CN100497466C - Aqueous dispersions of copolymers, production thereof and use of the same - Google Patents
Aqueous dispersions of copolymers, production thereof and use of the same Download PDFInfo
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- CN100497466C CN100497466C CNB2004800279033A CN200480027903A CN100497466C CN 100497466 C CN100497466 C CN 100497466C CN B2004800279033 A CNB2004800279033 A CN B2004800279033A CN 200480027903 A CN200480027903 A CN 200480027903A CN 100497466 C CN100497466 C CN 100497466C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
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- Chemical Kinetics & Catalysis (AREA)
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- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to aqueous dispersions of copolymers that can be obtained by: radical copolymerisation of (A) at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid containing between 4 and 8 C atoms, (B) at least one oligomer of branched or unbranched C3-C10 alkene, at least one oligomer having an average molecular weight Mn of between 300 and 5000 g/mol or being obtainable by oligomerisation of at least three equivalent C3-C10 alkenes, and (C) optionally at least one ethylenically unsaturated conomoner that is different from (A); followed by optional reaction with (D) at least one compound of general formula (Ia) or (Ib); and subsequent mixing with water. In formulae (Ia) and (Ib), the variables are defined as follows: A<1> represents the same or different C2-C20 alkylene, R<1> represents linear or branched C1-C30 alkyl, phenyl or hydrogen, n represents a whole number between 1 and 200, and the water content is between 30 and 99.5 wt. % in relation to the aqueous dispersion.
Description
The present invention relates to the aqueous dispersion of multipolymer, can be by following acquisition: free-radical polymerized following material
(A) at least a dicarboxylic acid deutero-ethylenically unsaturated dicarboxylic acid anhydride from an at least a 4-8 carbon atom,
(B) at least a branching or straight chain C
3-C
10The oligopolymer of-alkene, described at least a oligopolymer has molecular-weight average M
n300-5000g/mol maybe can pass through at least 3 normal C
3-C
10-alkene carries out oligomeric acquisition,
(C) the optionally at least a olefinic unsaturated comonomer different with (A) and optionally with
(D) compound of at least a following formula I a or Ib reaction
Add entry subsequently,
Wherein, in formula Ia and Ib,
A
1Be identical or different C
2-C
20Alkylidene group,
R
1Be the C of straight chain or branching
1-C
30Alkyl, phenyl or hydrogen and
N is the integer of 1-200,
Water-content is 30-99.5 weight %, based on the aqueous dispersion meter.
The method that the invention further relates to the new aqueous dispersion of preparation is used for the purposes of treatment of fibrous substrate thing with it.
The invention further relates to multipolymer, it can be by following acquisition: free-radical polymerized following material
(A) at least a dicarboxylic acid deutero-ethylenically unsaturated dicarboxylic acid anhydride from an at least a 4-8 carbon atom,
(B) at least a branching or straight chain C
3-C
10The oligopolymer of-alkene, described at least a oligopolymer has molecular-weight average M
nBe that 300-5000g/mol maybe can pass through at least 3 normal C
3-C
10-alkene carries out oligomeric acquisition,
(C) the optionally at least a olefinic unsaturated comonomer different with (A) and optionally with
(D) compound of at least a following formula I a or Ib reaction
Wherein, in formula Ia or Ib, variable is for as defined above.
In producing leather,, give water repelling property to prevent moist and dirty the playing an important role of leather or leatherware except such as soft and the plentiful characteristic.Other performance characteristic of leather such as the type of the water repelling property that feel is also given influence.Yet,, give water resisting property and also can play an important role for other fiber base thing such as fabric, paper, plate, leatheroid and timber.Dipping is an important career field for sheet base thing such as concrete and fragment of brick.
WO9 5/07944 discloses 20-60 mole % monoene and has belonged to unsaturated C
4-C
6The oligopolymer of-dicarboxylic acid or its acid anhydrides and at least a propylene of 10-70 mole % or branching 1-alkene such as iso-butylene and 1-50 mole % are at least a can be used to prepare the purposes of the oil soluble reaction product that can be suitable as lubricant and fuel with the multipolymer of the monoene ethylenically unsaturated compounds of above-mentioned monomer polymerization such as vinyl and alkyl allyl ethers and its.
WO 90/03359 and EP-A 0 657 475 disclose the alternating copolymer of maleic anhydride and polyisobutene, and it can be used as additive in lubricant and fuel after with amine or modified polyamine.
WO 01/55059 discloses maleic anhydride, one or more have more than the ter-polymers of the vinyl ester of the carboxylic acid of the alkene of 40 carbon atoms such as polyisobutene and 2-12 carbon atom and this ter-polymers purposes as the emulsifying agent of explosive.
WO 03/23070 discloses the emulsion oil-filling agent that is used for rawhide, and this emulsion oil-filling agent for example comprises polyisobutene or by carried out the product (going for the 6th page 29) of alkylene (ene) prepared in reaction by polyisobutene and suitable enophile (enophiles).
An object of the present invention is to provide the water-resisting agent that is used for the fiber base thing, it allows the happy feel of good moistureproofness and anti-water base thing.Another object of the present invention provides the method and the one object of the present invention that prepare water-resisting agent provides the new water-resisting agent of a kind of usefulness to give the method for fiber base thing water resistance.
We find that the aqueous dispersion of the multipolymer of definition was realized when these purposes were passed through beginning.
Below, copolymer dispersion is interpreted as being meant emulsion, suspension and the clear solution of multipolymer.
New aqueous dispersion comprises a kind of multipolymer, and it can be by following acquisition: free-radical polymerized following material:
(A) at least a dicarboxylic acid deutero-ethylenically unsaturated dicarboxylic acid anhydride from an at least a 4-8 carbon atom, as maleic anhydride, itaconic anhydride, citraconic anhydride or methylene radical malonic anhydride, preferred itaconic anhydride or maleic anhydride, preferred especially maleic anhydride;
(B) at least a branching or straight chain C
3-C
10The oligopolymer of-alkene, described at least a oligopolymer has molecular-weight average M
n300-5000g/mol maybe can pass through at least 3 normal C
3-C
10-alkene carries out oligomeric acquisition,
With
(C) the optionally at least a olefinic unsaturated comonomer different with (A), with its optionally with
(D) the compound reaction of at least a following formula I a or Ib, preferred Ia
Wherein
A
1Be C
2-C
20-alkylidene group, as-(CH
2)
2-,-CH
2-CH (CH
3)-,-(CH
2)
3-,-CH
2-CH (C
2H
5)-,-CH
2-CH is (different-C
3H
7)-,-CH
2-CH (n-C
4H
9)-,-(CH
2)
4-,-(CH
2)
5-,-(CH
2)
6-, preferred C
2-C
4-alkylidene group, particularly-(CH
2)
2-,-CH
2-CH (CH
3)-and-CH
2-CH (C
2H
5)-,
R
1Be phenyl, hydrogen, or preferred straight chain or branching C
1-C
30-alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-hexadecyl, Octadecane base and NSC 62789 base; More preferably C
1-C
4Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, special preferable methyl; With
N is the integer of 1-200, preferred 4-50.
Certainly, only when n for greater than 1 integer or when using the compound of different formula (D), group A
1Can be different.
In one embodiment of the invention, for example use the mixture of the different components (D) of formula Ia.Can use the mixture of formula Ia compound, wherein under each situation by mixture, at least 95 moles of %, preferred at least 98 moles of % are to the R that is no more than 99.8 moles of %
1Be C
1-C
30Alkyl and at least 0.2 mole of % are to being no more than 5 moles of %, preferably being no more than the R of 2 moles of %
1Be hydrogen.
In one embodiment of the invention, carrying out free-radical polymerized and if after suitable words and (D) reaction, add entry, water also can comprise Bronsted acid or preferred brnsted base.The example of acid is sulfuric acid, hydrochloric acid, tartrate and citric acid.The example of brnsted base is alkali metal hydroxide such as NaOH and KOH, alkaline carbonate such as Na
2CO
3And K
2CO
3, alkali metal hydrocarbonate such as NaHCO
3And KHCO
3, ammonia and amine such as Trimethylamine 99, triethylamine, diethylamine, thanomin, N, N-diethanolamine, N, N, N-trolamine and N-Mono Methyl Ethanol Amine.
In another embodiment of the present invention, water itself can add during free-radical polymerized.
The water-content that new dispersion has is 30-99.5 weight %, preferred 60-90 weight %, based on the gross weight meter of new dispersion.
