Aqueous polymer dispersion for paper with a copolymer of vinyl acetate and an acrylate monomer prepared in the presence of a starch derivative
The invention relates to a process for preparing an aqueous dispersion of a polymer P, which comprises the emulsion polymerization of vinyl acetate, an acrylate monomer, which is a C 1 -C 10 alkyl acrylate or a C 1 -C 10 methacrylate, an α,β-ethlyenically unsaturated C3-C8 carboxylic acid and at least one out of glycidyl methacrylate, glycidyl acrylate, allyl methacrylate and allyl acrylate, in the presence of a starch derivative. Optionally, an additional monomer is an ethylenically unsaturated sulfonic acid, an ethylenically unsaturated other monomer or both of them. Furthermore, the aqueous polymer dispersion obtainable from this process and a powder form thereof are disclosed. They are useful for a paper coating slip containing one of the aforementioned forms. A paper or a cardboard, which is coated with the paper coating slip, shows surface strength, which is expressed by a good dry pick resistance, a good wet pick resistance or good offset test results. The aqueous polymer dispersion or the powder form thereof is furthermore useful as a binder.
1. A process for preparing an aqueous dispersion comprising a polymer P, the process comprising:
emulsifying a mixture comprising monomers in an aqueous medium, and
polymerizing the monomers in the presence of a free-radical initiator and a starch derivative,
wherein the mixture consists of:
vinyl acetate, as a monomer (a),
at least one acrylate monomer, which is at least one selected from the group consisting of a C 1 -C 10 alkyl acrylate and a C 1 -C 10 alkyl methacrylate, as a monomer (b),
at least one α,β-ethylenically unsaturated C 3 -C 6 carboxylic acid, as a monomer (c),
at least one monomer selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl methacrylate and allyl acrylate, as a monomer (d),
optionally at least one ethylenically unsaturated sulfonic acid, as a monomer (e), and
optionally at least one ethylenically unsaturated other monomer, which is
different from the monomers (a), (b), (c), (d) and (e), as a monomer (f), and wherein
the content of the vinyl acetate monomer (a) is from 70 to 94.7 parts by weight of the monomers,
the content of the at least one acrylate monomer (b) is from 5 to 25 parts by weight of the monomers,
the content of the at least one α,β-ethylenically unsaturated C 3 -C 6 carboxylic acid monomer (c) is from 0.1 to 10 parts by weight of the monomers,
the content of the at least one monomer (d) selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl methacrylate and allyl acrylate is from 0.1 to 10 parts by weight of the monomers,
the optional content of the at least one ethylenically unsaturated sulfonic acid monomer (e) is from 0.1 to 5 parts by weight of the monomers,
the optional content of the at least one other ethylenically unsaturated monomer (f) is from 0.1 to 15 parts by weight of the monomers, and
the sum total of the parts by weight of the monomers (a), (b), (c), (d), (e) and (f) is 100.
2. The process according to claim 1 , wherein the content of the monomer (a) vinyl acetate is from 70 to 85 parts by weight of the monomers.
3. The process according to claim 1 , wherein the content of the starch derivative is from 10 to 65 parts by weight of the sum total of the parts by weight of the monomers (a), (b), (c), (d), (e) and (f).
4. The process according to claim 1 , wherein the starch derivative is a degraded starch having an intrinsic viscosity ηi of less than 0.07 dl/g.
5. The process according to claim 1 , wherein
the at least one acrylate monomer (b) is at least one selected from the group consisting of n-butyl acrylate and ethylhexyl acrylate, and
the at least one α,β-ethylenically unsaturated C 3 -C 6 carboxylic acid monomer (c) is at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic acid anhydride, 2-methyl maleic acid, 2-methyl maleic acid anhydride and itaconic acid.
6. The process according to claim 1 , wherein the at least one ethylenically unsaturated sulfonic acid monomer (e) is present and is at least one selected from the group consisting of vinyl sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid.
7. The process according to claim 1 , wherein
the at least one acrylate monomer (b) is n-butyl acrylate
the at least one α,β-ethylenically unsaturated C 3 -C 6 carboxylic acid monomer (c) is at least one selected from the group consisting of acrylic acid and methacrylic acid, and
the at least one ethylenically unsaturated sulfonic acid monomer (e) is present and is vinyl sulfonic acid.
8. The process according to claim 1 , wherein
the content of the vinyl acetate monomer (a) is from 75 to 85 parts by weight of the monomers,
the content of the at least one acrylate monomer (b) is from 7 to 19 parts by weight of the monomers,
the content of the at least one α,β-ethylenically unsaturated C 3 -C 6 carboxylic acid monomer (c) is from 0.5 to 5 parts by weight of the monomers,
the content of at least one monomer (d) selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, allyl methacrylate and allyl acrylate is from 0.5 to 8 parts by weight of the monomers,
the optional content of the at least one ethylenically unsaturated sulfonic acid monomer (e) is from 0.1 to 2 parts by weigh of the monomers,
the optional content of the at least one other ethylenically unsaturated monomer (f) is from 0.1 to 10 parts by weight of the monomers, and
the sum total of the parts by weight of the monomers (a b (c), (d), (e) and (f) is 100.
9. The process according to claim 1 , wherein
the at least one ethylenically unsaturated monomer, which is different from the monomers (a), (b), (c), (d) and (e) is present and is at least one selected from the group consisting of an alkene, a cycloalkane, a conjugated aliphatic C 4 -C 9 diene, an ester of vinyl alcohol and a C 2 -C 15 monocarboxylic acid, a C 5 -C 10 cycloalkyl acrylate, a C 5 -C 10 cycloalkyl methacrylate, di(C 1 -C 10 alkyl) maleinate, di(C 1 -C 10 alkyl) fumarate, a vinylaromatic compound, an ethylenically unsaturated C 3 -C 8 -monocarbonitrile, an ethylenically unsaturated C 4 -C 8 -dicarbonitrile, an ethylenically unsaturated C 3 -C 8 monocarboxamide, an ethylenically unsaturated C 4 -C 8 dicarboxamide, ureido methacrylate or ureido acrylate.
10. The process according to claim 1 , wherein a polymer seed is present during the polymerizing of the monomers in the presence of a free-radical initiator and a starch derivative.