers with good chemical stability. 
The silylation of the polyol R.sup.1 --(OH).sub.m with R.sup.2 
--(SiYX.sub.2).sub.n resulting in the C--O--Si formation is usually an 
equilibrium process, which can be controlled, e.g., shifted toward the 
desired R.sup.1 --C--O--Si--R.sup.2, by using an excess of a silane and/or 
removing a volatile X--H by-product. The reaction can be carried out with 
or without a catalyst primarily depending on the reactivity of the SiX. It 
is desired for storage stability, particularly moisture stability, to 
prepare a product essentially free of catalyst. Therefore, catalysts which 
can be effectively and conveniently removed from the products are 
preferred for the silylation. Particularly useful are heterogeneous 
catalysts such as fluorosulfonic acid (Nafion.RTM. NR-50; DuPont), which 
can be easily separated from the product. Other preferred catalysts are 
volatile catalysts such as trifluoroacetic acid, amines or thermofugitive 
catalysts such a tetraalkylammonium hydroxides, which can be substantially 
removed by a postheating. Many other useful catalysts can be employed and 
removed by passing the product through appropriate ion exchange or 
absorbing media. Examples of other useful catalysts include but are not 
limited to medium and strong acids or bases such as sulfonic acids, alkali 
bases; ammonium salts; tin containing compounds such as dibutyltin 
dilaurate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dioxide; 
titanates such as tetraisopropyl titanate, tetrabutyl titanate (DuPont 
Tyzor.RTM.), aluminum titanate, aluminum chelates, zirconium chelate and 
the like. 
Typically, the silylation reaction is conducted in a substantially 
moisture-free atmosphere, usually under a blanket of an inert dry gas such 
as nitrogen. The polyol R.sup.1 --(OH).sub.m and the silane R.sup.2 
--(SiYX.sub.2).sub.n, optionally with a catalyst, are heated for several 
hours at temperatures ranging from 60.degree. to 200.degree. C. with the 
distillation and removal of the low boiling, volatile reaction by-product 
such as an alcohol (typically methanol). The reaction progress is 
controlled by monitoring the amount of the by-product alcohol collected, 
reaction mixture viscosity changes, optionally substrate conversion and 
product formation by GC, MS and NMR. To minimize color in product, 
conventional methods can be employed such as anticolor additives 
containing active P--H groups or filtration through active carbon, silicon 
or other standard decolorizing media. The synthesis can be carried out 
without solvent or with a little of any aprotic solvents because the 
replacement of the H-bonded hydroxyl groups in the starting polyols by low 
polarity silyl groups results in a dramatic viscosity reduction of two to 
three orders of magnitude. This is a highly desired feature allowing 
significant volatile organic component (VOC) reduction. Typically, the 
silylated polyols useful for high solids coatings have viscosity in the 
range of 1 to 10,000 centipoise. 
The silylation of R.sup.1 --(OH)m with R.sup.2 --(SiYX.sub.2).sub.n usually 
gives a complex mixture composed of various oligomers and isomers as 
indicated by MS analysis. This is due to the statistical nature of the 
silylation involving multifunctional substrates and a contribution of the 
silane hydrolysis/condensation processes from usually adventitious water. 
An attractive property balance such as scratch, mar, chemical etch 
resistance, and appearance is often provided by a narrow operational 
window of a special product mixture composition. The oligomer composition 
can be varied widely by the substrate ratio and the extent of the 
oligomerization as controlled by catalyst choice, time and temperature 
shown in the Procedures presented hereafter. 
The silylated polyols I are storage stable. To enhance the storage 
stability, it is recommended to prevent the introduction of moisture by 
storing in airtight containers, under dry inert gas such as nitrogen. It 
is desired for stability to have a product essentially free of any 
catalyst; optionally to add conventional moisture scavengers such as 
orthoformates, orthoacetates or certain alcohols. 
Component (II) 
The dispersed polymer employed in the compositions of the present invention 
are characterized as polymer particles dispersed in an organic media, 
which particles are stabilized by what is known as steric stabilization. 
In the dispersed polymers, the dispersed phase or particle, sheathed by a 
steric barrier, will be referred to as the "macromolecular polymer" or 
"backbone." The stabilizer forming the steric barrier attached to this 
backbone, will be referred to as the "macromonomer chains" or "arms." 
The dispersed polymers solve the problem of cracking heretofore associated 
with silane coatings. These dispersed polymers, to reduce cracking to the 
desired minimum, must be used in higher amounts than dispersed polymers 
are typically used for other purposes. For example, while microgels have 
been used in basecoats for flow control at levels of not more than about 
5%, the present dispersed polymers are used in an amount varying from 
about 10 to 60% by weight, preferably about 15 to 40%, more preferably 
about 20 to 30%, of the total solids binder in the composition. The ratio 
of the silane polymer component of the composition suitably ranges from 
5:1 to 1:2, preferably 4:1 to 1:1. These relatively high concentrations of 
dispersed polymers, are made possible by the presence of reactive groups 
on the arms of the dispersed polymer, which reactive groups make the 
polymers compatible with the continuous phase of the system. 
The dispersed polymer contains about 10-90% by weight, preferably 50-80%, 
based on the weight of the dispersed polymer, of a high molecular weight 
backbone having a weight average molecular weight of about 50,000-500,000. 
The preferred average particle size is 0.1 to 0.5 microns. The arms, 
attached to the backbone, make up about 10-90% by weight, preferably 
20-50%, of the dispersed polymer, and have a weight average molecular 
weight of about 1,000-30,000, preferably 1,000-10,000. 
Preferably, the macromolecular backbone of the dispersed polymer is 
comprised of polymerized ethylenically unsaturated monomers. Suitable 
monomers include styrene, alkyl acrylate or methacrylate, ethylenically 
unsaturated monocarboxylic acid, and/or silane containing monomers. Such 
monomers as methyl methacrylate contribute to a high Tg (glass transition 
temperature) dispersed polymer, whereas such "softening" monomers as butyl 
acrylate or 2-ethylhexylacrylate contribute to a low Tg dispersed polymer. 
