CN114573768B - Water-dispersible polymer, composition containing same and application thereof - Google Patents
Water-dispersible polymer, composition containing same and application thereof Download PDFInfo
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- CN114573768B CN114573768B CN202210233817.8A CN202210233817A CN114573768B CN 114573768 B CN114573768 B CN 114573768B CN 202210233817 A CN202210233817 A CN 202210233817A CN 114573768 B CN114573768 B CN 114573768B
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a water-dispersible polymer which comprises a repeating unit generated by a monomer I, a repeating unit generated by a monomer II and repeating units generated by other monomers. The monomer I is an organosilicon modified acrylic monomer, the monomer II is an amino group-containing acrylic monomer, and the other monomer is at least one selected from a hydroxyl group-containing or polyoxyethylene group-containing monomer III, an anionic group-containing monomer IV and a functional group-containing monomer V. The polymer or the composition containing the polymer can be used for surface treatment of various articles such as textiles, paper, stone and the like, and endows the surfaces of the articles with water and oil repellent functions.
Description
Technical Field
The present invention relates to a water-dispersible polymer, a composition comprising the same, and uses thereof, which can be used for surface treatment of various articles and impart water and oil repellent functions to the surfaces of the articles.
Technical Field
For a long time, fluorine-containing polymers have been widely used for surface treatment of fabrics, leather, nonwoven fabrics, asbestos, fur, concrete, natural stone, paper, plastics and the like, which can impart water-repellent and oil-repellent functions to the surfaces of these articles. Taking textiles as an example, it is known that fluoropolymer water and oil repellent finishes can impart good water and oil repellency to textiles, commonly known as three-way finishes. CN103080267a describes the very good water and oil repellent properties of polymers formed with other monomers using fluorinated acrylates to textiles; CN100408649C describes the very good water and oil repellency properties of textiles with copolymers of fluorinated acrylates with other units.
In recent years, due to the increasing interest in polyfluoroalkyl compounds (PFAS) by international society, PFAS are considered to be highly stable and not easily degradable, and related reports have been published by the us environmental protection agency EPA: preliminary risk assessment of the development toxicity associated with exposure of perfluorooctanoic acid and its salts%http://www.epa.gov/opptintr/pfoa/ pfoara.pdf) Concerns about PFAS material-related environmental loads have been raised, and at the same time, the U.S. environmental agency published information about the possibility that telomers may produce PFAS by decomposition or metabolism, federal Register (FR Vol68, no.73/April 16,2003[ FRL-2303-8)],http://www.epa.gov/opptintr/pfoa/pfoar.pdf).EPA Environmental News For Release:Monday April 14,2003EPA intensifies scientific investigation of a chemical processing aid(http://www.epa.gov/opptintr/pfoa/ pfoafacts.pdf) Related telomer products are widely used in textile finishing, paper, leather, fire fighting foam, and care products, among others. While fluorine-containing treatments are considered to be one source of PFAS.
In view of the above, new non-fluorine compounds have been proposed to replace existing fluorine-containing finishes. CN107849187a proposes a polymer formed by copolymerizing acrylic acid ester and vinyl chloride, which has a good water repellent effect on textile finishing. CN110114435a proposes a copolymer of propylene ester, which is compounded with wax emulsion, etc. to finish textile, and has good water repellent effect. CN105377935B uses a polyurethane aqueous dispersion to finish textiles, and has a good water-repellent effect. However, these polymers have poor oil repellency.
Disclosure of Invention
The object of the present invention is to provide a novel water-dispersible polymer which is free of fluorine and which can treat various articles to impart water-and oil-repellent properties to the surfaces of the articles. Compared with the prior art, the prepared polymer has better water repellent effect and oil repellent performance, thereby improving the protective effect.