Suitable comonomer (B) is propylene or straight chain or preferred branched C
4-C
10The oligopolymer of-alkene, described at least a oligopolymer has molecular-weight average M
n300-5000g/mol maybe can pass through oligomeric at least 3, preferably at least 4 equivalent C
3-C
10Alkene obtains.Example be propylene, iso-butylene, 1-amylene, 2-methyl but-1-ene, 1-hexene, 2-methylpent-1-alkene, 2-methyl oneself-1-alkene, 2-ethyl penta-1-alkene, 2-ethyl oneself-1-alkene and 2-propyl group heptan-oligopolymer of 1-alkene, 1-octene and 1-decene, preferred especially iso-butylene.The ethylenically unsaturated group that comonomer (B) has can vinyl, vinylidene or alkyl vinylidene form exist.
Above-mentioned alkene mutually or with the vinyl-arene of 20 weight % (by (B)) at the most such as vinylbenzene and alpha-methyl styrene, C
1-C
4-ring-alkylated styrenes such as 2-, 3-and 4-vinyl toluene and 4-t-butyl styrene altogether-oligopolymer also is suitable.
Particularly preferred comonomer (B) is molecular-weight average M
nFor 300-5000 for example, preferred 400-3000, preferred especially 500-2300, more preferred 550-1200, especially up to the low polypropylene and the low polyisobutene of 1000g/mol (measuring) by gel permeation chromatography (GPC).Particularly preferred low polyisobutene and low polypropylene further are to pass through oligomeric at least 3, preferably at least 4 equivalent C
3-C
10Those that-alkene obtains.
In one embodiment of the invention, the polydispersity of comonomer (B) is 1.1 to 10,, preferably at the most 3, preferred especially 1.5 to 1.8.
In one embodiment of the invention, the polydispersity M of comonomer (B)
w/ M
nBe 1.1 to 3,, preferred 1.5 to 1.8.
In a specific embodiments of the present invention, oligopolymer (B) has bimodal molecular weight distribution, wherein maximum M
nIn the 500-1200g/mol scope, and local maximum M
nIn the 2000-5000g/mol scope.
Low polypropylene and low polyisobutene itself are known, and low polyisobutene for example can pass through in the presence of boron trifluoride catalyst with the oligomeric acquisition of iso-butylene, for example referring to DE-A 27 02 604.The suitable initial substance that contains iso-butylene is iso-butylene itself and the C that contains iso-butylene
4-hydrocarbon stream is as purified C
4Cut, from the C of dehydrogenation of isobutane
4Cut, from steam crackers or FCC cracker (FCC: C fluidized catalytic cracking)
4Cut, prerequisite are relevant C
4Cut has been substantially free of 1,3-butadiene.Iso-butylene is at C
4Concentration in the-hydrocarbon fluid is generally 40-60 weight %.Appropriate C
4-hydrocarbon fluid should comprise the 1,3-butadiene that is lower than 500, preferably is lower than 200ppm usually.
The preparation method of other oligopolymer (B) itself knows; These methods for example can find in WO96/23751 and WO 99/67347, embodiment 3.
The object lesson of the compound of formula Ia is:
-Shi HO-(CH
2CH
2O)
m-CH
3Polyoxyethylene glycol, wherein m=1-200, preferred 4-100, more preferably 4-50, it is by the methyl end groups end-blocking,
The segmented copolymer of-oxyethane, propylene oxide and/or butylene oxide ring, it is by the methyl end groups end-blocking and have molecular weight M
n300-5000g/mol,
The random copolymers of-oxyethane, propylene oxide and/or butylene oxide ring, it is by the methyl end groups end-blocking and have molecular weight M
n300-5000g/mol,
-alkoxylate C
2-C
30Alcohol, particularly fatty alcohol alkoxy compound, oxo process alcohol alkoxylate or Guerbet (Guerbet) alcohol alkoxylate, alkoxylation preferably carries out with oxyethane, propylene oxide and/or butylene oxide ring; Example is
-have a C of 3-30 ethylene oxide unit
13-C
15The oxo process alcohol ethoxylate,
-have a C of 3-30 ethylene oxide unit
13The oxo process alcohol ethoxylate,
-have a C of 3-30 ethylene oxide unit
12-C
14Fatty alcohol ethoxylate,
-have a C of 3-30 ethylene oxide unit
10The oxo process alcohol ethoxylate,
-have a C of 3-30 ethylene oxide unit
10-Guerbet alcohol ethoxylate,
-have a C of 2-20 ethylene oxide unit, a 2-20 propylene oxide units and/or 1-5 epoxybutane unit
4-C
20Alcohol alkoxylate,
-have a C of 2-20 ethylene oxide unit, a 2-20 propylene oxide units and/or 1-5 epoxybutane unit
9-C
11The oxo process alcohol alkoxylate,
-have a C of 2-20 ethylene oxide unit, a 2-20 propylene oxide units and/or 1-5 epoxybutane unit
13-C
15The oxo process alcohol alkoxylate,
-have a C of 2-20 ethylene oxide unit
4-C
20Alcohol ethoxylate.
The preferred example of the compound of formula Ib is formula H
2N-(CH
2CH
2O)
m-CH
3Polyoxamide, wherein m=1-200, preferred 4-100, more preferably 4-50, it is by the methyl end groups end-blocking.
Optionally to go into to be present in the multipolymer in the new dispersion monomeric one or more (C) different with (A) in copolymerization.The example of preferred monomer (C) is:
The C of formula II
3-C
8Carboxylic acid derivative
The carboxylic acid amide of formula III
The no cyclic amide of formula IVa and the cyclic amide of formula IVb
C
1-C
20Alkyl vinyl ether is as methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, 2-ethylhexyl vinyl ether or Octadecane base vinyl ether;
The N-ethenyl derivatives of nitrogenous aromatic compound, preferred N-vinyl imidazole, 2-methyl isophthalic acid-vinyl imidazole, N-Yi Xi oxazolones, N-vinyl triazole, 2-vinyl pyridine, 4-vinylpridine, 4-vinylpridine N-oxide compound, N-vinyl imidazole quinoline or N-vinyl-glyoxal ethyline quinoline;
α, alpha, beta-unsaturated nitriles such as propenyl or methacrylonitrile;
The alkoxylate unsaturated ethers of formula V
The ester of formula VI and acid amides
The unsaturated ester of formula VII
The comonomer of phosphorous acid esters, phosphonic acid ester, sulfuric ester and sulfonate ester group is as phosphoric acid [2-{ (methyl) acryloxy } ethyl] ester and 2-(methyl) acrylamido-2-methyl isophthalic acid-propanesulfonic acid;
The straight chain of 3-40, preferred 4-24 carbon atom or branching alpha-olefin, particularly iso-butylene, diisobutylene, 1-decene, 1-dodecylene, 1-vaccenic acid, 1-eicosylene, α-C
22H
44, α-C
24H
48Mixture with above-mentioned alpha-olefin;
Vinyl aromatic compounds is suc as formula the compound of VIII
Wherein
A
2And A
3Being identical or different, is C
2-C
20Alkylidene group is as-(CH
2)
2-,-CH
2-CH (CH
3)-,-(CH
2)
3-,-CH
2-CH (C
2H
5)-,-CH
2-CH is (different-C
3H
7)-,-CH
2-CH (n-C
4H
9)-,-(CH
2)
4-,-(CH
2)
5-,-(CH
2)
6-, preferred C
2-C
4-alkylidene group, particularly-(CH
2)
2-,-CH
2-CH (CH
3)-and-CH
2-CH (C
2H
5)-;
R
2And R
3For identical or different, and be selected from straight chain or branching C
1-C
5Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl or isopentyl, preferred especially C
1-C
4Alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl;
Be in particular hydrogen;
R
4For identical or different, and be branching or straight chain C
1-C
22Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl or NSC 62789 base; Preferred especially C
1-C
4Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl, or preferred especially hydrogen;
R
5Be hydrogen or methyl;
X is the integer of 2-6, preferred 3-5;
Y is 0 or 1, preferred 1 integer;
A is the integer of 0-6, preferred 0-2;
B is the integer of 1-200, preferred 4-50;
R
6And R
7Be identical or different, and be selected from hydrogen and straight chain defined above or branching C
1-C
10Alkyl;
X is oxygen or N-R
4
R
8Be [A
3-O]
b-R
4
R
9Be selected from straight chain or branching C
1-C
20Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base or NSC 62789 base; More preferably C
1-C
14Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, neo-pentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohexyl, Sec-Hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl or n-tetradecane base; Preferred especially hydrogen or methyl;
R
10And R
11Respectively do for oneself independently of one another hydrogen, methyl or ethyl, R
10And R
11The hydrogen of preferably respectively doing for oneself;
R
12Be methyl or ethyl;
K is 0-2, preferred 0 integer.