Other optional monomers are hydroxyalkyl acrylates or methacrylates or 
acrylonitrile. It is noted that such functional groups as hydroxy can 
react with silane groups in the organosilane polymer to produce more 
bonding in the composition. If the backbone is crosslinked, allyl acrylate 
or methacrylate, which crosslink with each other, can be used or an epoxy 
functional monomer such as glycidyl acrylate or methacrylate can be used, 
which can react with a monocarboxylic acid functional ethylenically 
unsaturated monomer to crosslink the backbone. 
There can be silane functionality for crosslinking purposes, in the 
backbone, which functionality can be provided by a small amount of one or 
more of the silane-containing monomers mentioned above with respect to the 
film forming organosilane polymer. About 2 to 10%, preferably less than 
5%, of the monomers making up the macromolecular backbone are silane 
monomers capable of crosslinking between themselves. Thus, crosslinking 
occurs by siloxane bonding (--Si--O--Si--). This silane crosslinking 
enables the backbone to behave as a non-crosslinked polymer before cure 
for good flow during application, resulting in improved appearance. The 
backbone can crosslink during and after curing, upon exposure to humidity 
and heat during curing and/or exposure to humidity in the environment 
after curing. A further advantage of silane being present in the backbone 
is that the cured film does not blush when exposed to humidity, which 
blushing was found to occur without the presence of silane. If the core is 
pre-crosslinked (before curing) by other means, such as acid/epoxy or 
diacrylates, then humidity sensitivity can be eliminated but the system 
may have poor flow and appearance. 
A distinctive feature of the dispersed polymers is the presence of 
macromonomer arms which are reactive, that is these arms have numerous 
reactive groups, referred to a "crosslinking functionalities," which are 
adapted to react with the organosilane polymer of the present composition. 
A substantial portion of these functionalities in the arms, preferably the 
majority thereof, react and crosslink with the film-former of the 
composition, which can exclusively consist of an organosilane polymer. Of 
course, if additional film-forming polymers are present, for exarnple, a 
polyol, then the arms can react with film-formers other than the 
organosilane polymer. Suitably, about 3 to 30% of the monomers which make 
up the macromonomer arms have reactive crosslinking functional groups. 
Preferably, about 10 to 20% of the monomers have such reactive groups. 
The arms of the dispersed polymer, should be anchored securely to the 
macromolecular backbone. For this reason, the arms are typically anchored 
by covalent bonds. The anchoring must be sufficient to hold the arms to 
the dispersed polymer after they react with the film-former polymer. The 
arms suitably comprise about 5 to 30% by weight, preferably 10 to 20%, 
based on the weight of macromonomer, of polymerized ethylenically 
unsaturated hydroxy, epoxide, silane, acid, anhydride, isocyanate, amine, 
or other crosslinking functionality containing monomers, or combinations 
thereof, and about 70-95% by weight, based on the weight of the 
macromonomer, of at least one other polymerized ethylenically unsaturated 
monomer without such crosslinking functionality. Preferably, the 
crosslinking functionality is a hydroxy, silane or epoxy containing 
monomer, since such reactive groups can be utilized in one package 
systems. When the crosslinking functionality is an acid, anhydride, or 
isocyanate, then a two package system, with the dispersed polymer in a 
first package and the organosilane in a second package, is generally 
required. Combinations of the above-mentioned crosslinking functional 
groups are also suitable, although it is noted that hydroxy and silane 
groups have limited compatibility and are preferably not on the same 
macromonomer chain. 
As an example, the macromonomer arms attached to the backbone can contain 
polymerized monomers of alkyl methacrylate, alkyl acrylate, each having 
1-12 carbon atoms in the alkyl group, as well as glycidyl acrylate or 
glycidyl methacrylate or ethylenically unsaturated monocarboxylic acid 
containing monomers for anchoring and/or crosslinking. Typically useful 
hydroxy containing monomers are hydroxy alkyl acrylates or methacrylates 
as described above. One skilled in the art will know how to prepare 
Component II. 
Component III 
Representative of the melamine component useful in the composition(s) of 
this invention are monomeric or polymeric alkylated melamine formaldehyde 
resins that are partially or fully alkylated. One preferred crosslinking 
agent is a methylated and butylated or is butylated melamine formaldehyde 
resin that has a degree of polymerization of about 1-3. Generally, this 
melamine formaldehyde resin contains about 50% butylated groups or 
isobutylated groups and 50% methylated groups. Such crosslinking agents 
typically have a number average molecular weight of about 500-1500. 
Examples of commercially available resins are "Cymel" 1168, "Cymel" 1161, 
"Cymel" 1158, "Resimine" 4514 and "Resimine" 354. Preferably, the 
crosslinking agent is used in the amount of about 5-50% by weight, based 
on the weight of the binder of the composition. Other crosslinking agents 
are alkylated urea formaldehyde, alkylated benzoguanamine formaldehyde and 
blocked isocyanates. 
Component IV 
Representative organic polyol film-formers useful in the compositions of 
this invention include acrylics, cellulosics, urethanes, polyesters, 
epoxides or mixtures thereof. One preferred optional film-forming polymer 
is a polyol, for example an acrylic polyol solution polymer of polymerized 
monomers. Such monomers may include any of the aforementioned alkyl 
acrylates and/or methacrylates and, in addition, hydroxy alkyl acrylates 
or methacrylates. The polyol polymer preferably has a hydroxyl number of 
about 50-200 and a weight average molecular weight of about 1,000-200,000 
and preferably about 1,000-20,000. 
