Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-08-24
2002-09-17
Sellers, Robert E. L. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C528S297000
Reexamination Certificate
active
06451929
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to glycidylester compositions, to a process for their preparation, to coating compositions and other curable compositions comprising the glycidylester compositions, and to cured products obtained by using the indicated curable compositions.
Coating compositions based on the reaction products of 2,2-bis-(4-hydroxyphenyl)propane and epichlorohydrin are known. The cured products prepared on the basis of these compositions are resistant against hydrolysis, however, they show a low ultraviolet resistance and are therefore not suitable for applications requiring a high degree of outdoor durability such as building parts or automotive topcoats.
Triglycidylesters which can be used in outdoor durable coatings and in moulding compositions are disclosed in European Patent Application No. 447360A (EP-A-447,360). The application discloses the product having high levels of hydrolyzable chlorine content. In example 2 of EP-A-447,360 which relates to the glycidation of the 2:1 adduct of hexahydrophthalic anhydride and dimethylolpropionic acid, the product obtained has a hydrolyzable chlorine content of 1.0% (10,000 mg/Kg). Such a high level of residual chlorine is generally undesirable in coating compositions.
European patent application No. 0518408A2, describes thermosetting resin compositions containing
(i) an advanced resin product obtainable by reacting
(a) a diglycidyl ester of an alpha,alpha′-dibranched dicarboxylic acid of the general formula I
with
(b) an alpha,alpha′-dibranched dicarboxylic acid of the general formula II
wherein
n is 0 or 1,
wherein R is independently selected from the group consisting of straight and branched chain alkyl, cycloalkyl, arylalkyl and aryl, or both R's may form part of a substituted or unsubstituted cycloaliphatic ring system comprising 5, 6 or 8 carbon atoms, in which case n should be 0, wherein R
1
is independently a hydrogen atom or a methyl group, wherein R
2
is a single bond, substituted or unsubstituted alkylene or arylene or a radical of the formula III
—(R
3
)
m
1
—X—(R
3
)
m
2
— (III)
wherein
m
1
and m
2
are independently 0 or 1,
wherein R
3
is independently selected from the group consisting of substituted or unsubstituted alkylene, and X is a single bond or one of the following bridging groups 1 to V
wherein R
4
is independently selected from the group consisting of C
1
to C
4
alkyl, with the proviso that when X is bridging group (V), m
1
is 0 and when X is bridging group (VI), m
2
is 0 and when n is 0, R
2
is a single bond; and
(ii) a curing compound selected from the group consisting of amino resins blocked or unblocked (cyclo)aliphatic isocyanates, alpha,alpha′-dibranched. cyclic anhydrides, acid-functional polyesters containing only alpha,alpha′-dibranched acid and ester groups, (cyclo)aliphatic amines, (cyclo)aliphatic polyamino amides, blocked or unblocked Lewis acids, and teritary amines.
The molar ratio of compounds (a) and (b) was preferably in the range of from 0.5 to 2.0.
Preferred reactants (a) are selected from diglycidyl ester of diethyl malonic acid, 2,2,5,5-tetramethyl adipic acid, sulphodipivalic acid and tetrapropyl adipic acid and preferred reactants (b) are selected from diethylmalonic acid, 2,2,5,5-tetramethyl adipic acid, sulphopivalic acid and tetrapropyl adipic acid.
It will be appreciated from the European patent application and other publications, referred to therein, that only very specifically structured diglycidyl esters of alpha,alpha′-dibranched dicarboxylic acid could be used as reactant in coating compositions that show a combination of acceptable hydrolytic stability, resistance of transesterification and acceptable weathering resistance.
International Application WO 96/11238 shows that epoxy resins containing cycloaliphatic nuclei have the disadvantage that they could only provide brittle coating films when cured. This brittleness made them unsuitable for coating applications, as brittleness often led to poor adhesion.
