Paper making and fiber liberation – Processes and products – Non-fiber additive
Reexamination Certificate
2001-05-04
2004-04-06
Chin, Peter (Department: 1731)
Paper making and fiber liberation
Processes and products
Non-fiber additive
C162S164600, C528S044000, C528S059000, C528S271000, C528S361000, C528S370000, C528S403000
Reexamination Certificate
active
06716311
ABSTRACT:
The present invention relates to modified cationic polymers which are obtainable by reacting water-soluble polymeric compounds containing NH groups with crosslinking agents, processes for their preparation and their use in papermaking.
EP-A-0438707 discloses a process for the production of paper, board and cardboard by draining paper stock containing interfering substances in the presence of hydrolyzed homo- and/or copolymers of N-vinylformamide having a degree of hydrolysis of at least 60% and cationic retention aids.
To inhibit the deposition of pitch in papermaking, according to the process of EP-A-0649941 a water-soluble polymer which contains at least 5 mol % of an N-alkyl-N-vinylcarboxamide, N-vinylformamide, N-vinylacetamide or partially hydrolyzed N-alkyl-N-vinylcarboxamides is added to the paper stock.
U.S. Pat. No. 5,536,370 discloses condensates of polyalkylenepolyamines which are converted into crosslinked polyalkylenepolyamines by partial amidation of polyalkylenepolyamines and subsequent condensation of the partially amidated polyalkylenepolyamines with at least bifunctional crosslinking agents. These products are used in papermaking as fixing agents for soluble interfering substances.
The non-prior-published DE-A-19719059.6 discloses reaction products of amino-containing polymers with reactive sizes, in particular alkyldiketenes. The reaction products are used as fixing agents for water-soluble and for water-insoluble interfering substances in the production of paper, board and cardboard from paper stocks containing interfering substances.
U.S. Pat. No. 5,324,787 discloses modified polymers which contain vinylamine units and are obtainable by reacting polymers containing vinylamine units with saturated aliphatic or aromatic glycidyl ethers. The reaction products are used as flocculants and for increasing the retention of crills in papermaking. The aliphatic glycidyl ethers used for the modification contain from 1 to 18, particularly 4 to 12, carbon atoms in the alkyl group. The use of butyl glycidyl ether as a modifier is preferred. JP-A-10-035090 discloses polymers which are obtainable by reacting water-soluble polymeric compounds which contain NH groups and which contain, as polymerized units, monomers containing carboxyl groups and/or anhydride groups or amino groups and/or monomers containing quaternary amonium salt groups with crosslinking agent which contain two or more oxazolinyl and/or oxazolidinyl groups. The reaction products are used for the waterproofing of inkjet papers.
It is an object of the present invention to provide novel polymers which are effective as fixing agents in papermaking.
We have found that this object is achieved, according to the invention, by modified cationic polymers which are obtainable by reacting
(a) water-soluble, polymeric compounds containing NH groups and selected from the group consisting of the polyalkylenepolyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and polymers containing vinylamine units with
(b) compounds which are at least bifunctional with respect to NH groups and contain at least one alkyl or alkylene radical of at least 8 carbon atoms and, as functional group, a halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom.
The present invention furthermore relates to a process for the preparation of modified cationic polymers by reacting
(a) water-soluble, polymeric compounds containing NH groups and selected from the group consisting of the polyalkylenepolyamines, polyamidoamines, polyamidoamines grafted with ethyleneimine and polymers containing vinylamine units with
(b) compounds which are at least bifunctional with respect to NH groups and have at least one alkyl or alkylene radical of at least 8 carbon atoms and, as functional group, a halohydrin, epoxy, carboxyl, chloroformate or isocyanate group or a halogen atom.
Compounds of group (a) are essentially water-soluble polymers containing amino and/or ammonium groups. Examples of such polymers are polyalkylenepolyamines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 3-(2-aminoethyl)aminopropylamine, 2-(diethylamino)ethylamine, 3-(dimethylamino)propylamine, dimethyldipropylentriamine, 4-aminoethyloctane-1,8-diamine, 3-(diethylamino)propylamine, N,N-diethyl-1,4-pentanediamine, dipropylenetriamine, bis(hexamethylene)triamine, N,N-bin(aminopropyl)methylamine, N,N-bis(aminopropyl)ethylamine, N,N-bis(aminopropyl)hexylamine, N,N-bis(aminopropyl)octylamine, N,N-dimethyldipropylenetriamine, N,N-bis(3-dimethylaminopropyl)amine, N-(aminoethyl)butylenediamine, N-(aminopropyl)butylenediamine, bis(aminopropyl)butylenediamine and polyethyleneimines. Preferably used polyalkylenepolyamines are polyethyleneimines which are prepared, for example, by polymerizing ethyleneimine in aqueous solution in the presence of acid-eliminating compounds, acids or Lewis acids. The polyethyleneimines have, for example, molar masses of from 1,000 to 5,000,000 g/mol. Polyethyleneimines having average molar masses of from 5,000 to 800,000 g/mol are particularly preferred.
Further suitable water-soluble, polymeric compounds containing NH groups are polyamidoamines which are obtainable, for example, by condensing dicarboxylic acids with polyamines. Suitable polyamidoamines are obtained, for example, by reacting dicarboxylic acids of 4 to 10 carbon atoms with polyethyleneimines (average molar masses of from 300 to 1,000 g/mol) or with polyalkylenepolyamines which contain from 3 to 10 basic nitrogen atoms in the molecule. Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. In the preparation of the polyamidoamines, it is also possible to use mixtures of dicarboxylic acids as well as mixtures of a plurality of polyalkylenepolyamines. Suitable polyalkylenepolyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine. For the preparation of the polyamidoamines, the dicarboxylic acids and polyalkylenepolyamines are heated to relatively high temperatures, for example to temperatures of from 120 to 220° C., preferably from 130 to 180° C. The water formed in the condensation is removed from the system. In the condensation, lactones or lactams of carboxylic acids of 4 to 8 carbon atoms may, if required, additionally be used. For example, from 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid. The weight average molecular weights of the polyamidoamines are preferably at least 1,000 g/mol.
Further amino-containing polymers are polyamidoamines grafted with ethyleneimine. They are obtainable from the polyamidoamines described above by reaction with ethyleneimine in the presence of acids, such as sulfuric acid, or Lewis acids, e.g. boron trifluoride etherates, at, for example, from 80 to 100° C. For example, from 1 to 100 parts by weight of ethyleneimine are grafted per 100 parts by weight of a polyamidoamine. Uncrosslinked polyamidoamines which may have been grafted with ethyleneimine are preferably used. Compounds of this type are described, for example, in DE-B-24 34 816.
Other suitable cationic polymers of group (a) are polyallylamines. Polymers of this type are obtained by homopolymerization of allylamine, preferably in a form neutralized with acids or in quaternized form, or by copolymerization of allylamine with other monoethylenically unsaturated monomers, as described below as comonomers for N-vinylcarboxamides.
Further water-soluble, polymeric compounds of group (a) which contain NH groups are polymers containing vinylamine units. They are prepared, for example, starting from open-chain N-vinylcarboxamides of the formula
where R
1
and R
2
may be identical or different and are each hydrogen or C
1
- to C
6
-alkyl. Suitable monomers are, for example, N-vinylformamide (R
1
=R
2
=H in formula I), N-viny
aus dem Kahmen Martin
Decker Jürgen
Dyllick-Brenzinger Rainer
Esser Anton
Gercke Martin
BASF - Aktiengesellschaft
Chin Peter
LandOfFree
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