The invention provides a water-dispersible polymer which comprises a repeating unit generated by a monomer I, a repeating unit generated by a monomer II and a repeating unit generated by other monomers, wherein the other monomers are at least one of a monomer III, a monomer IV and a monomer V,
a) The structural general formula of the monomer I is as follows:
CH 2 ＝C(R 1 )-X-Z
wherein X is selected from the group shown as X-1 and X-2,
-C(O)-O-(CH 2 )n-
X-1
-C(O)-N(R 2 )-(CH 2 )n-
X-2
R 1 and R is 2 Selected from hydrogen atoms or C 1- C 20 N is an integer from 1 to 20;
z is selected from the structures shown in the following,
in Z, R 3 Each independently is C 1 -C 20 Alkyl of C 6 -C 20 Aryl, C of (2) 1 -C 20 Alkoxy or R 4 -O-R 5 -a group, R4 is C 1 -C 10 Alkyl of R 5 Is C 1 -C 10 An alkylene group of 1.ltoreq.a.ltoreq.200;
Y 1 and Y 2 Each independently is C 1 -C 20 Alkyl or C of (2) 6 -C 20 Or an aryl group of the formula:
r7 are each independently C 1 -C 20 Alkyl or C of (2) 6 -C 20 Aryl of (a); r is R 8 Each independently is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 1 -C 20 Alkoxy or R 9 -O-R 10 -a group wherein R9 is C 1 -C 10 Alkyl of R 10 Is C 1 -C 10 The alkylene of (2) is more than or equal to 0 and less than or equal to 200;
b) The structural general formula of the monomer II is as follows:
CH 2 ＝C(R 1 )-P-N(R 3 R 4 )
wherein P is selected from the group represented by P-1 and P-2,
-C(O)-O-(CH 2 )n-
P-1
-C(O)-N(R 2 )-(CH 2 )n-
P-2
wherein R is 1 And R is 2 Selected from hydrogen atoms or C 1 -C 20 Alkyl, n is an integer from 1 to 20, for example an integer from 1 to 10, an integer from 1 to 5; r is R 3 And R is 4 Each independently is C 1 -C 8 Or R is an alkyl or benzyl group 3 And R is 4 Combine and form morpholino, piperidino, or pyrrolidino together with the nitrogen atom;
c) The structural general formula of the monomer III is as follows:
CH 2 ＝C(R 1 )-G-(R 2 O) q -R 3
wherein G is selected from the group shown in G-1 and G-2,
-C(O)-O-(CH 2 )n-
G-1
-C(O)-N(R 4 )-(CH 2 )n-
G-2
wherein R is 1 Represents a hydrogen atom or a methyl group, G is selected from the group represented by G-1 or G-2, R 2 Is C 2 -C 4 Alkylene groups of 1 may contain alkylene groups having different carbon numbers, q is an integer of 1 to 50, R 3 Represents a hydrogen atom or C 1 -C 20 Alkyl of R 4 Represents a hydrogen atom or a methyl group, n is an integer of 0 to 10, for example an integer of 1 to 5;
d) The monomer IV is a monomer with an anionic group and a polymerizable unsaturated group, and the anionic group is a carboxyl group or a sulfonic acid group;
e) The monomer V is selected from the group consisting of monomers containing pyrrolidone structures and polymerizable unsaturated groups, monomers having blocked isocyanate groups, alkoxysilyl groups, glycidyl groups, and polymerizable unsaturated groups.
According to some embodiments of the polymer of the invention, the mass content of the recurring units produced by the monomers I is from 30 to 90%, preferably from 40 to 85%, more preferably from 50 to 80%.
According to some embodiments of the polymer according to the invention, monomer II produces a repeating unit content by mass of 5 to 65%, preferably 10 to 40%, more preferably 15 to 35%.
According to some embodiments of the polymer of the invention, the other monomers produce repeating units in a mass content of 1 to 30%.
According to some embodiments of the invention, in X, R 1 And R is 2 Selected from hydrogen atoms or methyl groups.
According to some embodiments of the invention, in Z, R 3 Each independently is C 1 -C 10 Alkyl of C 6 -C 10 Aryl, C of (2) 1 -C 10 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl of R 5 Is C 1 -C 10 An alkylene group of 1.ltoreq.a.ltoreq.100; r is R 7 Each independently is C 1 -C 10 Alkyl or C of (2) 6 -C 10 Aryl of (a); r is R 8 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 1 -C 10 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 10 Alkyl of R 10 Is C 1 -C 10 And b is more than or equal to 0 and less than or equal to 100.
According to some embodiments of the polymers of the invention, in said structure P of monomer II, R 1 And R is 2 Selected from a hydrogen atom or a methyl group; r is R 3 And R is 4 Are respectively and independently C 1 -C 3 Or R is an alkyl group of 3 And R is 4 And combine with the nitrogen atom to form morpholino, piperidino, or pyrrolidino.
According to some embodiments of the polymers of the invention, the monomers described in I
Z is selected from the following structures: ,
me represents methyl, ph represents phenyl, 1.ltoreq.m+1.ltoreq.200, preferably 1.ltoreq.m+1.ltoreq.100; p is more than or equal to 0 and less than or equal to 200, preferably more than or equal to 1 and less than or equal to 100; q is more than or equal to 0 and less than or equal to 200, preferably more than or equal to 1 and less than or equal to 100; x is more than or equal to 1 and less than or equal to 20, preferably x is more than or equal to 1 and less than or equal to 10.
According to some embodiments of the polymer of the invention, monomer II is selected from one or more of dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, N-t-butylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide.
According to some embodiments of the polymer of the present invention, monomer III is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, N-methylolacrylamide, and the like.
According to some embodiments of the polymer of the invention, monomer IV is a monomer IV that is an unsaturated group having an anionic group and a polymerizable group, the anionic group being a carboxyl group or a sulfonic group, preferably monomer IV is (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide t-butylsulfonic acid, or salts thereof.
According to some embodiments of the polymer of the invention, monomer V is selected from the group consisting of monomers containing pyrrolidone structures and polymerizable unsaturated groups, monomers having blocked isocyanate groups, alkoxysilyl groups, glycidyl groups and polymerizable unsaturated groups.
According to some embodiments of the polymer of the invention, the other monomer produces repeating units with a mass content of less than 30%.
According to some embodiments of the polymer of the present invention, the weight average molecular weight of the polymer is 1,000-1,000,000, preferably 4,000 to 500,000. According to some embodiments of the polymers of the present invention, the polymers are in the form of ammonium salts or nitroxides.
