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Polymer of Acrylic Acid Oligomer, Its Preparation and Use in Coating And

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Polymer of Acrylic Acid Oligomer, Its Preparation and Use in Coating And Europaisches Patentamt European Patent Office © Publication number: 0 036 294 Office europeen des brevets A2 © EUROPEAN PATENT APPLICATION © Application number: 81301029.5 © int. ci 3: C 08 F 20/28 © Date of filing: 12.03.81 © Priority: 14.03.80 US 130323 © Applicant: Rohm and Haas Company Independence Mall West Philadelphia, Pennsylvania 191051US) @ Date of publication of application: 23.09.81 Bulletin 81/38 © Inventor: Merritt, Richard Foster 1811 Shelly Lane © Designated Contracting States: Fort Washington Pennsylvania 19034IUS) BE CH DE FR GB IT LI NL SE © Inventor: Larsson, Bjorn Eric Swamp Road Rushland Pennsylvania 18956(US) © Representative: Angell, David Whilton et al, Rohm and Haas Company Patent Department Chesterfield House Barter Street London WC1A2TP(GB) © Polymer of acrylic acid oligomer, its preparation and use in coating and/or impregnating compositions and the moderation of copolymer glass transition temperature using the oligomer. © Acrylic acidacid oligomeroligomer of thethe formulaformula: : 0 0 CH =CH-C-0(CH, •0) H @CH2C n where n has anan average value value (n) (n) of from greater thanthan 1 to 10 is polymerised, alone or with other ethylenicallyethylenicaliy unsaturated monomer, by emulsion or solution polymerisation. When When nn is from 2 to 10 any known polymerisation technique may be used, but emulsion or solution polymerization is preferred. The be used moderate the transition CM monomer may to glass of The polymer be used in < temperature copolymers. may coating and/or impregnating compositions such as inks, caulks, sealants, adhesives, fabric print pastes and non- Gi woven fabric binders. CM CD CO o Q. UJ Croydon Printing Company Ltd. This invention is concerned with the polymerization of certain acrylic acid oligomers forming either homopolymer of such oligomer or copolymer of the oligomer with one or more other ethylenically unsaturated monomers. The monomer may be used to moderate the glass transition temperature of copolymers. The invention also embraces use of the polymer in coating and/or impregnating compositions, such as inks, caulks, adhesives and non-woven binders, and articles treated therewith. West German published application No.2800357 discloses the preparation of acrylic acid oligomer of the formula: wherein n is from 1 to 6, by heating acrylic acid in the presence of 0.0001 to 1% polymeriza- tion inhibitor at a temperature of from 50 to 200°C. Example 6 of that application uses a mixture of such oligomers in an anaerobic adhesive. Polymer would consequently be formed by bulk polymerization between closely spaced substrate rather than in free form, unattached to substrate. The present applicants calculate that the mixture of oligomers used has an average value of m of 1.8 by fit of the mixture to a Poisson distribution. Yamada et al., in Polymer Letters Addition, John Wiley & Sons, New York, Vol. 14 pages 277-281, 1976, herein incorporated by reference, describes the preparation of the oligomer and the isolation of fractions having average values of n ranging from 0.9 to 13.5. In a communication to the editor of Macromolecules, Vol. 7, pages 256 to 258, 1974, herein incorporated by reference, Saegusa et al. teach an earlier preparation of the oligomers. The preparation of the molecule wherein n equals 1 is described by Burguette in U.S. Patent No.3,888,912 which further discloses certain polymers of that material. Other uses for the n equals 1 compound, acryloxy- propionic acid (referred to herein below as AOPA), are given in U.S. Patents 3,266,930 and 4,048,259 wherein AOPA, a vinyl monomer, is used as a reactive component in coatings and adhesives. According to the invention there is provided a method of preparing free-radical addition polymerized polymer by subjecting to solution or, more preferably, emulsion polymerisa- tion conditions one or more ethylenically unsaturated monomers comprising monomer having the formula: wherein n has an average value (n) of from greater than 1 to 10, preferably from 2 to 10, more preferably from.2 to 5. The invention provides a method of preparing free-radical addition polymerised polymer by subjecting to polymerisation conditions one or more ethylenically unsaturated monomers comprising monomer of formula I wherein n is from 2 to 10, preferably 2 to 5, any of the known addition polymerisation techniques may be used, such as bulk, solution or emulsion polymerisation. Solution polymerisation is the preferred method and emulsion polymerisation the most preferred. Monomer of the above formula may be referred to as oligomeric acrylic acid, which may be abbreviated herein to 0-AA. This monomer is Michael addition product of acrylic acid, being an oligomeric polyester