Other variable is as defined above.
The exemplary formula III compound of choosing is (methyl) acrylamide, as acrylamide, N methacrylamide, N,N-DMAA, N-ethyl acrylamide, N-propyl group acrylamide, N tert butyl acrylamide, uncle's N-octyl acrylamide, N-undecyl acrylamide or corresponding Methacrylamide.
The exemplary formula IV compound of choosing is a N-vinyl carboxylic acid amides, as N-vinyl formamide, N-vinyl-N-methylformamide, N-vinyl acetamide or N-vinyl-N-methylacetamide; The typical compound of the exemplary formula IVb that chooses is N-vinyl pyrrolidone, N-vinyl-4-piperidone and N-vinyl-ε-Ji Neixianan.
The exemplary formula VI compound of choosing is (methyl) acrylate and (methyl) acrylamide, as N, and N-dialkyl aminoalkyl (methyl) acrylate or N, N-dialkyl aminoalkyl (methyl) acrylamide; Example is vinylformic acid N, N-dimethyl aminoethyl ester, methacrylic acid N, N-dimethylaminoethyl ester, vinylformic acid N, N-diethyllaminoethyl ester, methacrylic acid N, N-diethyllaminoethyl ester, vinylformic acid N, N-dimethylamino-propyl ester, methacrylic acid N, N-dimethylamino-propyl ester, acrylate N, N-diethylin propyl diester, methacrylic acid N, N-diethylin propyl diester, 2-(N, the N-dimethylamino) ethyl acrylamide, 2-(N, the N-dimethylamino) ethyl-methyl acrylamide, 2-(N, N-diethylin) ethyl acrylamide, 2-(N, N-diethylin) ethyl-methyl acrylamide, 3-(N, the N-dimethylamino) propyl group acrylamide and 3-(N, N-dimethylamino) propyl methyl acid amides.
The exemplary formula VII compound of choosing is vinyl-acetic ester, allyl acetate, vinyl propionate base ester, butyric acid vinyl ester, 2 ethyl hexanoic acid vinyl ester or lauric acid vinyl ester.
Following compound is preferably used as comonomer (C) especially: vinylbenzene, vinylformic acid, diisobutylene, 1-dodecylene, 1-eicosylene, α-C
22H
44, α-C
24H
48, methacrylic acid, methyl acrylate, methyl methacrylate, acrylamide, vinyl n-butyl ether, vinyl isobutyl ether, N-vinyl formamide, N-vinyl pyrrolidone, 1-vinyl imidazole and 4-vinylpridine.
If with respect to (A), (B) with (C) that needs, the multipolymer that exists in the new dispersion can be segmented copolymer, alternating copolymer or random copolymers, preferred alternating copolymer.
In one embodiment of the invention, the part in the multipolymer or all anhydride groups after polymerization with hydrolysis and and if suitable in and form exist.
In one embodiment of the invention, the mol ratio that is dispersed in the multipolymer in the new aqueous dispersion is:
(A) 5-60 mole %, preferred 10-55 mole %,
(B) 1-95 mole %, preferred 10-60 mole %,
(C) 0-70 mole %, preferred 1-50 mole %, under each situation by multipolymer, (A), (B) and (C) sum be 100 moles of % and
(D) 0-50 mole %, preferred 1-30, preferred especially 2-20 mole % press multipolymer
All carboxyl meters.
In embodiment of the present invention, new aqueous dispersion has pH3 to 10, preferred 5 to 8.
In one embodiment of the invention, the multipolymer that is dispersed in the new aqueous dispersion has average molar mass M
w1000-50000, preferred 1100-25000g/mol for example measure as standard substance as solvent and polymethylmethacrylate or polystyrene with for example tetrahydrofuran (THF) or N,N-DIMETHYLACETAMIDE by size exclusion chromatography.
In one embodiment of the invention, be dispersed in the M of the multipolymer in the new dispersion
w/ M
nBe generally 1.1 to 20, preferred 1.5 to 10.
In one embodiment of the invention, new dispersion can comprise the comonomer of not introducing with the polymerized unit form (B), and its amount for example is 1-30 weight %, by the gross weight of new aqueous dispersion.
The invention further relates to a kind of method for preparing new aqueous dispersion, below be called new preparation process again.
Be to implement new preparation process, will (A), (B) and (C) (if suitable) be used as parent material and also carry out radical copolymerization mutually.Between polymerization period or preferably after polymerization, add entry, so that the water-content of new dispersion is 30-99.5 weight %.
In one embodiment of the invention, with (A), (B) with if suitable (C) as parent material and carry out radical copolymerization mutually, and reacts with (D).Between polymerization period or preferably after polymerization, add entry, so that the water-content of new dispersion is 30-99.5 weight %.
In a specific embodiments of the present invention, at first carry out (A), (B) and (C) (if suitable) free-radical polymerized, react with (D) then.
In another specific embodiments of the present invention, in the presence of the compound (D) that total amount or part are used, carry out (A), (B) and free-radical polymerized as if suitable (C).
In another specific embodiments of the present invention, at first, carry out free-radical polymerized then with (A) with as if suitable (C) and (D) reaction.
If multipolymer and (D) reaction or free-radical polymerized in the presence of (D) are desirable, then calculate the total amount of (D), make supposition (D) complete reaction and use at the most (D) (according to all carboxyl meters in the multipolymer) of 50 moles of %, preferred 1-30 mole %, preferred especially 2-20 mole %.Among the present invention, term " all carboxyls in the multipolymer " be interpreted as being meant from polymeric comonomer (A) and suitable if (C) with acid anhydrides, with C
1-C
4-alkyl ester or those carboxyls that exist with carboxylic acid formation.
Free radicals copolymerization reaction is advantageously by radical initiator such as superoxide or hydroperoxide initiation.The example of superoxide or hydroperoxide is di-t-butyl peroxides, cross sad tertiary butyl ester, cross the PIVALIC ACID CRUDE (25) tertiary butyl ester, mistake-2 ethyl hexanoic acid tertiary butyl ester, cross the toxilic acid tertiary butyl ester, cross the isopropylformic acid tertiary butyl ester, benzoyl peroxide, diacetyl peroxide, disuccinic acid peroxide, peroxidation be right-chlorobenzoyl and dicyclohexyl cross two carbonic ethers.It also is suitable using redox system, for example the combination of one of hydrogen peroxide or Sodium persulfate or above-mentioned superoxide and reductive agent.The example of appropriate reductant comprises xitix, tartrate, Fe (II) salt such as FeSO
4, sodium pyrosulfate and sal enixum.
Further suitable initiator comprises azo-compound, as 2,2 ' Diisopropyl azodicarboxylate, 2,2 ' two (the 2-methyl-prop amidine) dihydrochloride and 2,2 of azo ' azos two (4-methoxyl group-2,4-methyl pentane nitrile).
The consumption of initiator is generally 0.1-20 weight %, preferred 0.2-15 weight %, by the total mass of all comonomers.
This new preparation process can carry out in the existence of solvent and precipitation agent or not.Being used for free-radical polymerized suitable solvent is to acid anhydrides inert polar solvent, as acetone, tetrahydrofuran (THF) He diox.Suitable precipitation agent be for example toluene, ortho-xylene ,-dimethylbenzene and aliphatic hydrocrbon.
Embodiment preferred be solvent-free or only a small amount of, promptly 0.1 weight % carries out to the solvent that is no more than 10 weight % (by comonomer (A), (B) with as if the total mass of (C) of use).Solvent is meant under the condition of copolymerization and esterification or formation acid amides and is inert material, particularly aliphatic series and aromatic hydrocarbon.As hexanaphthene, normal heptane, Permethyl 99A., benzene, toluene, ethylbenzene, xylene different structure mixture, m-xylene or o-Xylol.If it is with the reaction of (D) is to carry out under an acidic catalyst or do not carry out and (D) reaction, then free-radical polymerized and if suitable words and (D) reaction also can be selected from ketone for example acetone or methylethylketone or be selected from cyclic ethers and acyclic ethers is for example carried out in the solvent of tetrahydrofuran (THF) or di-n-butyl ether.