The present invention further provides a composition comprising the water-dispersible polymer of the invention described above and a solvent comprising water and/or an organic solvent. Preferably, the organic solvent is one or more of acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, ethanol, isopropanol, N-propanol, butyl carbitol, dipropylene glycol monomethyl ether, dipropylene glycol methyl ether.
The invention also relates to a method for manufacturing the composition, which comprises the following steps:
(1) Polymerizing a monomer (including monomer I, monomer II, and at least one selected from monomers III, IV, and V) in an organic solvent to obtain a polymer solution;
(2) Adding water for dispersion as required, and simultaneously removing the organic solvent from the polymer solution, or removing the solvent first and then adding water for dispersion;
(3) Adding an organic acid to convert amino groups in the polymer into ammonium salts according to requirements;
(4) If desired, an oxidizing agent (e.g., hydrogen peroxide) is added to convert the amino groups of the polymer into nitroxides.
In addition, the invention also provides application of the water-dispersible polymer or the composition in surface coating and soaking treatment processes of fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, natural stone, paper or plastics.
In addition, the invention also provides a product treated by the water-dispersible polymer or the composition, and the product can be fiber fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper or plastic.
ADVANTAGEOUS EFFECTS OF INVENTION
The copolymers and the resulting compositions of the present invention are readily water dispersible and are useful in the surface treatment of a variety of articles such as fabrics, leather, non-wovens, asbestos, fur, concrete, natural stone, paper, plastics, in a manner including coating and dipping treatments which impart water and oil repellency to the surface of the article after treatment.
The specific embodiment is as follows:
the novel polymer comprises the following monomers,
the structural general formula of the monomer I is as follows:
CH 2 ＝C(R 1 )-X-Z
wherein X is selected from the group shown as X-1 and X-2,
-C(O)-O-(CH 2 )n-
X-1
-C(O)-N(R 2 )-(CH 2 )n-
X-2
R 1 and R is 2 Selected from hydrogen atoms or C 1- C 20 N is an integer from 1 to 20;
z is selected from the structures shown in the following,
in Z, R 3 Each independently is C 1 -C 20 Alkyl of C 6 -C 20 Aryl, C of (2) 1 -C 20 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl of R 5 Is C 1 -C 10 An alkylene group of 1.ltoreq.a.ltoreq.200;
Y 1 and Y 2 Each independently is C 1 -C 20 Alkyl or C of (2) 6 -C 20 Or an aryl group of the formula:
R 7 each independently is C 1 -C 20 Alkyl or C of (2) 6 -C 20 Aryl of (a); r is R 8 Each independently is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 1 -C 20 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 10 Alkyl of R 10 Is C 1 -C 10 The alkylene group of (2) is more than or equal to 0 and less than or equal to 200.
Specifically indicated, R 3 ，R 8 Representative is C 1 -C 10 Alkyl of C 1 -C 10 Alkoxy, C 6 -C 10 Of the aryl radicals, in particular C 1 -C 8 Alkyl of C 1 -C 4 Alkoxy groups of (a), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, and the like; aryl groups such as phenyl, tolyl, naphthyl, and the like. R is R 3 ，R 8 It is also possible to have such a structure (R 9 -O-R 10 )-，R 9 Is C 1 -C 10 Alkyl of R 10 Is C 1 -C 10 Alkylene groups of (2), more commonly such as CH 3 O(CH 2 ) x -and the like. R is R 7 Is a slave C 1 -C 20 Alkyl groups and C of (C) 6 -C 20 For example, an aryl group selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl and the like, and an aryl group such as phenyl, tolyl, naphthyl and the like.
For example, common Z is selected from the following structures: ,
me represents methyl, ph represents phenyl, 1.ltoreq.m+1.ltoreq.200, preferably 1.ltoreq.m+1.ltoreq.100; p is more than or equal to 0 and less than or equal to 200, preferably more than or equal to 1 and less than or equal to 100; q is more than or equal to 0 and less than or equal to 200, preferably more than or equal to 1 and less than or equal to 100; x is more than or equal to 1 and less than or equal to 20, preferably x is more than or equal to 1 and less than or equal to 10.
The structural general formula of the monomer II is as follows:
CH 2 ＝C(R 1 )-P-N(R 3 R 4 )
wherein P is selected from the group represented by P-1 and P-2,
-C(O)-O-(CH 2 )n-
P-1
-C(O)-N(R 2 )-(CH 2 )n-
P-2
wherein R is 1 And R is 2 Selected from hydrogen atoms, C 1 -C 20 Alkyl, n is an integer from 1 to 20, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.; r is R 3 And R is 4 Each independently is C 1 -C 8 Or R is an alkyl or benzyl group 3 And R is 4 And combine with the nitrogen atom to form morpholino, piperidino, or pyrrolidino.
R 3 And R is 4 Alkyl groups having 1 to 8 carbon atoms are preferred, and methyl or ethyl groups are particularly preferred.
The polymerization unit in the polymer derived from the amino monomer II may be 1 or more.
Examples of amino monomers II are dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, N-t-butylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, and the like.
The nitrogen in the amino monomer is a tertiary nitrogen atom, which can be converted into amine oxide under the condition of an oxidant, and can also be converted into cationic ammonium salt by adding acid, so that the properties of the polymer, such as water-soluble stability and the like, can be further enhanced.