To provide the hydroxy functionality in the polyol, up to about 90% by 
weight, preferably 20 to 50%, of the polyol comprises hydroxy-functional 
polymerized monomers. Suitable monomers include hydroxyalkyl acrylates and 
methacrylates, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, 
hydroxyisopropyl acrylate, hydroxybutyl acrylate, hydroxyethyl 
methacrylate, hydroxypropyl methacrylate, hydroxyisopropyl methacrylate, 
hydroxybutyl methacrylate and the like, and mixtures thereof. 
Other polymerizable non-hydroxy containing monomers can be included in the 
polyol polymer, in an amount up to about 90% by weight, preferably 50 to 
80%. Such polymerizable monomers include, for example, styrene, 
methylstyrene, acrylamide, acrylonitrile, methacrylonitrile, 
methacrylamide, methylol methacrylamide, methylol acrylamide, and the 
like, and mixtures thereof. 
One example of an acrylic polyol polymer comprises about 10-20% by weight 
of styrene, 40-60% by weight of alkyl methacrylate or acrylate having 1-8 
carbon atoms in the alkyl group, and 10-50% by weight of hydroxy alkyl 
acrylate or methacrylate having 1-4 carbon atoms in the alkyl group. One 
such polymer contains about 15% by weight styrene, about 29% by weight 
isobutyl methacrylate, about 20% by weight of 2-ethylhexyl acrylate, and 
about 36% by weight of hydroxypropyl acrylate. 
Component V 
Contemplated silane-functional polymers include reaction products 
comprising ethylenically unsaturated non-silane containing monomers and 
ethylenically unsaturated silane-containing monomers. Suitable 
ethylenically unsaturated non-silane containing monomers are alkyl 
acrylates, alkyl methacrylates and any mixtures thereof, where the alkyl 
groups have 1-12 carbon atoms, preferably 1-8 carbon atoms. 
Suitable alkyl methacrylate monomers used to form the organosilane polymer 
are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl 
methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl 
methacrylate, octyl methacrylate, nonyl methacrylate, lauryl methacrylate 
and the like. Similarly, suitable alkyl acrylate monomers include methyl 
acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl 
acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, 
lauryl acrylate and the like. Cycloaliphatic methacrylates and acrylates 
also can be used, such as trimethylcyclohexyl methacrylate, 
trimethylcyclohexyl acrylate, isobutylcyclohexyl methacrylate, 
t-butylcyclohexyl acrylate, t-butylcyclohexyl methacrylate, cyclohexyl 
methacrylate, cyclohexyl acrylate, isobornyl methacrylate, and isobornyl 
acrylate. Aryl acrylate and aryl methacrylates also can be used, such as 
benzyl acrylate and benzyl methacrylate, and mixtures of two or more of 
the above mentioned monomers are also suitable. 
In addition to alkyl acrylates or methacrylates, other non-silane 
containing polymerizable monomers, up to about 50% by weight of the 
polymer, can be used in the acrylosilane polymer for the purpose of 
achieving the desired properties such as hardness, appearance, mar 
resistance, and the like. Exemplary of such other monomers are styrene, 
methyl styrene, acrylamide, acrylonitrile, methacrylonitrile, and the 
like. Styrene can be used in the range of 0-50% by weight. 
A suitable silane containing monomer useful in forming the acrylosilane 
polymer is an alkoxysilane having the following structural formula: 
##STR2## 
wherein R.sup.4 and R.sup.5 are as described above; and are independently 
either H, CH.sub.3, CH.sub.3 CH.sub.2, and n is 0 or a positive integer 
from 1 to 10. R.sup.6 is selected from H and C.sub.1 to C.sub.12 alkyl. 
Preferably, R.sup.4 is CH.sub.3, CH.sub.3 O or CH.sub.3 CH.sub.2 O, 
R.sup.6 is methyl, and n is 1. 
Typical alkoxysilanes are the acrylatoalkoxy silanes, such as 
gamma-acryloxypropyl-trimethoxy silane and the methacrylatoalkoxy silanes, 
such as gamma-methacryloxypropyltrimethoxy silane, and 
gamma-methacryloxypropyltris(2-methoxyethoxy)silane. 
Other suitable alkoxy silane monomers have the following structural 
formula: 
##STR3## 
wherein R.sup.4 and R.sup.5 are described above and n is 0 or a positive 
integer from 1 to 10. 
Examples of such alkoxysilanes are the vinylalkoxy silanes, such as 
vinyltrimethoxy silane, vinyltriethoxy silane and 
vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane and 
allyltriethoxysilane. 
Other suitable silane containing monomers are ethylenically unsaturated 
acryloxysilanes, including acrylatoxysilane, methacrylatoxysilane and 
vinylacetoxysilanes, such as vinylmethyldiacetoxysilane, 
acrylatopropyltriacetoxysilane, and methacrylatopropyltriacetoxysilane. Of 
course, mixtures of the above-mentioned silane-containing monomers are 
also suitable. 
Silane functional macromonomers also can be used in forming the silane 
polymer. These macromonomers are the reaction product of a silane 
containing compound, having a reactive group such as epoxide, amine or 
isocyanate, with an ethylenically unsaturated non-silane containing 
monomer having a reactive group, typically a hydroxyl or an epoxide group, 
that is co-reactive with the silane monomer. An example of a useful 
macromonomer is the reaction product of a hydroxy-functional ethylenically 
unsaturated monomer such as a hydroxyalkyl acrylate or methacrylate having 
1-4 carbon atoms in the alkyl group and an isocyanatoalkylalkoxysilane 
such as isocyanatopropyltrimethoxysilane. 
Typical of silane-functional macromonomers are those having the following 
structural formula: 
##STR4## 
wherein R.sup.4, R.sup.5, and R.sup.6 are as described above; R.sup.7 is 
alkylene of 1 to 8 carbons and n is a positive integer from 1 to 8. 
Component VI 
Preferred representatives of Component VI are selected from the group 
consisting of the reaction product of an isocyanoalkylalkoxysilane with 
one or more organic polyols R.sup.3 --(OH).sub.p described above for use 
in the preparation of I, or selected from the group R.sup.1 --(OH).sub.m 
described above for use in the preparation of Component VI. 
