Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
1999-06-21
2001-05-08
Hampton-Hightower, P. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C528S061000, C526S217000, C526S310000, C526S324000, C525S063000, C525S064000, C525S066000, C525S111000, C525S123000, C525S330500, C525S421000, C525S438000, C525S452000, C525S471000, C525S528000, C525S530000, C525S531000, C525S902000, C524S504000, C524S555000
Reexamination Certificate
active
06228971
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to polymeric aldimine and ketimine functional compositions and their use in curable film-forming compositions.
BACKGROUND OF THE INVENTION
Curable film-forming compositions (coatings) have been used in automotive and other industrial manufacturing for decades. Curable compositions (as opposed to lacquers) offer better protection to substrates because of their abilities to resist damage by solvents, acids, and other chemicals, and effects of weathering. Depending on the cure chemistry, some compositions are curable at ambient temperature; others require heating to effect cure.
A variety of curing agents having different types of functional groups (and hence different chemistries) may be utilized in curable film-forming compositions. Examples of curing agents which are suitable for use in compositions that are curable at ambient temperatures include, inter alia, polyanhydrides, polyisocyanates, and polyepoxides. Each type of curing agent contains different chemical functional groups, providing unique properties to a cured composition.
Coating compositions having superior durability, hardness, chemical resistance, and similar properties are sought after in virtually all industries that use coatings.
It would be desirable to provide compositions that may be cured at ambient or higher temperatures with a variety of curing agents, providing film-forming compositions that exhibit excellent properties.
SUMMARY OF THE INVENTION
In accordance with the present invention, an addition copolymer having imine functional groups is provided containing a plurality of groups of the structure:
&Brketopenst;A&Brketclosest;
x
&Brketopenst;B&Brketclosest;
m
(I)
wherein A is
R
1
is hydrogen or methyl; R
2
is hydrogen or an alkyl group having from about 1 to about 10 carbon atoms; R
3
is an alkyl or aryl group having from about 1 to about 10 carbon atoms, or R
3
is bonded to R
2
and forms part of a five- or six-membered ring; Y is a divalent linking group having from about 3 to about 15 carbon atoms; B is the residue of an ethylenically unsaturated monomer or mixture of monomers copolymerized with and different from A; x is about 10 to about 50 percent by weight; and m is about 50 to about 90 percent by weight; based on the total solid weight of monomers used to prepare the copolymer. Also provided are curable film-forming compositions comprising the copolymer described above and a curing agent having functional groups that are reactive with imine groups.
DETAILED DESCRIPTION
The imine functional addition copolymer of the present invention contains a plurality of groups of the structure:
wherein R
1
is hydrogen or methyl; R
2
is hydrogen or an alkyl group having from about 1 to about 10 carbon atoms; R
3
is an alkyl or aryl group having from about 1 to about 10 carbon atoms, or R
3
is bonded to R
2
and forms part of a five- or six-membered ring; and Y is a divalent linking group having from about 3 to about 15 carbon atoms. The alkyl groups of R
2
and R
3
may independently be linear, branched, or cyclic. Examples of alkyl groups include methyl, ethyl, isobutyl, isopropyl, n-propyl, n-butyl, hexyl, cyclohexyl, methylethyl, octyl, and the like. Aryl groups include, inter alia, phenyl, benzyl, and mono- or polysubstituted derivatives thereof.
It is understood that the groups of structure (II) may be in equilibrium with isomers such as enamines, having the structure:
The divalent linking group Y may have from about 3 to about 15 carbon atoms and may be alkyl or aryl, including alkaryl and aralkyl, and may be linear, cyclic, or branched. The linking group may additionally include functional groups such as, for example, ester, ether, urethane, etc.
In a preferred embodiment of the invention, Y has the structure:
wherein the aromatic ring is bonded to the backbone carbon of the copolymer in the meta position. In this embodiment, R
2
is typically hydrogen such that the imine group of structure (II) is an aldimine.