As the amino monomer II, the following examples can be listed.
CH 2 ＝C(R)COO(CH 2 ) 2 N(CH 3 ) 2 ；
CH 2 ＝C(R)COO(CH 2 ) 3 N(CH 3 ) 2 ；
CH 2 ＝C(R)COO(CH 2 ) 2 N(CH 2 CH 3 ) 2 ；
CH 2 ＝C(R)COO(CH 2 ) 3 N(CH 2 CH 3 ) 2 ；
CH 2 ＝C(R)COOCH 2 CH(OH)CH 2 N(CH 3 ) 2 ；
CH 2 ＝C(R)COOCH 2 CH(OH)CH 2 N(CH 2 CH 3 ) 2 ；
CH 2 ＝C(R)-CONH(CH 2 ) 2 N(CH 3 ) 2 ；
CH 2 ＝C(R)-CONH(CH 2 ) 3 N(CH 3 ) 2 ；
CH 2 ＝C(R)-CONH(CH 2 ) 2 N(CH 2 CH 3 ) 2 ；
CH 2 ＝C(R)-CONH(CH 2 ) 3 N(CH 2 CH 3 ) 2 ；
Wherein R is a hydrogen atom or comprises C 1 -C 4 Is a hydrocarbon group.
The repeating units having an ammonium salt may be produced by adding an acid to react. Examples of acids are mineral acids (such as hydrogen halides (hydrochloric acid, hydrogen bromide or hydrogen iodide), sulfuric acid, nitric acid and organic acids such as formic acid, acetic acid, glycolic acid, malic acid, citric acid, itaconic acid, etc.) organic acids are more commonly used, formic acid and acetic acid being more volatile and having a greater odor due to their smaller molecules, the amount of acid added can be from 10% molar equivalents to 200% molar equivalents, most commonly 100% molar equivalents, relative to the molar equivalents of ammonia in monomer II, relative to 1 molar equivalent of amino groups in repeat unit II having amino groups.
The monomers II can also be converted into N-oxides by addition of peroxides, examples of oxidizing agents being peroxycarboxylic acids such as hydrogen peroxide, persulphuric acid, m-chloroperoxybenzoic acid, etc. The amount of oxide added may be from 5% molar equivalents to 100% molar equivalents, most commonly 50% molar equivalents, relative to 1 molar equivalent of amino groups in repeat unit II having amino groups.
The structural general formula of the monomer III is as follows:
CH 2 ＝C(R 1 )-G-(R 2 O) a -R 3
wherein G is selected from the group shown in G-1 and G-2,
-C(O)-O-(CH 2 )n-
G-1
-C(O)-N(R 4 )-(CH 2 )n-
G-2
wherein R is 1 Represents a hydrogen atom or a methyl group, G is selected from the group represented by G-1 or G-2, R 2 Is C 2 -C 4 Alkylene groups of 1 may contain alkylene groups having different carbon numbers, q is an integer of 1 to 50, R 3 Represents a hydrogen atom or C 1 -C 20 Alkyl of R 4 Represents a hydrogen atom or a methyl group, n is an integer of 0 to 10;
as monomer III, the following compounds are preferred.
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, N-methylolacrylamide, and the like, having the typical structural formula:
CH 2 ＝C(R)-C(O)-O-CH 2 CH 2 OH；
CH 2 ＝C(R)-C(O)-(CH 2 CH 2 O) 2 H；
CH 2 ＝C(R)-C(O)-O-(CH 2 CH 2 O) 3 H；
CH 2 ＝C(R)-C(O)-O(CH 2 CH 2 O)11H；
CH 2 ＝C(R)-C(O)-O-(CH 2 CH 2 O) 12 H；
CH2＝C(R)-C(O)-N(R)-CH 2 OH
CH 2 ＝C(R)-C(O)O-CH 2 CH 2 OCH 3 ；
CH 2 ＝C(R)-C(O)O-CH 2 CH 2 OCH 2 CH 3 ；
CH 2 ＝C(R)-C(O)O-CH 2 CH 2 OCH 3 ；
CH 2 ＝C(R)-C(O)O-CH 2 CH 2 OCH 2 CH 3 ；
wherein R is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms.
Monomer IV is a monomer having an anionic group, which may be a carboxyl group or a sulfonic acid group, and a polymerizable unsaturated group. The method comprises the following steps: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide t-butylsulfonic acid, or salts thereof, and the like. Most commonly used is (meth) acrylic acid.
Monomer V: the polymer with better performance of the copolymer also contains a monomer V:
the method comprises the following steps: a polymerizable unsaturated group-containing monomer having a pyrrolidone structure, a blocked isocyanate group, an alkoxysilyl group, a glycidyl group, and a polymerizable unsaturated group-containing monomer.
As the monomer having a pyrrolidone structure and polymerizable unsaturated groups, there may be exemplified compounds including N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-3, 3-dimethyl-2-pyrrolidone.
Examples of the monomer having a blocked isocyanate and a polymerizable unsaturated group include the following compounds.