Other Ingredients 
A catalyst is typically added to catalyze the crosslinking of the silane 
moieties of the silane polymer with itself and with other components of 
the composition, including the dispersed polymer. Typical of such 
catalysts are dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin 
dioxide, dibutyl tin dioctoate, tin acetate, titanates such as 
tetraisopropyl titanate, tetrabutyl titanate (DuPont Tyzor.RTM.), aluminum 
titanate, aluminum chelates, zirconium chelate and the like. 
Amines and acids or combinations thereof are also useful for catalyzing 
silane bonding. Preferably, these catalysts are used in the amount of 
about 0.1 to 5.0% by weight of the composition. 
In addition, the coating composition can include a structured polymer 
and/or a star polymer. 
To improve weatherability of a clear finish produced by the present coating 
composition, an ultraviolet light stabilizer or a combination of 
ultraviolet light stabilizers can be added in the amount of about 0.1-5% 
by weight, based on the weight of the binder. Such stabilizers include 
ultraviolet light absorbers, screeners, quenchers, and specific hindered 
amine light stabilizers. Also, an antioxidant can be added, in the about 
0.1-5% by weight, based on the weight of the binder. 
Typical ultraviolet light stabilizers that are useful include 
benzophenones, triazoles, triazines, benzoates, hindered amines and 
mixtures thereof. The composition can also include other conventional 
formulation additives such as flow control agents, for example such as 
Resiflow.RTM. S (polybutylacrylate), BYK 320 and 325 (polyether-modified 
polysiloxanes); rheology control agents, such as fumed silica, and the 
like. 
The coating composition of this invention based on Components I through VI 
is typically formulated as a one-package system by conventional methods, 
although two-package systems are also possible as will occur to one 
skilled in the art. 
EXAMPLES AND PROCEDURES 
Procedures. 
Method for Making Silanated 4-vinyl-1-cyclohexene (Intermediate of I) 
A 2-neck 100 ml round-bottom flask was equipped with a magnetic stirring 
bar, heating mantle, solids addition funnel, and condenser. The condenser 
was fitted with a Claisen adapter and a polytetrafluoroethylene-clad 
thermocouple was inserted through the Claisen adapter and condenser to 
reach the liquid layer of the flask. The other arm of the Claisen adapter 
was connected to a 50 ml liquid addition funnel fitted with a Dewar 
condenser. The entire assembly was purged with nitrogen prior to the 
reaction and a positive pressure of nitrogen was maintained during the 
reaction. 
The round bottom flask was charged with 4-vinyl-1-cyclohexene (22 g, 0.20 
mole). The solids addition funnel was charged with 3 g of Vazo.RTM. 64. 
The liquid addition funnel was charged with trichlorosilane (57 g, 0.42 
mole). The condenser on the flask and the condenser on the solids addition 
funnel were cooled to -10.degree. C. Stirring was started and the flask 
contents were heated. Once the flask temperature exceeded 90.degree. C., 
enough trichlorosilane was added to bring the flask temperature to about 
85.degree. C. Small quantities of Vazo.RTM. 64 were added intermittently. 
The temperature was maintained between 85-95.degree. C. by adding 
trichlorosilane and small amounts of initiator as needed. 
Excess trichlorosilane in the reaction mixture was evaporated by passing 
nitrogen over the reaction mixture and recondensing trichlorosilane in the 
liquid addition funnel. At this point, the temperature was allowed to rise 
to 125.degree. C., then held for 1 hour. The total reaction time was 15 
hours. The reaction mixture was then cooled to ambient temperature and the 
product isolated by standard inert atmosphere techniques. After isolation 
GC analysis using an internal standard indicated that the vinylcyclohexene 
was consumed giving both monosubstituted product: 
4-(2-trichlorosilylethyl)cyclohex-1-ene and isomers thereof and 
distributed product: 4-(2-trichlorosilylethyl)-1-trichlorosilylcyclohexane 
and isomers thereof. Bis(trimethoxysilylated) product (4-VCHSi.sub.2) was 
obtained by a conventional methoxylation of the reaction mixture and 
isolated by a vacuum distillation. 
Preparation of 4-VCH--Si.sub.2 /HBPA Silane/Silicate Hybrid Oligomers 
In a five-liter flask equipped with a magnetic stirrer, Vigreux fractional 
distillation head under nitrogen blanket, were heated at 100-120.degree. 
C., hydrogenated bisphenol A HBPA (700 g, 2.91 mole), 4-VCH--Si.sub.2 
(2400 g, 6.82 mole), Nafion.RTM. NR-50 (100 g), trifluoroacetic acid 
(TFAA, 5 g). In about 6 hours, the pot temperature increased from 105 to 
119.degree. C. and about 240 ml MeOH was collected. Crude product: 
viscosity 12 poise, color a=-1.3, b=+6.4. Optionally, the crude product 
was diluted with about 500 ml hexanes, filtered through a multilayer 
system composed of: a Whatman 50 filter paper; silica gel desiccant, grade 
12; silica gel 60; and decolorizing carbon, Norit.RTM. 211. Volatiles were 
removed in 1 hour at 75.degree. C. under vacuum (20 Torr) on a 
rotary-evaporator. Yield: 2700 g, viscosity 15 poise, Mn=1750, Mw/Mn=1.45 
(by MALDI MS), color a=-0.79, b=+3.8. 
