Claims
- 1. In the method of manufacturing paper wherein an opacifying agent is used to provide opacity in the final paper product, either by means of a coating or by means of internal addition to the paper pulp, the improvement wherein there is employed as at least a portion of the opacifying agent water-insoluble graft copolymer particles consisting essentially of the free radical catalyzed graft copolymerization product of (1) at least one ethylenically unsaturated monomer and (2) a water-soluble cationic prepolymer having an RSV of about 0.1 to about 2.5 (1 M NaCl, 1%, 25.degree. C.), the prepolymer moiety of the graft copolymer particles being present on the surface of the particles,
- said monomer (1) being selected from the group consisting of methyl alpha-chloroacrylate, ethyl alpha-chloroacrylate, methyl methacrylate, isopropyl methacrylate, phenyl methacrylate, vinyl chloride, acrylonitrile, methacrylonitrile, and monomers having the formula ##STR20## wherein R is hydrogen or methyl, Y is methyl or chlorine, and n is 0, 1, 2, or 3, and said prepolymer (2) being the addition polymerization product of
- (i) about 5 mole per cent to 100 mole per cent of at least one cationic monomer selected from the group consisting of ##STR21## wherein R.sub.1 is hydrogen or methyl, R.sub.2 is hydrogen or a C.sub.1 -C.sub.4 alkyl, R.sub.3 is hydrogen, a C.sub.1 -C.sub.4 alkyl, ##STR22## where Y is hydroxyl or halogen, ##STR23## and --CH.sub.2 CH.sub.2 O).sub.n H where n is an integer 1 or more and X.sup.- is an anion, ##STR24## wherein R.sub.1 is hydrogen or a C.sub.1 -C.sub.4 alkyl, R.sub.2 is hydrogen, alkyl or substituted alkyl, and R.sub.3 and X.sup.- are as defined in forumula (I), ##STR25## wherein R.sub.1, R.sub.2, R.sub.3 and X.sup.- are as defined in formula (I), ##STR26## wherein R.sub.1, R.sub.3 and X.sup.- are as defined in formula (I), ##STR27## wherein R.sub.1, R.sub.2, R.sub.3 and X.sup.- are as defined in formula (I), and n is an integer 1, 2 or 3 and ##STR28## wherein R.sub.1, R.sub.2, R.sub.3 and X.sup.- are as defined in formula (I), and
- (ii) from about 95 mole per cent to 0 mole per cent of at least one ethylenically unsaturated nonionic monomer selected from the group consisting of N-vinyl pyrrolidone, ethylenically unsaturated monomers having amide functionality, and ethylenically unsaturated monomers having hydroxyl functionality,
- the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 1 part to about 25 parts by weight for each 100 parts by weight of monomer (1) employed, said prepolymer moiety of the particles having chemically bonded thereto a cellulose reactive group.
- 2. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (I) and (ii) of prepolymer (2) is a mono-ethylenically unsaturated amide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 3. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (II) and (ii) of prepolymer (2) is a mono-ethylenically unsaturated amide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to 1.0.
- 4. The method of claim 1 wherein in the water-insoluble graft copolymer particles monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (III) and (ii) of prepolymer (2) is a mono-ethylenically unsaturated amide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 5. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (IV) and (ii) of prepolymer (2) is a mono-ethylenically unsaturated amide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 6. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (V) and (ii) of prepolymer (2) is a mono-ethylenically unsaturated amide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 7. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (VI) and (ii) of prepolymer (2) is a mono-ethylenically unsaturated amide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 8. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (I) and (ii) of prepolymer (2) is acrylamide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 9. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (II) and (ii) of prepolymer (2) is acrylamide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 10. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (III) and (ii) of prepolymer (2) is acrylamide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 11. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (IV) and (ii) of prepolymer (2) is acrylamide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 12. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (V) and (ii) of prepolymer (2) is acrylamide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 13. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and (i) of prepolymer (2) is the monomer of formula (VI) and (ii) of prepolymer (2) is acrylamide, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0.
- 14. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 70 mole % to about 98 mole % acrylamide and from about 30 mole % to about 2 mole % dimethyldiallylammonium choride, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
- 15. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 67 mole % to about 98 mole % acrylamide and from about 33 mole % to about 2 mole % methyldiallylammonium chloride, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
- 16. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 70 mole % to about 98 mole % acrylamide and from about 30 mole % to about 2 mole % methyldiallylammonium acetate, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
- 17. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 70 mole % to about 95 mole % acrylamide and from about 30 mole % to about 5 mole % methacryloyloxyethyltrimethylammonium methyl sulfate, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
- 18. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 82 mole % to about 90 mole % acrylamide and from about 18 mole % to about 10 mole % dimethyldiallylammonium chloride, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
- 19. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 67 mole % to about 89 mole % acrylamide and from about 33 mole % to about 11 mole % methyldiallylammonium chloride, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
- 20. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 82 mole % to about 91 mole % acrylamide and from about 18 mole % to about 9 mole % methyldiallylammonium acetate, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
- 21. The method of claim 1 wherein in the water-insoluble graft copolymer particles, monomer (1) is styrene and the prepolymer (2) is prepared from about 70 mole % to about 88 mole % acrylamide and from about 30 mole % to about 12 mole % methacryloyloxyethyltrimethylammonium methyl sulfate, the amount of prepolymer (2) employed in preparing the graft copolymer particles being from about 2 parts to about 10 parts by weight for each 100 parts by weight of monomer (1) employed, and the RSV of the prepolymer being about 0.1 to about 1.0, and the cellulose reactive group is an aldehyde.
Parent Case Info
This is a division of application Ser. No. 161,805, filed 23 June 1980, which is a division of application Ser. No. 909,606, filed 25 May 1978, now U.S. Pat. No. 4,235,982 which is a continuation-in-part of application Ser. No. 803,330, filed June 3, 1977 now abandoned.
US Referenced Citations (25)
Foreign Referenced Citations (1)
Number |
Date |
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22922 |
Apr 1971 |
JPX |
Divisions (2)
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Number |
Date |
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Parent |
161805 |
Jun 1980 |
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Parent |
909606 |
May 1978 |
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Continuation in Parts (1)
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Number |
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803330 |
Jun 1977 |
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