This new preparation process preferably under anaerobic for example in nitrogen or argon gas atmosphere, preferably in nitrogen gas stream, carry out.
Conventional equipment such as autoclave and jar can be used for new preparation process.
The addition sequence of comonomer can carry out according to variety of way.
In an embodiment of novel method, at first drop into (D) and mixture (A), then initiator is added with (B) with as if (C) that use.Here preferably with (B) with if suitable (C) adds by reinforced method.
In one embodiment of the invention, at first drop into (D) and mixture (A), then with initiator with (B) with if (C) that uses together adds by reinforced method, initiator (B) and be dissolved in separately in (D) wherein as if suitable (C).
In one embodiment of the invention, at first drop into (D) and mixture (A), then with initiator with (B) with (C) by reinforced method adding, (B) that wherein chooses is different with the feed rate of (C).
In another embodiment of the present invention, at first drop into (D) and mixture (A), add with (C) passing through to feed in raw material with initiator and (B) then, (B) that wherein chooses is identical with the feed rate of (C).
In another embodiment of the present invention, at first drop into (B) and suitable if (C) and add initiator and (A), then if suitable words and (D) reaction by reinforced method.
In another embodiment of the present invention, at first add (B), and add initiator, (A) and if suitable (C), then if suitable words and (D) reaction by reinforced method.
In another embodiment of the present invention, at first drop into (A), (B) and if suitable (D), and add initiator and (C) by reinforced method.(A), (B) and if suitable (D) also can drop in the solvent.In one embodiment of the invention, adding (B) and if adding another initiator during suitable (C).
In one embodiment of the invention, (A), (B) and if the copolymerization temperature of suitable (C) is 80-300 ℃, preferred 100-200 ℃.
Pressure can be for example 1-10 crust, preferred 1-5 crust.
Can use conditioning agent, as C
1-to C
4-alkyl aldehydes, formic acid and the compound such as 2 mercapto ethanol, 2-mercaprol, Thiovanic acid, tert-butyl mercaptan or the n-dodecyl mercaptan that contain organic SH-.The consumption of polymerization regulator is generally 0.1-10 weight %, by the total mass of the comonomer that uses.Preferably do not use conditioning agent.
During copolymerization, can add a spot of one or more polymerization retarders, as Hydroquinone monomethylether.Polymerization retarder can be advantageously with (B) and if suitable (C) metering.The appropriate amount of polymerization retarder is 0.01-1 weight %, preferred 0.05-0.5 weight %, by the Mass Calculation of all comonomers.When copolymerization is being higher than when carrying out under 80 ℃, it is particularly preferred adding polymerization retarder.
At (A) and (B), if suitable (C), if suitable (D) and if suitable initiator is reinforced finish after, reaction is continued.
The free-radical polymerized time be generally 1-12, preferred 2-9, preferred 3-6 hour especially.
With reaction times of (D) can be 1-12, preferred 2-9, preferred 3-6 hour especially.
If this new preparation process according to (A), (B) and (C) (if suitable) copolymerization mode is carried out in the presence of (D) of total amount, then suitable reaction total time is 1-12 for example, preferably 2-10, especially preferably 3-8 hour.
Can for example carry out in the presence of sulfuric acid, methylsulfonic acid, tosic acid, dodecyl Phenylsulfonic acid, hydrochloric acid or the acid ion exchangers in the presence of the catalyst-free or at catalyzer, particularly acidic acid catalyzer with the reaction of (D).
If carry out with being reflected under the catalyzer existence of (D), then the reaction times can be 0.5-2 hour.
In another variation of aforesaid method, carry out with being reflected under the entrainer existence that can form azeotrope of (D) with any water of generation in the reaction.
Under the above-mentioned steps condition, usually will (D) completely or partially with the carboxyl of copolymerization acid anhydrides (A) and if suitable words and from the carboxyl reaction of (C).Usually, residual unreacted (D) that is lower than 40 moles of %.
Can be by known method itself such as extraction and from the multipolymer that can obtain by new preparation process, separate unconverted (D).
In one embodiment, can save from another step according to separation unreacted (D) the multipolymer of the present invention's preparation.In the present embodiment, unreacted (D) of polymkeric substance and certain percentage is used from the treatment of fibrous substrate thing.
Multipolymer obtains by above-mentioned copolymerization method.The gained multipolymer can come purifying by ordinary method, removes unreacted monomer as redeposition or extraction.If use solvent or precipitation agent, then they can for example be removed by distillation after copolymerization finishes.
For the present invention, water is added by in the multipolymer that as above prepares, the water yield of calculating adding is to obtain the new dispersion that water content is 30-99.5 weight %, by new dispersion total mass.
In one embodiment of the invention, free-radical polymerized and if suitable words with (D) add entry after the reaction.Also can comprise Bronsted acid or preferred brnsted base in the water.The example of Bronsted acid is sulfuric acid, hydrochloric acid, tartrate and citric acid.The example of brnsted base is alkali metal hydroxide such as NaOH and KOH, alkaline carbonate such as Na
2CO
3And K
2CO
3, alkali metal hydrocarbonate such as NaHCO
3And KHCO
3, ammonia and amine, as Trimethylamine 99, triethylamine, diethylamine, thanomin, N, N-diethanolamine, N, N, the concentration of N-trolamine or N-Mono Methyl Ethanol Amine, Bronsted acid or preferred brnsted base is generally 1-20 weight %, by the gross weight of water and Bronsted acid or water and brnsted base.
Water itself can add during free-radical polymerized, but does not preferably add water, up to free-radical polymerized end.If free-radical polymerized and exist down and carry out with the solvent that is reflected at of (D), then preferably at first for example by distillation except that desolvating, and only add entry after this.
In a specific embodiments of the present invention, desolvate with for example removing after the water reaction by vapor distillation.
By adding entry (as suitable, it can comprise Bronsted acid or preferred brnsted base), the some or all of carboxylic acid anhydride groups that exist in the multipolymer can be hydrolyzed.
After adding entry (can comprise Bronsted acid or preferred brnsted base), can make this be reflected at 20-100 ℃, preferably carry out 10 minutes to 4 hours under 90 ℃ at the most as suitable words.
In one embodiment of the invention, at first drop into water (it can comprise Bronsted acid or preferred brnsted base) down, and add if suitable words have been heated to 50-100 ℃ multipolymer by reinforced method at 50-100 ℃.
In another embodiment of the present invention, at first drop into multipolymer down, and add if suitable words have been heated to 50-100 ℃ water by reinforced method at 50-100 ℃, this water also can comprise Bronsted acid or preferred brnsted base.
In one embodiment of the invention, add if suitable words have been heated to 50-100 ℃ multipolymer at first at 50-100 ℃ of mixture that drops into water (it also can comprise Bronsted acid or preferred brnsted base) and nonionogenic tenside down, and by reinforced method.The example of suitable nonionogenic tenside is polyalkoxylated C
12-C
30-alcohol, preferred degree of alkoxylation is the C of 3-30
12-C
30-alcoholization.
In another embodiment of the present invention, at first drop into multipolymer down at 50-100 ℃, and add the mixture of entry (it also can comprise Bronsted acid or preferred brnsted base) and nonionogenic tenside by reinforced method, be heated to 50-100 ℃ multipolymer as if the suitable described mixture of words.The example of suitable nonionogenic tenside is polyalkoxylated C
12-C
30-alcohol, preferred degree of alkoxylation is the C of 3-30
12-C
30-alcohol.
The invention further relates to new aqueous dispersion and be used for the purposes of treatment of fibrous substrate thing.The invention further relates to method, below be called new treatment process again with new aqueous dispersion treatment of fibrous substrate thing.
In the present invention, the example of fiber base thing is:
-textiles, it is interpreted as being meant textile fibres, textile fibres sheet structure, weaving work in-process and finished product and in the present invention by the finished article of its production, these article except Clothing industry with the textiles, also comprise carpet and other household textiles and play the textile constructions of technical purpose.These also comprise not molding structure, as flock, linear structure such as cord, line, yarn, macrofiber, rope, rope and warp thread, and three-dimensional structure such as felt, textile fabric, nonwoven fabric and oakum.These textiless can be natural origin such as wool, flax or particularly cotton, or synthetic source is as polymeric amide and polyester;
-paper, plate and card board kai box;
-timber and wood composites are as shaving board;
-leatheroid, Alcantara or Lefa promptly from the leather fiber of leather castoff, obtain the synthetic fibrous texture of producing with leather castoff with binding agent or plastic resin treatment;
Preferred especially
-leather, it is interpreted as through pre-tanning with preferably by the animal hides of the combination tanning of non-essential chrome tanning agent, mineral tanning agent, Polymer Tanning Agent, synthetic tanning agent, vegetable tanning agent, resin tanning agent or above-mentioned at least two kinds of tanning agents.