Procedure for Making Acrylic Polyol 
In a 5-liter nitrogen inerted flask equipped with 2 addition inlets charge 
198 g of ethylene glycol monobutyl acetate and 198 g of aromatic 
hydrocarbon solvent (155.degree. C. to 177.degree. C. boiling range, e.g., 
Cyclosol.RTM. 100 from Shell Chemical Co.). Heat to reflux. Add the 
following two mixtures over an eight hour period; (1) 834.8 g of styrene, 
973.9 g of hydroxypropyl acrylate, 556 g of isobutyl methacrylate, 417.4 g 
of butyl acrylate, 43.2 g of the above mentioned aromatic hydrocarbon 
solvent and 43.2 g of ethylene glycol monobutyl acetate. Dissolve in 
mineral spirits: (2) 107.3 g of ethylene glycol monobutyl acetate, 107.3 g 
of aromatic hydrocarbon solvent and 292.9 g of a 75 weight percent 
solution of t-butylperoxyacetate. Hold the mixture at reflux for 30 
minutes after addition and then cool and empty. 
Preparation of Acrylic Polyol Silicate 
In a five-liter flask equipped with a magnetic stirrer, Vigreux fractional 
distillation head under nitrogen blanket were heated at 85-120.degree. C. 
acrylic polyol (2000 g, 65 weight percent in aromatic spirit, copolymer 
containing 31 weight percent of styrene, 22 weight percent of 
cyclohexylmethacrylate, 8 weight percent of isobutylmethacrylate, 39 
weight percent of hydroxypropylmethacrylate, 3.52 mole OH), 
methyltrimethoxylsilane (MTMOS, 1100 g, 8.08 mole), Nafion.RTM. NR-50 (137 
g). In about 6 hours, the pot temperature increases from 95 to 120.degree. 
C. and 154 ml of distillate containing mostly MeOH is collected. The 
Vigreux column is replaced by a short path distillation head and an excess 
of MTMOS is distilled off at a pot temperature up to 125.degree. C. The 
crude product is diluted with about 500 ml of EtOAc, filtered through a 
multilayer system composed of a Whatman 50 filter paper; silica gel 
desiccant, grade 12; silica gel 60; decolorizing carbon, Norit 211. 
Volatiles are removed in 1 hour at 75.degree. C. under vacuum (20 Torr) on 
a rotary-evaporator. Yield: 1837 g, viscosity &gt;100 poise. 
Procedure for Acrylosilane Resin 
In a 5-liter, nitrogen inerted flask, charge 900 g of n-pentyl propionate. 
Heat to reflux. To the flask, add the following mixture over the course of 
six (6) hours: 1,896 g of styrene, 1164.8 g of 
gamma-methacryloxypropyltrimethoxy silane, 179.2 g of 
2-ethylhexylmethacrylate, 170.2 g of Vazo.RTM. 67 
(2,2'-azobis(2-methylbutanenitrile). Hold the mixture at reflux for 30 
minutes. Then add 60 g of n-pentyl-propionate and 9 g of Vazo.RTM. 67 over 
a 30 minute period. Hold the mixture at reflux for 30 minutes and then 
cool to recover the product. 
Synthesis of Cyclohexanedimethanol/Silane Adduct 
Melt cyclohexanedimethanol in laboratory oven. When melted, take 294.7 g of 
cyclohexanedimethanol along with 0.11 g dibutyl tin dilaurate and place in 
a flask at about 35.degree. C. Add 419.5 g of 
isocyanatopropyltrimethoxysilane over 75 minutes. Then hold for two hours. 
Cool and empty. 
Stabilizer Package 
A mixture of the following ingredients is used for the stabilization 
package: 
xylene 67.5 grams, 
2-(3',5'-bis(1-methyl-1-phenylethyl)-2'-hydroxyphenyl)benzotriazole, and 
ultraviolet absorber, Tinuvin.RTM. 900 purchased from Ciba Corporation/7.5 
grams, 
Hindered amine light stabilizer, Tinuvin.RTM. 123 purchased from Ciba 
Corporation/12.43 grams, 
Reaction product of 
beta-3-(2H-benzotriazole-2-yl)-4-hydroxy-5-tert-butylphenyl propionic 
acid, methyl ester and polyethylene glycol 300, ultraviolet absorber, 
Tinuvin.RTM. 1130 from Ciba Corporation/12.57 grams, and 
Acid catalyst solution/5.33 grams. This solution consists of Cycat.RTM. 600 
(aromatic sulfonic acid from American Cyanamid) 48% AMP-95.RTM. (amine 
from Angus Chemical) 11% and methanol 41%. 
Preparation of Microgel 
A dispersed polymer microgel was prepared by charging the following 
constituents into a polymerization reactor equipped with a heat source and 
a reflux condenser. Microgel when used in following examples was prepared 
by this procedure. 
______________________________________ 
Parts by Weight 
______________________________________ 
Portion I 
Mineral Spirits (b.p. 157-210.degree. C.) 
97.614 
Heptane 37.039 
2,2'-azobis(2-methylbutanenitrile) 
1.395 
Methacrylate copolymer stabilizer 
4.678 
Methyl methacrylate monomer 
15.187 
Portion II 
Methyl methacrylate monomer 
178.952 
Styrene monomer 75.302 
Hydroxyethyl acrylate monomer 
23.455 
Mineral Spirits (b.p. range 157-210.degree. C.) 
32.387 
Heptane 191.896 
N,N-dimethylethanolamine 
1.108 
Glycidyl methacrylate monomer 
2.816 
Methacrylate copolymer stabilizer 
58.271 
Methacrylic acid monomer 
2.816 
Portion III 
Toluene 12.938 
Heptane 30.319 
2,2'-azobis(2-methylbutanenitrile) 
2.024 
Portion IV 
Heptane 16.204 
Portion V 
Methylated/butylated melamine formaldehyde resin 
246.300 
Total 1067.300 
______________________________________ 
Portion I was charged to the reaction vessel and heated to its reflux 
temperature. It was held at reflux for 60 minutes. Then Portions II and 
III were added simultaneously over a 180 minute period, while maintaining 
the resulting reaction mixture at its reflux temperature. Then Portion IV 
was dumped to the reactor and the reaction mixture was held a reflux for 
120 minutes. Excess solvent (246.3 parts) was then stripped off and the 
reactor contents cooled to 215.degree. F. After cooling, Portion V was 
added and mixed 30 minutes while continuing to cool to 140.degree. F. The 
resulting dispersion was at 70.0% weight solids. 