2-butanone oxime adduct of ethyl ester of 2-isocyanato (meth) acrylate, pyrazole adduct of ethyl ester of 2-isocyanato (meth) acrylate, 3, 5-dimethylpyrazole adduct of ethyl ester of 2-isocyanato (meth) acrylate, 3-methylpyrazole adduct of ethyl ester of 2-isocyanato (meth) acrylate, epsilon-caprolactam adduct of ethyl ester of 2-isocyanato (meth) acrylate, 2-butanone oxime adduct of ethyl ester of 3-isocyanato (meth) acrylate, pyrazole adduct of ethyl ester of 3-isocyanato (meth) acrylate, 3, 5-dimethylpyrazole adduct of ethyl ester of 3-isocyanato (meth) acrylate, 3-methylpyrazole adduct of ethyl ester of 3-isocyanato (meth) acrylate, epsilon-caprolactam adduct of ethyl ester of 4-isocyanato (meth) acrylate, 2-butanone oxime adduct of ethyl ester of 4-isocyanato (meth) acrylate, pyrazole adduct of 3-isocyanato ethyl ester of 3-isocyanato (meth) 3, 5-dimethylpyrazole adduct of ethyl ester of 3-isocyanato (meth) acrylate, epsilon-caprolactam adduct of 4-isocyanatoethyl (meth) acrylate.
As the monomer containing an alkoxysilyl group and a polymerizable unsaturated group, there may be exemplified compounds including 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl dimethoxy methylsilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl diethoxyethylsilane, allyl trimethoxysilane.
Examples of the monomer having a glycidyl group and a polymerizable unsaturated group include glycidyl (meth) acrylate and the like.
In the present invention, the mass content of the monomer I varies from 30 to 90%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc., preferably 40 to 85%, more preferably 50 to 80%;
the mass content of monomer II varies from 5 to 65%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, etc., preferably 10 to 40%, more preferably 15 to 35%;
the mass content of the monomer III varies from 1 to 30%, for example 1%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, etc., which can improve the affinity with the fiber, preferably 1 to 15%;
The mass content of the monomer IV varies from 1 to 30%, for example 1%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, etc., which can improve the water solubility of the polymer, preferably 1 to 15%;
the mass content of the monomers V varies from 1 to 30%, for example 1%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, etc., which may improve certain properties of the polymer, preferably 1 to 15%;
the copolymers of the invention formed from the above I-IV monomers may have a weight average molecular weight of 1,000-1,000,000, preferably 4,000 to 500,000. The weight average molecular weight can be measured by gel chromatography in terms of polystyrene.
The polymerization method of the copolymer is not particularly limited, and conventional radical polymerization methods such as bulk polymerization, solution polymerization in an organic solvent, and emulsion polymerization in water can be employed.
In the present invention, it is preferable that the solvent is removed after adding water after polymerization (for example, solution polymerization or emulsion polymerization) to obtain an aqueous dispersion; water may also be added after removal of the solvent to obtain an aqueous dispersion.
The organic solvent is selected from ketones, esters and alcohols, such as acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, ethanol, isopropanol, N-propanol, butyl carbitol, dipropylene glycol monomethyl ether, dipropylene glycol methyl ether, etc., and can be used alone or in combination.
After emulsion polymerization or solution polymerization, various general-purpose emulsifiers of anionic, cationic and nonionic type can be used as the emulsifier to be added for emulsification in water.
As the initiator for the polymer, a peroxide, azo compound or persulfate compound may be used, and the polymerization initiator may be an oil-soluble or water-soluble initiator depending on the polymerization system.
Examples of the oil-soluble polymerization initiator are preferably 2,2 '-azobis (2-methylpropanenitrile), 2' -azobis (2-methylbutanenitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), 1 '-azobis (cyclohexane-1-carbonitrile), dimethyl-2, 2' -azobis (2-methylpropionate), benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate and the like.
Examples of the water-soluble polymerization initiator are preferably 2,2 '-azobisisobutylaminidine dihydrochloride, 2' -azobis (2-methylpropionamidine) hydrochloride, 2 '-azobis [2- (2-imidazolin-2-yl) propane ] sulfate hydrate, 2' -azobis [2- (5-methyl-imidazolin-2-yl) propane ] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, and the like.
The initiator for polymerization is preferably a peroxide or an even compound having a half-life of 10 hours and a decomposition temperature of 40℃or higher, such as t-butyl peroxypivalate, 2' -azobis (2, 4-dimethylvaleronitrile), etc.
The initiator is added in an amount of 0.1 to 5 parts by weight relative to 100 parts by weight of the monomer.
In the polymerization, a certain amount of a molecular weight regulator may be added as needed, and examples of common use are mercapto compounds such as 2-mercaptopropionic acid, 2-mercaptoethanol, alkylthiol, mercaptopropionic acid, etc. The molecular weight regulator is added in an amount of 0 to 10 parts, preferably 0.01 to 5 parts, relative to 100 parts by weight of the monomer.
A typical solution polymerization process of the present invention is as follows,
firstly adding a solvent, then adding a corresponding monomer for dissolution, introducing nitrogen to replace oxygen in the solvent, then adding an initiator, heating to a reaction temperature of 40-120 ℃ and reacting for 4-20 hours.
Another common polymerization method is emulsion polymerization, which can be carried out by emulsifying monomers with emulsifying agent, adding monomers and emulsifying agent into water, stirring for emulsification, introducing nitrogen for replacement, adding water-soluble initiator, and heating to reaction temperature of 40-90 ℃ for 4-20 hours.