In one embodiment of the invention, leather is animal hides (wet blue) or the work in-process produced by chrome tanning agent.
New dispersion can be used for tanning and is preferred in the retanning, below is called new tanning and new retanning method.New dispersion can be used in the independent treatment step.
This new tanning can be carried out usually in such a manner: with new dispersion or novel copolymers by a or many parts before tanning, add at once or during tanning.This new tanning is preferably carried out under pH2.5-8, preferred 3-5.5, observes the about 0.3-3 of a pH increase unit when carrying out new tanning usually.
In one embodiment of the invention, pH can increase about 0.3-3 unit by adding alkalizing agent.
In one embodiment of the invention, new tanning can begin under pH4-8, and can by add acidic components for example formic acid under pH3-3.5, novel copolymers is fixed.
This new tanning is carried out under 10-45 ℃, preferred 20-30 ℃ usually.The time that has proved 10 minutes to 12 hours, preferred 1-3 hour is suitable.New tanning can be in being customarily used in any required container of tanning for example by bucket or in rotating cylinder rotary drum processing carry out.
In a variation of new tanning, with new dispersion or novel copolymers with one or more conventional tanning agents as with chrome tanning agent, mineral tanning agent, preferably use with synthetic tanning agent, Polymer Tanning Agent or vegetable tanning agent, as at Ullmann ' s Encyclopedia of Industrial Chemistry, the A15 volume, p259 to 282 and particularly 268 pages rise., the 5th edition, (1990) are described among the Verlag Chemie Weinheim.
In a variation of new tanning, new dispersion or novel copolymers are used with emulsion oil-filling agent such as natural glycerin three esters, white oil, paraffin, wax, silicone oil and other emulsifying agent.
In a variation of new tanning, new dispersion or novel copolymers are used with conventional tanning agents and emulsion oil-filling agent (but not having silicone oil).
In new tanning, can use new dispersion or the novel copolymers of 0.5-40 weight %, preferred 2-20 weight %, by pelt weight.
Handling the novel method of leather can preferably carry out as the method for using new dispersion or novel copolymers retanning leather.This new retanning method be from conventional tanning promptly for example with the chrome tanning preparation, based on the mineral tanning agent of Al, Ti, Zr, Fe and Si, preferably use the work in-process of Polymer Tanning Agent, vegetable tanning agent, synthetic tanning agent or resin tanning agent tanning initial, or initial from the work in-process of producing according to the invention described above method.For carrying out new retanning method, this novel copolymers is acted on the work in-process.
This new retanning method can be carried out under other normal condition.Choose one or more, i.e. 2 to 6 soaking steps, and used water washing between these soaking steps easily.Temperature during each soaking step is 5-60 ℃ under each situation, preferred 20-45 ℃.
In this new retanning method, can use new dispersion or the novel copolymers of 0.5-40 weight %, preferred 2-20 weight %, based on shaving leather weight meter.
Certainly, usually the composition that during retanning, uses, for example fat liquor, Polymer Tanning Agent, based on acrylate and/or methacrylic ester or based on the emulsion oil-filling agent of siloxanes, can add in the new dispersion or novel copolymers of new tanning or retanning method based on the retanning agent of resin and the combination of vegetable tanning agent, filler, leather dyestuff or emulsifying agent or above-mentioned at least two kinds of materials.
In one embodiment of the invention, new treatment process and preferred new retanning method are to use at least a molecular-weight average M
nBranching or straight chain C for 300-5000g/mol
3-C
10The oligopolymer of-alkene or use can be passed through oligomeric at least 3 equivalent C
3-C
10The oligopolymer that-alkene obtains carries out.At least a oligopolymer preferably is equivalent to be used to prepare the comonomer (B) of novel dispersion or novel copolymers.Polymeric (B) can be 1:0.1 to 1:10 with the ratio of another oligopolymer.
In one embodiment of the invention, new retanning method in the presence of emulsifying agent for example at nonionogenic tenside such as many alkoxide C
7-C
30-alkanol, preferably has a C of 3-30 alkoxide degree
7-C
30Alkanol carries out under existing.If need to use emulsifying agent, then can use the emulsifying agent of 1-30 weight %, by novel copolymers.
In one embodiment of the invention, in new retanning method, exempt and add water-resisting agent or based on the emulsion oil-filling agent of siloxanes.
By new treatment process, make the fiber base thing become waterproof or by emulsion oil-filling.
The invention further relates to the fiber base thing, preferred leather for example based on the leather of wet-white leather or wet blue, is preferably based on wet-white leather, especially by new treatment process production.They have happy especially feel.
The present invention relates on the other hand by new tanning or new retanning method or by the leather of the combinations produce of new tanning and new retanning method.This new leather has general favourable quality, as happy especially feel and particularly soft and plentiful.New leather comprises above-mentioned multipolymer, and infiltration is abundant especially in the microcell of basic fiber for it.
Another aspect of the present invention comprises new leather, for example based on the new leather of wet-white leather or wet blue, be preferably based on the new leather of wet-white leather, particularly be used for the purposes of production dress-goods, furniture parts or trolley part based on new leather with the wet-white leather of vegetable tanning agent production.Another aspect of the present invention comprise with new leather, for example based on the new leather of wet-white leather or wet blue, be preferably based on the method for new leather production dress-goods, furniture parts or the trolley part of wet-white leather.Among the present invention, dress-goods comprises for example jacket, trousers, footwear, particularly sole, belt or braces.According to the present invention, furniture parts comprises and contains the leather component as seat surface or all that furniture parts on arm rest.Example is take one's seat furniture such as seat, chair and sofa.The example of trolley part is an automotive seat.
Another aspect of the present invention comprises and contains dress-goods new leather or that produced by new leather.The present invention comprises on the other hand and contains furniture new leather or that produced by new leather.The present invention comprises on the other hand and contains trolley part new leather or that produced by new leather.
The invention further relates to multipolymer, it can be by following acquisition: at least a dicarboxylic acid deutero-ethylenically unsaturated dicarboxylic acid anhydride of free-radical polymerized following material (A) from an at least a 4-8 carbon atom,
(B) at least a branching or straight chain C
3-C
10The oligopolymer of-alkene, described at least a oligopolymer has molecular-weight average M
n300-5000g/mol maybe can pass through at least 3 normal C
3-C
10-alkene carries out oligomeric acquisition,
(C) the optionally at least a olefinic unsaturated comonomer different with (A),
With with
(D) compound of at least a following formula I a or Ib reaction
Wherein, in formula Ia and Ib,
A
1Be identical or different C
2-C
20Alkylidene group,
R
1C for straight chain or branching
1-C
30Alkyl, phenyl or hydrogen and
N is the integer of 1-200.
Certainly, have only when n greater than 1 or when using the different compound of formula Ia and/or Ib, group A
1Can be different.
In one embodiment of the invention, for example use the mixture of the different components (D) of formula Ia.Particularly, can use those mixtures of the compound of formula Ia, wherein under each situation by mixture, at least 95 moles of %, preferred at least 98 moles of % are to the R that is no more than 99.8 moles of %
1Be C
1-C
30Alkyl and at least 0.2 mole of % are to being no more than 5 moles of %, preferably being no more than the R of 2 moles of %
1Be hydrogen.
In one embodiment of the invention, novel copolymers or the dicarboxylic anhydride (A) in novel copolymers, introduced as polymerized unit partially or completely with hydrolysis and if suitable words with in and form exist.