Preparation of Non-Aqueous Dispersion (NAD) 
A nonaqueous acrylic resin dispersion was prepared by charging the 
following constituents into a reaction vessel equipped with a stirrer, a 
heating source and a reflux condenser: 
______________________________________ 
Parts by Weight 
______________________________________ 
Portion 1 
Isopropanol 179.26 
Acrylic Polymer Solution 
2254.05 
(52% solids of an acrylic polymer of 15% styrene, 
28% butyl methacrylate, 30% butyl acrylate, 
10% hydroxyethyl acrylate, 2% acrylic acid and 
15% ethyl methacrylate having a weight average 
MW of 10,000 in a solvent mixture of 82.2% xylene 
and 17.8% butanol) 
Mineral spirits 255.65 
Heptane 1912.46 
Portion 2 
Heptane 28.75 
t-butyl peroctoate 4.68 
Portion 3 
Methylmethacrylate monomer 
1459.69 
Hydroxyethyl acrylate monomer 
784.81 
Styrene monomer 156.97 
Portion 4 
Acrylic Polymer solution 
1126.52 
(53% solids of an acrylic polymer of 15% styrene 
28% butyl methacrylate, 30% butyl acrylate, 
10% hydroxyethyl acrylate, 2% acrylic acid 
and 15% ethyl methacrylate 2.7% glycidyl 
methacrylate having a weight average Mw of 
10,000 in a solvent mixture of 82.2% xylene 
and 17.8% butanol) 
Methyl methacrylate monomer 
125.57 
Methyl acrylate monomer 565.06 
Glycidyl methacrylate monomer 
47.05 
Heptane 17.25 
Portion 5 
Mineral spirits 638.63 
t-butyl peroctoate 47.14 
Isobutanol 127.31 
Portion 6 
t-butyl peroctoate 30.96 
Isobutanol 255.65 
Portion 7 
Heptane 167.25 
Total 10,184.71 
______________________________________ 
Portion 1 is charged into the reaction vessel and heated to its reflux 
temperature. Portion 2 is added to the reaction vessel, mixed, and held at 
reflux temperature for 2 minutes. Then Portions 3 and 4 are added 
simultaneously with Portion 5 over a 210 minute period to the reaction 
vessel while maintaining the resulting reaction mixture at its reflux 
temperature. Then the mixture is held at its reflux temperature for an 
additional 45 minutes. Portion 6 is added over a 90 minute period while 
maintaining the reaction mixture at its reflux temperature and then held 
at this temperature for an additional 90 minutes. Portion 7 is added and 
excess solvent is stripped off to give a 60% solids acrylic resin 
dispersion. 
TABLE 1 
__________________________________________________________________________ 
Where Component I is 4-VCH-Si.sub.2 /HBPA (Silanated 
4-Vinyl-1-Cyclohexene/Hydrogenated Bis-Phenol A) Silane/Silicate 
Hybrid Oligomers 
Proce- 
dure 
VCH/ 
Catalyst(%).sup.a 
Temp. 
Time 
MeOH 
Conv..sup.c 
Visc. 
Color (b).sup.d 
No. OH Nafion .RTM. 
TFA (.degree. C.) 
(hour) 
(%).sup.b 
VCH 
VCH/OH 
(poise) 
Crude 
Filter 
__________________________________________________________________________ 
1 1.17 
3.1 0.19 
119 6 
85 22 73 22 1.8 
2 1.17 
3.1 0.19 
120 5 86 9.8 
120 7 89 66 0.87 14 3.9 1.2.sup.f 
3 1.17 
3.1 0.19 
120 3 82 6.1 
120 5 86 64 0.87 12 2.7 0.7.sup.f 
4 1.20 
0.77 0.77 
120 5 87 5.6 6.5 
120 8 89 65 0.88 7.0 7.6 1.8 
5 1.20 0.77 
120 5 84 6.2 7.5 
120 8 89 61 0.82 7.9 10.1 
1.6 
6 1.20 0.15 
142 2 82 4.9 3.1 
142 5 87 60 0.83 7.3 6.6 0.8 
7 1.20 0.15 
135 5 87 5.0 2.1 
+0.15 
136 9 90 60 0.80 7.6 2.7 0.5.sup.e 
P-H.sup.f 
8 0.78 
0.50 0.10 
140 2 78 80 0.80 83 2.9 0.3 
9 0.90 
0.50 0.10 
120 5 66 18 
95 8 73 75 0.92 30 2.6 0.8 
10 1.10 
3.8 0.15 
120 5 87 15 4.7 
120 8 90 82 0.99 19 5.5 2.7 
11 1.15 
3.8 0.15 
120 5 87 10 6.9 
120 8 90 75 0.96 15 8.9 3.7 
12 1.20 
3.8 0.15 
120 5 89 8.0 5.8 
120 8 92 72 0.94 12 8.0 3.1 
13 1.25 
3.8 0.15 
120 5 86 5.4 6.6 
120 8 89 73 1.03 7.8 8.5 3.1 
__________________________________________________________________________ 
.sup.a Nafion = NR50; TFA = CF.sub.3 CO.sub.2 H 
.sup.b MeOH yield (%) = MeOH collected/2 .times. HBPA (mole/mole) .times. 
100% 
.sup.c VCH conversion (%) by GC; VC/OH = VCH conversion/MeOH yield 
(mole/mole) 
.sup.d Filtr. after filtration through carbon/celite/silica/filter paper 
.sup.e Filtration through celite/silica/filter paper only 
.sup.f decolorizer added (P-H = 9, 
10dihydro-9-oxa-10-phospha-phenanthrene-10-oxide) 
TABLE 2 
__________________________________________________________________________ 
Where Component I is 4-VCH-Si.sub.2 /HBPA Hybrid Oligomers 
Proce- 
dure 
VCH/ 
Catalyst(%).sup.a 
Temp. 