In order to obtain a stable polymer dispersion, the polymer system may be strongly dispersed and emulsified using a high-pressure homogenizing emulsifying machine or an ultrasonic dispersing device, so that the monomers are first formed into very stable fine particles and then the polymerization is initiated. As the widely used emulsifier, it is possible to select the species including anionic, cationic or nonionic, and the amount of the emulsifier is 0.5 to 10 parts by weight relative to 100 parts by weight of the monomer. It is usually 1 to 5 parts by weight.
The treatment composition of the present invention is in the form of a solution or emulsion. The treating agent comprises copolymer, water and organic solvent, wherein the mass content of the copolymer is 1-50% of the mass content of the effective parts, preferably 2-30% of the mass content of the effective parts.
The process for producing the treating agent composition of the present invention comprises the following steps:
(1) Placing at least one of monomers I, II, III, IV and V into an organic solvent according to a certain proportion, and adding an initiator to polymerize;
(2) Adding water to disperse after the polymerization is completed according to the need, and removing the organic solvent;
(3) Adding an acid as needed to convert amino groups in the polymer into ammonium salts;
(4) Adding an oxidizing agent to the dispersion according to the need for treatment;
The removal of the organic solvent of the polymer solution may be carried out by distillation under reduced pressure with heating, the temperature may be controlled to 40℃or higher, preferably 60 to 120℃and, after the removal of the solvent, water may be added in an amount of 100 to 2000 parts by weight relative to 100 parts by weight of the polymer for dispersion.
The amine groups contained in the class II monomers can be converted to N-oxides by adding an oxidizing agent. The hydrogen peroxide is added in an amount of 0.1 to 10 parts per 100 parts by weight of the polymer.
The article to be treated which can be treated with the water-dispersible treating agent composition of the present invention is not particularly limited, and includes fiber fabrics, leather, nonwoven fabrics, asbestos, fur, concrete, natural stone, paper, plastic and other fiber fabrics, among which fiber fabrics, paper and natural stone are preferable.
The fiber fabric comprises natural fibers of cotton, hemp, wool, silk and the like, synthetic fibers of polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene and the like, semisynthetic fibers of rayon, acetate and the like, inorganic fibers of glass fibers, carbon fibers, asbestos fibers and the like or mixed fiber fabrics thereof.
Method for testing fiber fabrics-fabric treatment
The fabrics treated in this study may be dyed 100% polyester fabrics and 100% kakier fabric, and a cloth sample was placed in a 3% strength aqueous solution of the treating agent composition of the present invention for impregnation treatment (60% pick-up), and then dried at 130 ℃ for 3 minutes. The water repellency and oil repellency of the resulting swatches were evaluated.
Method for testing water resistance of fiber fabrics
According to the Teflon global specification and quality control test method, the samples are tested by using liquids with different isopropanol volume contents, and the degree of surface wetting is observed and determined. This test provides a rough index of resistance to water staining. The higher the water resistance rating, the better the resistance of the final substrate to water-based materials, the composition of the standard test liquids is shown in Table 1 below, table 1, water resistance rating composition
| Water resistance rating | Composition by volume, isopropanol | Make up volume percent, water |
| 1 | 2 | 98 |
| 2 | 5 | 95 |
| 3 | 10 | 90 |
| 4 | 20 | 80 |
| 5 | 30 | 70 |
| 6 | 40 | 60 |
| 7 | 50 | 50 |
| 8 | 60 | 40 |
| 9 | 70 | 30 |
| 10 | 80 | 20 |
| 11 | 90 | 10 |
| 12 | 100 | 0 |
Method for testing fiber fabrics-spray test
The dynamic water resistance of the treated substrates was measured according to the American textile dyeing chemical Association (AATCC) TM-22, reference being made to published standards.
100 minutes indicates no adhering wetting of the surface;
a score of 90 indicates a slight sticking wetting;
a score of 80 indicates partial wetting;
lower values indicate progressively greater wetting and penetration.
Method for testing oil resistance of fiber fabrics
The oil repellency was evaluated according to the test method of AATCC-TM118, the basic principle being to apply test oil drops of different surface tension to the test cloth, the higher the rating, the better the oil repellency, the composition of the standard test liquid being shown in Table 2 below.
Table 2 fabric oil repellency test grade composition
| Oil repellency rating | Test solution | Surface tension mN/m |
| 8 | N-heptane | 20.0 |
| 7 | N-octane | 21.8 |
| 6 | N-decane | 23.5 |
| 5 | N-dodecane | 25.0 |
| 4 | N-tetradecane | 26.7 |
| 3 | N-hexadecane | 27.3 |
| 2 | 65 parts of liquid paraffin and 35 parts of n-hexadecane | 29.6 |
| 1 | Liquid paraffin | 31.2 |
Paper processing and testing method
The treatable paper includes tissue, thick paper, cardboard, or pulp molding, etc., from a unit area (meter 2 ) Up to 300 grams of cartons, again per unit area (meter 2 ) Kraft paper up to 80 grams, from a unit area (meter 2 ) Up to 100 grams of tissue paper, to a unit area (meter 2 ) Up to 200 g of paper-plastic product, can be processed.