In one embodiment of the invention, novel copolymers comprises at least a comonomer (C) of polymerized unit form, and it is selected from
The unsaturated C of the olefinic of formula II
3-C
8Carboxylic acid derivative
The carboxylic acid amide of formula III
The no cyclic amide of formula IVa or the cyclic amide of formula IVb
C
1-C
20Alkyl vinyl ether;
The N-ethenyl derivatives of nitrogenous aromatic substance;
α, alpha, beta-unsaturated nitriles;
The alkoxylate unsaturated ethers of formula V
The ester of formula VI or acid amides
The unsaturated ester of formula VII
The comonomer of phosphorous acid esters, phosphonic acid ester, sulfuric ester and sulfonate ester group;
The straight chain of 3-40, preferred 4-24 carbon atom or branching alpha-olefin, particularly iso-butylene, diisobutylene, 1-decene, 1-dodecylene, 1-vaccenic acid, 1-eicosylene, α-C
22H
44, α-C
24H
48Mixture with above-mentioned alpha-olefin;
The vinyl aromatic compounds of formula VIII;
Wherein, in the formula
A
2And A
3Be identical or different, and be C
2-C
20Alkylidene group;
R
2And R
3Be identical or different, and be selected from hydrogen, straight chain or branching C
1-C
5Alkyl and COOR
4,
R
4Be identical or different, and be selected from hydrogen and branching or straight chain C
1-C
22Alkyl,
R
5Be hydrogen or methyl,
X is 2 to 6 integer,
Y is selected from 0 and 1 integer,
A is the integer of 0-6,
B is the integer of 1-200,
R
6And R
7Be identical or different, and be selected from hydrogen and straight chain or branching C
1-C
10Alkyl,
X is oxygen or N-R
4,
R
8Be [A
3-O]
b-R
4,
R
9Be identical or different and be selected from hydrogen and straight chain or branching C
1-C
10Alkyl,
R
10And R
11Respectively do for oneself independently of one another hydrogen, methyl or ethyl,
R
12Be selected from methyl and ethyl,
K is the integer of 0-2.
Other variable is as defined above.
In one embodiment of the invention, the mol ratio of the comonomer of introducing as polymerized unit in novel copolymers is as follows:
(A) 5-60 mole %, preferred 10-55 mole %,
(B) 1-95 mole %, preferred 10-60 mole %,
(C) 0-70 mole %, preferred 1-50 mole %, under each situation by multipolymer, (A),
(B) and (C) sum be 100 moles of % and
(D) 0-50 mole %, preferred 1-30 mole %, preferred especially 2-20 mole % are by all carboxyls of novel copolymers.
In one embodiment of the invention, the average molar mass M of novel copolymers
wBe 1000-50000, preferred 1100-25000g/mol, for example measure as standard substance as solvent and polymethylmethacrylate or polystyrene with for example tetrahydrofuran (THF) or N,N-DIMETHYLACETAMIDE by gel permeation chromatography.
If with respect to (A), (B) with suitable (C), novel copolymers can be segmented copolymer, alternating copolymer or random copolymers, preferred alternating copolymer.
The polydispersity M of novel copolymers
w/ M
nBe generally 1.1 to 20, preferred 1.5 to 10.
The invention further relates to the method for preparing novel copolymers.
The invention further relates to the method for the new aqueous dispersion of preparation, below be called new preparation process again.
In implementing new preparation process, will (A), (B) and if suitable (C) also carries out free-radical polymerized mutually as parent material and react with (D).With being reflected at before the copolymerization of (D), during or carry out afterwards.
In one embodiment of the invention, carrying out free-radical polymerized and if after suitable words and (D) reaction, water is hydrolyzed, water also can comprise Bronsted acid or preferred brnsted base.The example of Bronsted acid is sulfuric acid, hydrochloric acid, tartrate and citric acid.The example of brnsted base is alkali metal hydroxide such as NaOH and KOH, alkaline carbonate such as Na
2CO
3And K
2CO
3, alkali metal hydrocarbonate such as NaHCO
3And KHCO
3, ammonia and amine such as Trimethylamine 99, triethylamine, diethylamine, thanomin, N, N-diethanolamine, N, N, N-trolamine or N-Mono Methyl Ethanol Amine.
Novel copolymers is usually with the form of the aqueous dispersion or the aqueous solution or acquisition in statu quo.Novel copolymers can be separated from new aqueous dispersion by the known method of those skilled in the art itself, for example by vaporize water or pass through spraying drying.
Another aspect of the present invention comprises the purposes that novel copolymers is used for the treatment of fibrous substrate thing.
The invention further relates to the purposes that new aqueous dispersion or novel copolymers are used to flood sheet base thing.The method that the invention further relates to new dispersion and novel copolymers dipping sheet base thing is also referred to as new dipping method hereinafter.This new dipping method for example can be undertaken by handling sheet base thing with at least a new aqueous dispersion or at least a novel copolymers.
In the present invention, sheet base thing can be for example concrete or fragment of brick.
The embodiment that below works is used to illustrate the present invention.
1. the synthetic method that is used for copolymerization and esterification
All are reflected under the nitrogen atmosphere carries out, except as otherwise noted.
The average molar mass M of novel copolymers
wBe to measure as standard substance as solvent and polymethylmethacrylate with N,N-DIMETHYLACETAMIDE by size exclusion chromatography.
1.1. be used for the general method of bulk copolymerization and esterification
At first with comonomer (B) with if suitable (C) (according to table 1) drops in the 2L jar and be heated to 150 ℃ in the nitrogen gas stream of gentleness.After reaching this temperature, monomer (A) was metered into liquid form as the melt under about 70 ℃ in 5 hours and will be metered in 5.5 hours as if suitable (C) (according to table 1) and the di-t-butyl peroxide of described amount.Adding the method for comonomer (C) or the comonomer (C) of adding (as if suitable) provides in table 1.Continue heating 1 hour down at 150 ℃ then.
When appropriate, add (D) then.Add in the experiment of (D) therein, the gained mixture is heated to 150 ℃ under nitrogen, heated 3 hours.
Then the gained reaction mixture is further handled under each situation, obtained new dispersion thus.
The gained reaction mixture is cooled to 90 ℃, and adds sodium hydroxide, under each situation, the mol ratio of NaOH/ maleic anhydride is 0.6:1.0.Then, stirred 4 hours down, then be cooled to room temperature at 90 ℃.Obtain to have separately the new dispersion of pH5.5-6.5.
The further details for preparing new dispersion provides in table 1.
1.2. preparation comprises the method for the dispersion of copolymer 13
At first 245g (2.5mol) maleic anhydride is dropped in the 400g o-Xylol in the 2L jar that is equipped with the dry ice water cooler, and in gentle nitrogen gas stream, is heated to 120 ℃.After reaching this temperature, in 3 hours, be metered into the low polyisobutene (M of 250g (0.25mol)
w=1000g/mol), in 5 hours, add 140g (2.5mol) iso-butylene and in 5.5 hours, add 10.4g and cross sad tertiary butyl ester, continue heating 1 hour down at 120 ℃.After being cooled to 90 ℃, adding 660g water and remove o-Xylol by vapor distillation.The gained reaction mixture is cooled to 60 ℃, and adds the sodium hydroxide solution of 400g concentration 25%.Stirred 1 hour down at 60 ℃ then, then be cooled to room temperature.Obtain dispersion 13 of the present invention.The pH of dispersion 13 of the present invention is 6.9, and water-content is 74%.M
wBe 10000.
2. characteristic test
Data in weight % are based on the shaving tare weight under each situation, except as otherwise noted.
2.1. the application in the retanning leather-production vamp leather
Two kinds of commercial ox wet blues (available from Packer, USA) are spread to thickness 1.8-2.0mm and be cut into eight bars of about 1000g separately.Then with the sodium formiate of 2 weight % and the NaHCO of 0.4 weight %
3Add in these bars in the rotary drum (50L) with naphthene sulfonic acid/formaldehyde condensation products (according to US 5,186,846, title is the embodiment preparation of " dispersion agent 1 ") of 1 weight %, wherein flowing fluid ratio is that 200 weight % and pitch time are 10-minute.After 90 minutes, get rid of liquid.Then these bars are dispensed to isolating 7 rotary drum processing barrels.
With the water of 100 weight %, concentration 50 weight % (solid content) aqueous dye solutions of each 1 weight % are metered under 25-35 ℃ in the rotary drum 1 to 7, the solid of described solution has following composition:
The dyestuff of 70 weight parts, from EP-B 0 970 148, embodiment 2.18,
The Acid Brown 75 (iron complex) of 30 weight parts, color index 1.7.16;
And carry out rotary drum and processed 10 minutes.
Subsequently, as shown in table 2, add each the new dispersion that provides in the table 1 of 6 weight %, and with this mixture rotary drum processing 30 minutes.Add the sulfone tanning agent (from EP-B 0 459 168, embodiment K1) of 8 weight % then and rotary drum processing 30 minutes again under 15 rev/mins.Subsequently, with these bars each vegetable tanning agent with 3 weight %
Handle with each above-mentioned dye solution of 1.5 weight %.