Time 
MeOH 
Conv..sup.c 
Visc. 
Color (b).sup.d 
No. OH R.sub.4 NOH 
(.degree. C.) 
(hour) 
(%).sup.b 
VCH 
VCH/OH 
(poise) 
Crude 
Filter 
__________________________________________________________________________ 
14 1.20 
1.26 105 5 68 4.8 (H)1.3 
(Me) 110 7 71 5.2 (H)1.1 
140 9 75 59 0.94 6.3 (H)1.4 
0.05 
15 1.20 
0.30 107 5 79 5.1 (H)1.2 
(Me)/MS 
145 8 85 53 0.75 5.6 (H)1.1 
0.5e 
16 1.20 
0.19 106 5 74 6.0 (H)1.3 
(Bu) 135 7 81 58 0.86 8.1 (H)2.5 
0.10 
17 1.20 
0.19 110 5 79 5.3 1.0 
(Bu)/MS 
110 7 80 0.9 
138 8.5 84 61 0.87 7.3 1.2 0.02 
__________________________________________________________________________ 
.sup.a R.sub.4 NOH, where R = Me, Bu MSpurified over molecular sieves 
.sup.b MeOH yield (%) = MeOH collected/2 .times. HBPA (mole/mole) .times. 
100% 
.sup.c VCH conversion (%) by GC VCH/OH = VCH conversion/MeOH yield 
(mole/mole) 
.sup.d Filtr. after filtration through carbon/celite/silica/filter paper 
.sup.e Filtration through celite/silica/filter paper only 
H = hazy. 
TABLE 3 
__________________________________________________________________________ 
Polyol Silicates (Component I) 
Proce- Product 
dure Reaction Mixture Viscosity 
Color 
No. Polyol/Silane Si/OH 
(poise) 
(b) 
__________________________________________________________________________ 
18 Hydrogenated Bisphenol A/(MeO).sub.4 Si 
1.30 
3.6 +8.3 
19 Hydrogenated Bisphenol A/Me(MeO).sub.3 Si 
1.57 
3.2 
20 Cyclohexanedimethanol/(MeO).sub.4 Si 
1.20 
0.6 +7.6 
21 Cycloxexanedimethanol/Me(MeO).sub.3 Si 
1.32 
0.4 
22 Cyclohexanedimethanol/Pr(MeO).sub.3 Si 
1.32 
0.2 
23 Neopentyl Glycol/(MeO).sub.4 Si 
1.32 
0.1 
24 Neopentyl Glycol/Me(MeO).sub.3 Si 
1.34 
0.1 +0.03 
25 1,4-Cyclohexanediol/Me(MeO).sub.3 Si 
1.37 
0.1 
26 2,5-Dimethyl-2,5,hexanediol/Me(MeO).sub.3 Si 
1.34 
0.1 
27 Pinacol/Me(MeO).sub.3 Si 
2.39 
0.1 
28 1,6-Hexanediol/Me(MeO).sub.3 Si 
1.30 
0.1 
29 1,8-Octanediol/Me(MeO).sub.3 Si 
1.34 
0.1 
30 1,10-Decadiol/Me(MeO).sub.3 Si 
1.60 
0.1 
31 1,12-Dodecanediol/Me(MeO).sub.3 Si 
1.34 
0.2 
32 Polycaprolactone diol (MW530)/Me(MeO).sub.3 Si 
1.95 
2.1 
__________________________________________________________________________

EXAMPLE 1 
A clearcoat was formulated by blending together the following constituents 
in the order: 
______________________________________ 
Parts by 
Material Company Code Weight 
______________________________________ 
Methylated/Butylated 
Resimene .RTM. CE-6550 
15.34 
Melamine formaldehyde resin 
Monsanto Company 
Non-aqueous Dispersion 
NAD, Procedure Given 
38.17 
Hydrogenated Bisphenol-A/ 
HBPA/4-VCH 22.81 
Disilanated 4-vinylcyclohexene 
Procedure Given 
Stabilizer Package 
Procedure Given 11.60 
Acrylic Polyol Procedure Given 17.60 
CHDM/Bis(isocyanatopropyl 
Procedure Given 11.86 
trimethoxysilane) 
Acid Catalyst Solution 
Cycat .RTM. 600, Cytec 
5.30 
Dibutyltin dilaurate 
Fascat 4202, Elf Atochem 
0.20 
Acrylosilane Resin (V) 
Procedure given 14.47 
Acrylic Terpolymer 
Resiflow .RTM. S 
0.40 
Estron Chemical 
______________________________________ 
The coating was sprayed over a black, solvent-borne basecoat which was not 
previously cured. The coating was cured for 30 minutes at 141.degree. C. 
The coating exhibited significantly better mar resistance than a standard 
clearcoat. 
Example 2 
A clearcoat was formulated by blending together the ingredients in Example 
1 except that the acrylic polyol was replaced with 23.88 parts silanated 
acrylic polyol (procedure given) and acrylosilane resin and 
CHDM/Bis(isocyanatopropyltrimethoxysilane) were replaced with 20.46 parts 
of dual functional acrylosilane resin. 
The coating was sprayed over a black, solvent-borne basecoat which was not 
previously cured. The coating was cured for 30 minutes at 141.degree. C. 
to give a hard glossy clearcoat. 
Example 3 
A clearcoat was formulated by blending together the following constituents 
in the order: 
______________________________________ 
Parts by 
Material Company Code Weight 
______________________________________ 
Microgel Rheology Agent 
Procedure Given 43.1 
Methylated/Butylated 
Resimene .RTM. CE-6550 
65.5 
Melamine formaldehyde resin 
Monsanto Company 
Trimethylorthoformate 
Huls America 30.2 
Benzotriazole UV Screener 
Tinuvin .RTM. 384 
2.0 
Light Stabilizer Tinuvin .RTM. 123 
2.0 
Acrylic Terpolymer 
Resiflow .RTM. S, 
0.4 
Estron Chem. 