The paper stock may be chemically bleached pulp or unbleached pulp, crushed wood pulp, chemimechanical pulp, mechanical pulp, etc., and it is also possible to add resin components such as polyamide, polyolefin, polyvinyl alcohol, etc. to these pulp sheets. The paper processing method is as follows:
(1) Surface coating example:
test paper manufacture: paper weight 230 g/m 2
The paper is formed by compounding five layers, wherein the bottom layer and the top layer are chemical pulp board LBKP (broad-leaved tree bleached kraft pulp) and NBKP (needle-leaved tree bleached kraft pulp) with the proportion of 7:3, and the middle three layers are formed by compounding chemical mechanical pulp or mechanical pulp board on a paper machine to form the paper with the weight of 230 g/m 2 Is a paperboard of (a) a paperboard.
The coating starch is tapioca coating starch MS-1 produced by Guangxi Ming Yangyang Biochemical company. The concentration of starch is 20%, water is added into the starch and the temperature is increased to more than 90 ℃ for gelatinization, and the synthesized paper treating agent is added after gelatinization is finished, wherein the concentration is 1-20%. The starch temperature is controlled to be not lower than 50 ℃, and the starch is coated on the top layer of the paperboard by a paper coating machine, wherein the coating weight is 3-8 g/m 2 。
(2) Examples of surface sizing treatments:
test paper preparation: paper weight 50 g/m 2
The chemical pulp board LBKP (broad-leaved tree bleached kraft pulp) and NBKP (needle-leaved tree bleached kraft pulp) are adopted, the proportion is 5:5, the pulp board is buckled and unbuckled, and the buckling and unbuckling degree is 200ml of Canadian freedom degree. Cationic starch MC-2 starch produced by Guangxi Ming Yang Biochemical company is added in the paper making process, the addition amount is 2% of the weight of the pulp board, and a fourdrinier paper machine is used for making paper with the weight of 50 g/m 2 Is a tissue of (3).
The starch solution adopts nonionic modified starch hydroxyethyl starch, and Penford Gum290 starch produced by Penford company with the concentration of 5%. Heating the starch solution to above 90 ℃ for gelatinization, and adding the synthesized treating agent after gelatinization is completed, wherein the concentration is 1-20% by weight. The temperature of the starch solution is controlled to be not lower than 70 ℃, the paper is subjected to surface sizing treatment, the liquid absorption amount exceeds 70%, and then the paper is subjected to drying treatment, so that the treated paper is obtained.
(3) Wet end treatment: paper-plastic weight 350 g/m 2
Directly pulping the sugarcane pulp plate, wherein the buckling degree is 600ml of Canadian freedom degree, the concentration of the paper pulp is 0.3%, sequentially adding sizing agents of Alkyl Ketene Dimer (AKD) with the addition amount of 2% of the weight of the paper pulp, and then adding the synthesized treating agent with the addition amount of 1-20%.
The pulp was poured into a 10 inch disc mold screen at a prescribed weight, and then the water was removed by vacuum suction. The water repellency and oil repellency of the dishes were evaluated by drying in a mold at 150℃for 120 seconds.
Evaluation of water repellency and oil repellency,
the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these descriptions. The following experiments were carried out in such a manner that the addition amounts% were all parts by weight unless otherwise specified.
The test methods used below are as follows.
Evaluation of oil repellency test
(1) Evaluation of oil repellency TAPPI test kit
The oil repellency (kit method) was determined according to TAPPI T-559 cm-02. In the test, a test reagent prepared by mixing castor oil, toluene and n-heptane in the volume ratio shown in the following table was used, and the results of the test are shown by numbers, and the higher the number, the better the oil repellency. Placing the treated paper on a pollution-free plane, dripping a test reagent on the surface of the paper, after the paper stays for 15 seconds, wiping the test reagent by using absorbent paper, observing whether the paper is permeated or not, if the paper is not permeated, passing, and then carrying out higher-level test.
The test agents were formulated according to the formulation of table 3.
Table 3, paper oil resistance Kit test agent formulation table
(2) Thermal oil resistance test
The treated paper was made into a container capable of holding liquid, hot oil (salad oil, peanut oil, rapeseed oil) at 85 ℃ was poured into the paper container, observed for 20 minutes, and rated for penetration. The test method is mainly applicable to the pulp molding industry.
5, the surface is not discolored;
4, the surface is slightly discolored;
3, the surface is discolored and slightly permeated;
2 is classified as severe penetration;
evaluation of Water repellency-Cobb test
(1) Cobb test
The test is performed according to GB/T1540-2002 or ISO 535:1991,
the principle is that the height of supporting 10mm of water is measured to be 100cm 2 The weight (g) of water absorbed in 1 minute on the paper of (2) was converted into a weight (g/m) per 1 square meter 2 )。
Cobb absorbency testers typically employ a roll-over cylinder tester. The metal cylinder is a cylinder, and the internal cross-sectional area of the metal cylinder is generally (100+/-0.2) cm 2 The corresponding inner diameter is (112.8.+ -. 0.2) mm. If a small area cylinder is used, the recommended area should be not less than 50 square meters, and the volume of water should be correspondingly reduced at this time to ensure a water level of 10 mm. The cylinder height was 50mm, and the portion of the cylinder annulus in contact with the sample should be smooth and sufficiently rounded to prevent damage to the sample by the cylinder edge. In order to prevent water leakage, a layer of elastic rubber pad or gasket which does not absorb water is added on the turnover cylinder cover and the flat pressing base, the roller width of the metal pressing roller is 200+/-0.5 mm, the mass is 10+/-0.5 kg, and the surface is smooth.