Be acidified to pH3.6-3.8 with formic acid.After 20 minutes,, discharge then by the optical method assessment liquid that is used to find time.Obtain new leather 2.1.1 to 2.1.7.Subsequently with of the water washing of these new leathers with 200 weight %.At last, the emulsion oil-filling agent (preparing according to the description under 3) with 2 weight % is metered in 100% water under 50 ℃.After the rotary drum processing 45 minutes, carry out acidifying with the formic acid of 1 weight %.
With washed leather drying and draw soft.
New leather 2.1.1 to 2.1.7 show good fullness ratio, flexibility and feel and with the good dyestuff penetration combination of fiber.In addition, leather shows outstanding water-repellancy under need not handling based on the water-resisting agent of silicone compounds, this new water resistance even can be above the effect of silicone oil.
Comparative example C1
For comparative example C1, operation as above but different is, replaces multipolymer, divides two portions to be metered into the emulsion oil-filling agent from 3 of 8 weight % altogether, at first with 4 weight % emulsion oil-filling agent with
Add together with dye solution, after the acidifying first time, add above-mentioned second section 4 weight % simultaneously.
Table 2: the characteristic of new leather 2.1.1 to 2.1.7 and contrast leather C1
| No. | Multipolymer (table 1) | Fullness ratio | The grain tightness | Pliability | Water-absorbent 2h 1[weight %] | Water permeability, dynamically 2 | Dyeing uniformity |
| C1 | - | 3 | 3.5 | 3 | 62 | 26 | 3 |
| 2.1.1 | 2 | 3 | 3 | 3.5 | 49 | 180 | 2.5 |
| 2.1.2 | 5 | 1.5 | 2 | 1.5 | 11 | 42000 | 1.5 |
| 2.1.3 | 6 | 2 | 2 | 2 | 19 | 10500 | 2 |
| 2.1.4 | 7 | 3 | 2.5 | 3 | 38 | 1200 | 3 |
| 2.1.5 | 8 | 1 | 3 | 2 | 16 | 15000 | 2 |
| 2.1.6 | 10 | 2.5 | 3 | 3 | 43 | 240 | 3 |
| 2.1.7 | 12 | 2.5 | 2.5 | 1 | 40 | 400 | 1.5 |
Note:
Evaluation to fullness ratio, grain tight type, pliability and dyeing uniformity is carried out according to the hierarchical system from 1 (very good) to 5 (poor).
1: water-absorbent is according to Kubelka, and based on DIN 53330 (5.78), Das Leder 12 (1961), and 36-37 measures, penetration time: 2h
2: under dynamic loads, measure behavior with respect to water,
The Maeser test, according to ASTM D 2099,
Das Leder 12 (1961), 38-40, the water permeate after bending repeatedly.
2.2 embodiment: 2.2.1 to 2.2.7: the half-finished new retanning method of wet-white leather
The ox-hide of southern German is converted into corresponding wet-white leather work in-process by standard method, is whittled into thickness 1.8mm thickness and is cut into the bar of about 500g separately.
With the sodium formiate of 2 weight % and the NaHCO of 0.4 weight %
3Add in the work in-process bar in the rotary drum (50L) with naphthene sulfonic acid/formaldehyde condensation products (according to US 5,186,846, title is the embodiment preparation of " dispersion agent 1 ") of 1 weight %, wherein flowing fluid ratio is that 150 weight % and pitch time are 10 minutes.After 90 minutes, expel liquid.Then these bars are dispensed to isolating 7 rotary drum processing barrels.
Then, add each table 1 and the novel copolymers dispersion of table 3 and each sulfone tanning agent of 8 weight % of 10 weight %, and carry out rotary drum processing 45 minutes with leather from EP-B 0 459 168 embodiment K1.Be metered into the vegetable tanning agent Tara (BASF Aktiengesellschaft) of 6 weight % and concentration 50 weight % (solid content) aqueous dye solutions of 2 weight % then, the solid of described solution has following composition:
The dyestuff of 70 weight parts, from EP-B 0 970 148, embodiment 2.18,
The Acid Brown 75 (iron complex) of 30 weight parts, color index 1.7.16;
And carry out rotary drum again and processed 2 hours.After 2 hours, be adjusted to 3.6 with formic acid.At last, under each situation, add 1.5%
OK, and be acidified to pH3.2 with formic acid after 60 minutes process periods at further rotary drum.Obtain new leather 2.2.1 to 2.2.7.
Should new leather each with 100% water washing twice, the hygrometric state store overnight, part is dry, then under 50 ℃ in crank drying on the net.Scrape soft after, by following assessment leather.
This assessment is carried out according to the hierarchical system of 1 (very good) to 5 (well).Liquid drains assessment with the naked eye to carry out according to the standard of residual dye (disappearance) and muddiness (emulsion oil-filling agent).In embodiment 2.2.6 and 2.2.7, be metered into
Be metered into the silicone emulsion of 1.5 weight % before the OK according to 4 (faces as follows).
Table 3: embodiment 2.2.1 to 2.2.7
| No. | Multipolymer (table 1) | Fullness ratio | The grain tightness | Pliability | Water-absorbent *2h [weight %] | Water permeability **, dynamically | Dyeing uniformity |
| 2.2.1 | 12 | 2.5 | 3.5 | 2.5 | 58 | 120 | 2.5 |
| 2.2.2 | 5 | 2.5 | 2.5 | 1.5 | 19 | 18000 | 1.5 |
| 2.2.3 | 6 | 2 | 3 | 2 | 26 | 4300 | 2 |
| 2.2.4 | 7 | 3.5 | 2.5 | 3.5 | 46 | 180 | 3 |
| 2.2.5 | 8 | 1 | 2 | 2 | 34 | 7500 | 2 |
| 2.2.6 | 5 | 1.5 | 2.5 | 1 | 12.8 | 45000 | 1.5 |
| 2.2.7 | 8 | 2 | 1.5 | 1 | 20.5 | 22000 | 2 |
*According to DIN 53328
*According to ASTM D 2099
3. the preparation of emulsion oil-filling agent
Following material is mixed in the 2L jar:
The 230g polyisobutene, it has M
n=1000g/mol and M
w=1800g/mol
30g n-C
18H
37O-(CH
2CH
2O)
25-OH
5g n-C
18H
37O-(CH
2CH
2O)
80-OH
40g oleic acid
The oxidation triolein of 230g sulfitation
This mixture under agitation is heated to 60 ℃, and adds 470g water and 10gn-C
16H
33O-(CH
2CH
2O)
7-OH.Then with the gained emulsion through the slit homogenizer.Obtain finely divided stable emulsion.
4. the preparation of silicone emulsion
Following component in being housed, is mixed by the 2L container of agitator:
The siloxanes of 150g following formula, dynamic viscosity 600mm
2/ s
As the random cocondensation compound with q=3 and p=145 (under each situation, being mean value)
130g N-oleoyl sarcosine
15g NaOH (solid)
(36/38 ° of 153g slack wax; Shell)
450ml water
The pH of gained silicone emulsion is 8.5.
Claims (20)
1. the aqueous dispersion of a multipolymer is by following acquisition: free-radical polymerized following material
(A) at least a dicarboxylic acid deutero-ethylenically unsaturated dicarboxylic acid anhydride from an at least a 4-8 carbon atom,
(B) oligopolymer of at least a iso-butylene, the molecular-weight average M of described at least a oligopolymer
nBe 300-5000g/mol,
(C) the optionally at least a olefinic unsaturated comonomer different with (A) and
Compound reaction with (D) at least a following formula I a or Ib
Add entry subsequently
Wherein, in formula Ia and Ib,
A
1Be identical or different C
2-C
20Alkylidene group,
R
1Be the C of straight chain or branching
1-C
30Alkyl, phenyl or hydrogen and
N is the integer of 1-200,
Water-content is 30-99.5 weight %, based on the aqueous dispersion meter;
Wherein the mol ratio with the comonomer in the polymerized unit form introducing multipolymer is as follows:
A) 5-60 mole %,
B) 1-95 mole %,
C) 0-70 mole %, under each situation by multipolymer, (A), (B) and (C) sum be 100 moles of % and
D) 1-50 mole % is based on all carboxyl meters of multipolymer.