acid comprising one or more polyester units and terminating in an acid unit. A monomer or mixture of monomers of formula I may be polymerised in this invention. n above represents the average degree of oligomeriza- tion of acrylic acid. In the case of a single compound n is an integer. In the case of a mixture of compounds, in a given sample the average of these integers is the value of n which, of course, need not be integral, individual molecules may have integral values of n from 0 t 0 ery large numbers but molecules with values of n being very large, perhaps greater than 30, are very few. For the most part the 0-AA in this invention comprises molecules of formula I in which the molecules have integral values of n in the range 0 to 30.. Formula I wherein n equals 0 represents acrylic acid (AA) the precursor from which the oligomers are normally prepared. Formula I wherein n equals 1 represents acryloxypropionic acid (AOPA), the Michael addition dimer of acrylic acid. As will be seen in more detail below, each of these acids, AA and AOPA, is a hardening acid by which is meant that its incorporation in a high polymer contributes to the glass transition temperature (Tg) of the polymer being above room temperature (20°C). In marked contrast we have found that 0-AA, in this invention, contributes to the Tg being below room temperature. Surprisingly, it may be an effective softening monomer in copolymers. In 0-AA samples having low values of n there are appreciable amounts of AA and AOPA along with molecules having higher n values. Samples of 0-AA having high values of n will have little if any AA or AOPA and will consist predominently of molecules having higher values of n. Homopolymer and copolymer data indicate that the Tg of high polymers of 0-AA is far below room temperature, such as the neighbor- hood of -25°C (and may range up or down from this value by 10°C or more depending on the value of n). Thus the 0-AA mer units in a polymer contribute a remarkable Tg lowering effect, to copolymers in which these mers are employed, when compared with commonly used acid mer units such as AA (105°C), methacrylic acid (230°C), and itaconic acid (105°C); the numbers in parenthesis being high molecular weight Tg values. One embodiment of this invention provides a method of moderating the glass transition temperature (Tg) of a copolymer which comprises providing therein, as Tg moderating monomer, units of monomer of formula I. The polymer may be prepared by any conventional polymerisa- tion technique, but solution polymerisation is preferred and emulsion polymerisation more preferred. Preferred comonomers are discussed below. This method allows partial or complete substitution in a copolymerisation of 0-AA for acid monomer which would otherwise contribute to raising the Tg of the polymer. In one embodiment of the methods, polymer and compositions of this invention the ethylenically unsaturated monomer, including that of formula I, is free of acrylic acid. One of the outstanding features of 0-AA is that it copolymerises in free radical initiated polymerisation with great facility, being comparable with AA, methacrylic acid and itaconic acid in this respect. The acid group in polymers comprising 0-AA mer units is surprisingly reactive, leading to faster and more complete reaction with various chemicals such as crosslinking reactants and other polymers. In both of the latter types of reactions incomplete reaction with the polymer is commonplace and slow reactions, particularly in polymer-polymer reactions are usual. Although we do not wish to be bound by any hypothesis in respect of the reaction mechanism, but it is presumed that the long length of the chain between the polymer backbone and the acid group in 0-AA mers is responsible for the high rate and degree of reaction. The reason for this is believed to be the comparatively free accessability of the carboxyl: group in the 0-AA polymer whereas in the case of the other acid mer units the folding of the polymer chain, in its usual configurations, tends to occlude the carboxyl group. Thus thickener polymers employ- ing 0-AA mer units develop their full viscosity rapidly when treated with base in aqueous systems and exhibit unexpectedly little pH drift compared to polymers employing other acid mer units. Polymers employing oligomers wherein n is 2 to about 5 are preferred. At least 0.1% by weight of oligomer of formula I is usually present in the monomers used to make the polymer but more usually the amount is from 0.5 to 75%,preferably from 1 to 25% by weight. In the polymer and methods of this invention, monomer of formula I may be used alone or in combination with one or more comonomers. Comonomers are preferably alpha,beta ethylenically unsaturated and include polyunsaturated monomers, which are preferably present in small amounts such as less than 5%. preferably from 0.1 to 0.5% by weight of the monomers.
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