The divalent linking group Y may also have the structure:
and R
4
is hydrogen or an alkyl group having from about 1 to about 10 carbon atoms. The alkyl group of R
4
may be linear, branched, or cyclic. Examples of alkyl groups include methyl, ethyl, isobutyl, isopropyl, n-butyl, hexyl, octyl, and the like. In this embodiment, the imine group of structure (II) is an ester of acrylic or methacrylic acid.
The imine functional addition copolymer of the present invention may be prepared using conventional free radical polymerization techniques. The copolymer may be prepared by reacting together the following:
1) an ethylenically unsaturated material having the structure:
wherein R
1
and Y are as defined above;
2) at least one other ethylenically unsaturated monomer; and
3) an aldehyde or ketone.
The material of 1) may be any ethylenically unsaturated amino functional monomer. A preferred example is dimethyl-eta-isopropenyl benzyl amine.
The ethylenically unsaturated monomer of 2) may be selected from acrylic and vinyl monomers. The acrylic monomers include alkyl esters of acrylic acid or methacrylic acid, wherein the alkyl group may contain from about 1 to about 12 carbon atoms. Suitable alkyl esters of acrylic acid or methacrylic acid include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, isobutyl methacrylate, lauryl methacrylate, and the like. Suitable other copolymerizable ethylenically unsaturated monomers include vinyl aromatic compounds such as styrene, alpha-methyl styrene, and vinyl toluene; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride and vinyl esters such as vinyl acetate. Mixtures of ethylenically unsaturated monomers may be used.
The ethylenically unsaturated monomer of 2) is most often selected from the group consisting of styrene, butyl acrylate, alpha-methyl styrene, isobornyl methacrylate, and mixtures thereof.
The aldehyde or ketone of 3) may have from about 2 to about 10 carbon atoms, and is typically selected from the group consisting of isobutyraldehyde, acetaldehyde, benzaldehyde, trimethylacetaldehyde, methylethyl ketone, diisopropyl ketone, methylisobutyl ketone, and acetone. Mixtures of aldehydes and/or ketones may also be used.
In forming the composition of the present invention, the material of 1) may be polymerized with the ethylenically unsaturated monomer(s) of 2) using solution polymerization techniques in the presence of suitable initiators such as organic peroxides or azo compounds, for example, benzoyl peroxide or N,N-azobis(isobutyronitrile). The polymerization may be carried out in an organic solution in which the monomers are soluble by techniques conventional in the art.
After polymerization, the resultant amine functional copolymer may be reacted with the aldehyde or ketone of 3) to form an imine functional copolymer. Alternatively, the ethylenically unsaturated material of 1) and the aldehyde or ketone of 3) may be reacted together first to form an aldimine- or ketimine-functional monomer, followed by polymerization with the ethylenically unsaturated monomer(s) of 2). In this alternative embodiment, which is preferred, no solvents are required but may be present. The reaction conditions to form aldimines and ketimines is dependent on the structures of the amine, aldehyde and ketone. For example, a more sterically hindered amine will react more slowly and require heat to react with an aldehyde or ketone. The reaction conditions at which a primary amine will react with an aldehyde is ambient temperature to about 80° C. The equilibrium favors aldimine formation. Water is removed during or after aldimine synthesis using an appropriate dehydrating solvent that forms an azeotrope with water. Water can also be removed by an appropriate dehydrating agent, for example, molecular sieves. Water can be removed after aldimine formation by reduced pressure. With ketimine formation, the reaction requires the removal of water to force the rea
Carney Joseph M.
Jennings Robert E.
Martz Jonathan T.
Hampton-Hightower P.
PPG Industries Ohio Inc.
Uhl William J.
LandOfFree
Polymeric imine functional compositions and their use in... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Polymeric imine functional compositions and their use in..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Polymeric imine functional compositions and their use in... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2565189