2. according to the aqueous dispersion of claim 1, wherein after polymerization with all the anhydride group waters or the alkali aqueous solution hydrolysis of a part of anhydride group or the multipolymer of multipolymer.
3. according to the aqueous dispersion of claim 1 or 2, wherein (C) is selected from the unsaturated C of olefinic of formula II
3-C
8Carboxylic acid derivative
The carboxylic acid amide of formula III
The no cyclic amide of formula IVa or the cyclic amide of formula IVb
C
1-C
20Alkyl vinyl ether;
The N-ethenyl derivatives of nitrogenous aromatic substance;
α, alpha, beta-unsaturated nitriles;
The alkoxylate unsaturated ethers of formula V
The ester of formula VI or acid amides
The unsaturated ester of formula VII
The comonomer of phosphorous acid esters, phosphonic acid ester, sulfuric ester and sulfonate ester group;
The alpha-olefin of 3-40 carbon atom;
The vinyl aromatic compounds of formula VIII
Wherein, in the formula,
A
2Be C
2-C
20Alkylidene group;
R
2And R
3Be identical or different, and be selected from hydrogen, straight chain or branching C
1-C
5Alkyl and COOR
4,
R
4Be identical or different, and be selected from hydrogen and branching or straight chain C
1-C
22Alkyl,
R
5Be hydrogen or methyl,
X is the integer of 2-6,
Y is selected from 0 and 1 integer,
A is the integer of 0-6,
R
6And R
7Be identical or different, and be selected from hydrogen and straight chain or branching C
1-C
10Alkyl,
X is oxygen or N-R
4,
R
8Be [A
3-O]
b-R
4,
A
3Be C
2-C
20 alkylidene group,
B is the integer of 1-200,
R
9Be selected from hydrogen and straight chain or branching C
1-C
10Alkyl,
R
10And R
11Respectively do for oneself independently of one another hydrogen, methyl or ethyl,
R
12Be selected from methyl and ethyl,
K is the integer of 0-2.
4. according to the aqueous dispersion of claim 1 or 2, it comprises the oligopolymer of at least a iso-butylene, the molecular-weight average M of described at least a oligopolymer
nBe 300-5000g/mol.
5. method for preparing according to the aqueous dispersion of claim 1 or 2 wherein at first drops into (B) and (C), adds initiator and (A) by reinforced method, (A), (B) and (C) carry out free-radical polymerizedly mutually, reacts with (D) then and also adds entry then.
6. according to the method for claim 5, wherein with the reaction of (D) at (A), (B) with if carry out during needing (C) to carry out copolymerization or afterwards with (D).
7. the purposes that is used for the treatment of fibrous substrate thing according to the aqueous dispersion of claim 1 or 2.
8. the method for a treatment of fibrous substrate thing is used any one the aqueous dispersion according to claim 1-4.
9. method according to Claim 8, wherein the fiber base thing is selected from leather, textiles, paper, plate, timber, wood composites, leatheroid and Lefa.
10. according to the method for claim 9, wherein leather is a wet-white leather.
11. fiber base thing by handling according to each method of claim 8-10.
12. according to the fiber base thing of claim 11, wherein said basic thing is a leather.
13. according to the fiber base thing of claim 12, wherein said leather is based on wet-white leather.
14. the purposes that is used to produce clothing item or furniture parts or trolley part according to each fiber base thing of claim 11-13.
15. a multipolymer is by following acquisition: free-radical polymerized following material
(A) at least a dicarboxylic acid deutero-ethylenically unsaturated dicarboxylic acid anhydride from an at least a 4-8 carbon atom,
(B) oligopolymer of at least a iso-butylene, the molecular-weight average M of described at least a oligopolymer
nBe 300-5000g/mol,
(C) the optionally at least a olefinic unsaturated comonomer different with (A) and
Compound reaction with (D) at least a following formula I a or Ib
Wherein, in formula Ia and Ib,
A
1Be identical or different C
2-C
20Alkylidene group,
R
1Be the C of straight chain or branching
1-C
30Alkyl, phenyl or hydrogen and
N is the integer of 1-200,
Optionally be hydrolyzed;
Wherein the mol ratio with the comonomer in the polymerized unit form introducing multipolymer is as follows:
A) 5-60 mole %,
B) 1-95 mole %,
C) 0-70 mole %, under each situation by multipolymer, (A), (B) and (C) sum be 100 moles of % and
D) 1-50 mole % is based on all carboxyl meters of multipolymer.
16. according to the multipolymer of claim 15, wherein (C) is selected from the unsaturated C of olefinic of formula II
3-C
8Carboxylic acid derivative
The carboxylic acid amide of formula III
The cyclic amide of the no cyclic amide of formula IV a or formula IV b
C
1-C
20Alkyl vinyl ether;
The N-ethenyl derivatives of nitrogenous aromatic substance;
α, alpha, beta-unsaturated nitriles;
The alkoxylate unsaturated ethers of formula V
The ester of formula VI or acid amides
The unsaturated ester of formula VII
The comonomer of phosphorous acid esters, phosphonic acid ester, sulfuric ester and sulfonate ester group;
The alpha-olefin of 3-40 carbon atom;
The vinyl aromatic compounds of formula VIII
Wherein, in the formula,
A
2Be C
2-C
20Alkylidene group;
R
2And R
3Be identical or different, and be selected from hydrogen, straight chain or branching C
1-C
5Alkyl and COOR
4,
R
4Be identical or different, and be selected from hydrogen and branching or straight chain C
1-C
22Alkyl,
R
5Be hydrogen or methyl,
X is the integer of 2-6,
Y is selected from 0 and 1 integer,
A is the integer of 0-6,
R
6And R
7Be identical or different, and be selected from hydrogen and straight chain or branching C
1-C
10Alkyl,
X is oxygen or N-R
4,
R
8Be [A
3-O]
b-R
4,
A
3Be C
2-C
20Alkylidene group,
B is the integer of 1-200,
R
9Be selected from hydrogen and straight chain or branching C
1-C
10Alkyl,
R
10And R
11Respectively do for oneself independently of one another hydrogen, methyl or ethyl,
R
12Be selected from methyl and ethyl,
K is the integer of 0-2.
17. be used for the purposes of treatment of fibrous substrate thing according to the multipolymer of claim 15 or 16.
18. according to claim 1-4 any one aqueous dispersion or the purposes that is used to flood sheet base thing according to the multipolymer of claim 15 or 16.
19. a method of flooding sheet base thing, wherein this sheet base thing is used according to claim 1-4 any one aqueous dispersion or handle according to the multipolymer of claim 15 or 16.
20. according to the method for claim 19, wherein sheet base thing is concrete or fragment of brick.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2003145094 DE10345094A1 (en) | 2003-09-26 | 2003-09-26 | Producing aqueous copolymer dispersions, e.g. useful for treating leather, comprises copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and an alkene oligomer and adding water |
| DE10345094.7 | 2003-09-26 | ||
| DE10353557.8 | 2003-11-14 | ||
| DE10355402.5 | 2003-11-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1856538A CN1856538A (en) | 2006-11-01 |
| CN100497466C true CN100497466C (en) | 2009-06-10 |
Family
ID=34353160
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800279033A Expired - Fee Related CN100497466C (en) | 2003-09-26 | 2004-09-18 | Aqueous dispersions of copolymers, production thereof and use of the same |
| CNA2004800280204A Pending CN1860268A (en) | 2003-09-26 | 2004-09-18 | Method for treating fibrous substrates |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800280204A Pending CN1860268A (en) | 2003-09-26 | 2004-09-18 | Method for treating fibrous substrates |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN100497466C (en) |
| DE (1) | DE10345094A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1900756A1 (en) * | 2006-09-14 | 2008-03-19 | Basf Se | Process for the preparation of an aqueous polymer dispersion |
| CN118005351B (en) * | 2024-02-02 | 2024-07-16 | 义乌中国小商品城房地产开发有限公司 | Foam concrete and preparation process thereof |
-
2003
- 2003-09-26 DE DE2003145094 patent/DE10345094A1/en not_active Withdrawn
-
2004
- 2004-09-18 CN CNB2004800279033A patent/CN100497466C/en not_active Expired - Fee Related
- 2004-09-18 CN CNA2004800280204A patent/CN1860268A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1860268A (en) | 2006-11-08 |
| DE10345094A1 (en) | 2005-04-21 |
| CN1856538A (en) | 2006-11-01 |
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