Acrylosilane Resin 
Procedure Given 313.2 
Silica/Melamine Dispersion 
DuPont 58.4 
Non-aqueous Dispersion 
NAD, Procedure Given 
230.2 
Acrylic Polyol Procedure Given 53.7 
CHDM/Bis(isocyanatopropyl 
Procedure Given 75.4 
trimethoxysilane) 
Tris(methoxy/diethoxysilylpropyl)- 
OSI 75.4 
isocyanurate 
Dibutyltin diacetate 
Fascat 4200, EIf Atochem 
0.8 
Acid Catalyst Solution 
Cycat .RTM. 600, Cytec 
20.1 
______________________________________ 
The coating was sprayed over a solvent-borne basecoat which was not 
previously cured and cured for 30 minutes at 129.degree. C. This clearcoat 
showed very good appearance with 20.degree. gloss of 90 and distinctness 
of image of 87. Compared to a totally melamine crosslinked system which 
has an acid rain resistance rating of 12 (on a scale of 0-12 with 0 best) 
this system had a very good rating of 5. This acid rain resistance is at 
least equal to isocyanate systems but this clearcoat has the advantage of 
being a stable one component system, not requiring mixing just prior to 
use. 
Example 4 
A clearcoat was formulated by blending together the ingredients in Example 
3 except that the tris(methoxy/diethoxysilylpropyl)isocyanurate was 
eliminated and 150.8 parts of CHDM/Bis(isocyanatopropyltrimethoxysilane) 
were added. 
The coating was sprayed over a solvent-borne basecoat which was not 
previously cured and cured for 30 minutes at 129.degree. C. This clearcoat 
showed very good appearance with 20.degree. gloss of 92 and distinctness 
of image of 89. This system had a very good acid rain resistance rating of 
4 and very good mar performance on a Taber Abraser of 70 (scale 0-100, 100 
best). 
Example 5 
A clearcoat was formulated by blending together the ingredients in Example 
3 except that the tris(methoxy/diethoxysilylpropyl)isocyanurate was 
replaced with 75.4 parts of an adduct of 
2-vinyl-4-ethyl-4-hydroxyethyl-1,3-dioxane/caprolactone/tetraethyl 
orthosilicate. 
The coating was sprayed over a solvent-borne basecoat which was not 
previously cured and cured for 30 minutes at 129.degree. C. This clearcoat 
showed excellent appearance with 20.degree. gloss of 93 and distinctness 
of image of 93. This clearcoat had a mar resistance rating of 80 (scale 
0-100, 100 best) as measured in an aluminum oxide slurry rubtest evaluated 
by optical imaging. 
Example 6 
A clearcoat was formulated by blending together the ingredients in Example 
3 except that the tris(methoxy/diethoxysilylpropyl)isocyanurate was 
replaced with 75.4 parts of a di-adduct of 1,4-cyclohexanedimethanol and 
tetramethyl orthosilicate. 
The coating was sprayed over a solvent-borne basecoat which was not 
previously cured and cured for 30 minutes at 129.degree. C. This clearcoat 
showed excellent appearance with 20.degree. gloss of 94 and distinctness 
of image of 89. This clearcoat showed a balance of very good etch, (rating 
of 5), and scratch and mar resistance, (rating of 74). 
Example 7 
The clearcoat from Example 6 was applied over a waterborne basecoat that 
had been baked for 5 minutes at 180.degree. F. Excellent appearance with 
20.degree. Gloss of 91 and Distinctness of image of 88 was found. Acid 
rain and mar resistance were identical to the coating applied over the 
solvent borne basecoat. 
Example 8 
A clearcoat was formulated by blending together the ingredients in Example 
3 except that the microgel, melamine and acrylic polyol resin were 
eliminated and the amount of tris(methoxy/diethoxysilylpropyl)isocyanurate 
was increased to 218.2 parts. 
The coating was sprayed over a solvent-borne basecoat which was not 
previously cured and cured for 30 minutes at 129.degree. C. This clearcoat 
showed excellent appearance with 20.degree. gloss of 96 and distinctness 
of image of 85. This clearcoat had particularly good scratch and mar 
resistance with a rating of 83. 
Example 9 
A clearcoat was formulated by blending together the following constituents 
in the order: 
______________________________________ 
Parts by 
Material Company Code Weight 
______________________________________ 
Non-aqueous Dispersion 
NAD, Procedure Given 
264.6 
Alkylated amino resin 
Cymel .RTM. 1161, Cytec 
65.0 
CHDM/Bis(isocyanatopropyl 
Procedure Given 462.3 
trimethoxysilane) 
Acrylosilane Resin 
Procedure Given 184.5 
Dibutyltin diacetate 
Fascat 4200, Elf Atochem 
1.7 
Acid Catalyst Solution 
Cycat .RTM. 600, Cytec 
19.3 
Ethyl-3-ethoxy propionate 
Eastman Chemicals 
2.6 
______________________________________ 
The coating was sprayed over a solvent-borne basecoat which was not 
previously cured and cured for 30 minutes at 141.degree. C. This clearcoat 
showed very good appearance with 20.degree. gloss of 88 and distinctness 
of image of 90. The scratch and mar resistance is very good with a rating 
of 83. This clearcoat gives a hard (14.75 knoop), solvent (100 MEK rubs) 
and impact (180 in/lbs) resistant finish. The particular advantage of this 
clearcoat is the very low Volatile Organic Content (VOC) of less than 1.5 
lb/gal which compares to 3.8 lb/gal for current commercial materials. 
Example 10 
The clearcoat formula in Example 9 with the addition of 15.9 parts of 
Benzotriazole UV Screener Tinuvin.RTM. 384, and 15.1 parts of light 
stabilizer, Tinuvin.RTM. 123, to provide a coating with improved outdoor 
durability.