European patent application No. 0634434 A2 describes a process for the preparation of linear tertiary aliphatic carboxyl functional polyester resins, by reacting:
(a) at least one compound A′ comprising one mono-functional primary- or secondary hydroxyl group and/or at least one compound A″ comprising one primary- or secondary hydroxyl group and one tertiary aliphatic carboxyl group;
(b) at least one aromatic or cycloaliphatic dicarboxylic acid compound B comprising two aromatic- or secondary aliphatic carboxyl groups or the anhydride thereof;
(c) at least one diol compound C comprising two aliphatic hydroxyl groups, which may independently be a primary or a secondary hydroxyl group; and
(d) at least one dihydroxymonocarboxylic acid compound D comprising a tertiary aliphatic carboxyl group and two aliphatic hydroxyl groups, which may each independently be primary or secondary hydroxyl,
the molar ratio of compounds A′:A″:B:C:D being
M:N:X+Y+1:X:Y
wherein M+N=2, X ranges from 2 to 8 and Y ranges from 2−N to 8, at a temperature of from 100 to 240° C., until essentially all the non-tertiary carboxyl groups as initially present in the reaction mixture have been reacted. The linear tertiary aliphatic carboxyl functional polyesters were reacted with an excess epihalohydrin in the presence of a suitable base and optional catalyst to produce polyglycidylester resins.
The European patent application No. 0720997A2 describes certain linear tertiary carboxyl functional polyesters and epoxy functional polyester resins. These polyester resins were obtained by reaction of:
a) at least one aromatic and/or cycloaliphatic carboxylic acid compound A comprising two aromatic- and/or secondary aliphatic carboxyl groups or the anhydride thereof,
b) at least one hydroxyl compound B comprising two aliphatic hydroxyl groups, which groups each independently may be primary or secondary hydroxyl groups,
c) at least one hydroxyl substituted carboxylic acid compound C comprising at least one tertiary aliphatic carboxyl group and two aliphatic hydroxyl groups, which groups each independently may be primary or secondary hydroxyl groups, and
d) optionally one carboxylic acid compound D comprising one carboxyl group,
the molar ratio of compounds A:B:C:D being
(X+Y−1):X:Y:Z,
wherein X ranges from 2 to 8, Y ranges from 2 to 8, and Z ranges from 0 to 2.
The International Patent Application WO 98/23661 describes linear, tertiary carboxyl functional polyester resins obtainable by reaction of a) at least one compound A
1
, comprising the reaction product of (i) a glycidylester of a mixture of synthetic highly branched saturated monocarboxylic acids isomers of formula (R
1
)(R
2
)(R
3
)—C—COOH wherein R
1
, R
2
and R
3
are alkyl groups of from 1 to 15 carbon atoms, of which at least one is methyl, each acid containing from 5 to 19 and preferably from 5 to 13 carbon atoms, and (ii) a mixture of said synthetic highly branched saturated monocarboxylic acids, in a molar ratio of 1:1; said component A
1
being optionally mixed with hydroxy pivalic acid (A
2
) and/or hydrogenated diphenylolpropane (A
3
); b) at least one aromatic or cycloaliphatic dicarboxylic acid compound B, comprising two aromatic- or secondary aliphatic carboxyl groups or the anhydride thereof; optionally c) a dihydroxymonocarboxylic acid compound C comprising a tertiary aliphatic carboxyl group and two aliphatic hydroxyl groups, which may each independently be primary or secondary hydroxyl; and optionally (d) a diol compound D comprising two aliphatic hydroxyl groups which may each independently be a primary or a secondary hydroxyl group; the molar ratio of compounds A
1
:A
2
+A
3
:B:C:D being A
1
:(2−A
1
):X+Y+1:X:Y, wherein A
1
ranges from 0.1 to 2, wherein Y ranges from 0 to 6 and X ranges from 2 to 8, at a temperature of from 100 to 225° C., until essentially all the non-tertiary carboxyl groups as initially present in the reaction mixture have b
Kooijmans Petrus Gerardus
Li Simon Ming
Marx Edward John
Smits Josef Jacobus Titus
Resolution Performance Products LLC
Sellers Robert E. L.
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