The treated paper sample was cut into 10 pieces (5 pieces on the front and back) of (125.+ -.5) mm square or phi (125.+ -.5) mm round samples. For instruments with small test areas, the sample size should be slightly larger than the outer diameter of the cylinder to avoid water leakage caused by too small sample, and also to avoid operation influence caused by too large sample.
Before placing the sample, the cylindrical annulus, the pad, in contact with the sample should be ensured to be dry, while the hand should not contact the test area. 100mL of water was poured into the cylinder using a graduated cylinder, and then the weighed sample was placed on the annular face of the cylinder with the test face down. The gland is placed over the sample and clamped to secure it to the cylinder.
The cylinder was turned 180 ° and the stopwatch was turned on to take 60 seconds. And before the water absorption is finished, the cylinder is turned over for 10-15 s, the gland clamping device is loosened, and the sample is taken down. Note that after 5 tests, the test water should be replaced so as not to affect the test results. At the moment when the prescribed water absorption time is reached, the sample removed from the cylinder is placed with the water absorption surface facing down on the pre-laid water absorption paper. And then placing a piece of absorbent paper on the sample, immediately rolling the sample by a metal press roll for one time in a reciprocating way without applying other pressure for 4 seconds, and absorbing the residual water on the surface of the sample. The sample is taken out rapidly, the water absorbing surface is folded inwards, and then is weighed after being folded once again, and the weight is accurate to 0.001g. For thick cardboard, the sample may not fold easily, in which case a second weighing should be performed as soon as possible.
Cobb values are represented by the following formula: c= (g 2-g 1)/F
Wherein: a C cobb value;
g 2-weight of the sample after water absorption;
g1- -weight of sample before water absorption;
F—100cm 2 testing area;
(2) Hot water resistance test
The method is to directly test the hot water resistance of paper, is relatively simple, generally uses the treated paper as a container capable of holding liquid, pours boiled water at 100 ℃ into the container, observes for 30 minutes to see whether leakage exists or not, and is suitable for pulp molding products.
The stone treatment and test method comprises the following steps:
the treatable natural stone includes: marble, granite, sandstone, slate, etc.
Taking sandstone as an example, diluting the treating agent into 3% liquid by using water, taking a sandstone sample to soak the liquid, taking out the sandstone sample, naturally airing the sandstone sample for 48 hours, and then respectively dripping salad oil, mustard sauce, coffee, vinegar and the like on the surface of the sandstone to observe the wetting state. If impermeable, the better the impedance is explained.
5, the surface is not discolored;
4, the surface is slightly discolored;
3, the surface is discolored and slightly permeated;
2 is classified as severe penetration;
example 1
Into a 500ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 77 g of CH was charged 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (molecular weight 500, noted Si-5), 15 g of dimethylaminoethyl methacrylate CH 2 ＝C(CH 3 )C(O)-O-CH 2 CH 2 N(CH 3 ) 2 (noted as DM) 8 g of hydroxyethyl methacrylate CH 2 ＝C(CH 3 )-C(O)-O-CH 2 CH 2 OH (HEMA) and 100 g of Methyl Ethyl Ketone (MEK) are added, nitrogen is introduced for 30 minutes, the temperature is slowly raised to 50-60 ℃, 1.4 g of tert-butyl pivalate peroxide as a peroxide initiator is added in portions, the reaction temperature is controlled to be 60 ℃ for 20 hours, and about 200 g of polymer A solution with the solid content of about 50% is obtained.
295 g of water and 5.8 g of glacial acetic acid were added, and the mixture was stirred at 70℃for 1 hour or more while maintaining the temperature, and MEK in the polymer A solution was distilled off under reduced pressure to give an aqueous dispersion having a solids content of 25%.
Example 2
Into a 500ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 77 g of CH was charged 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (molecular weight 1000) (designated Si-10), 15 g of dimethylaminoethyl methacrylate CH 2 ＝C(CH 3 )C(O)-O-CH 2 CH 2 N(CH 3 ) 2 (noted as DM) 8 g of hydroxyethyl methacrylate CH 2 ＝C(CH 3 )-C(O)-O-CH 2 CH 2 OH (HEMA) and 100 g of Methyl Ethyl Ketone (MEK) are added, nitrogen is introduced for 30 minutes, the temperature is slowly raised to 50-60 ℃, 1.4 g of tert-butyl pivalate peroxide as a peroxide initiator is added in portions, the reaction temperature is controlled to be 60 ℃ for 20 hours, and about 200 g of polymer A solution with the solid content of about 50% is obtained.
295 g of water and 5.8 g of glacial acetic acid were added, and the mixture was stirred at 70℃for 1 hour or more while maintaining the temperature, and MEK in the polymer A solution was distilled off under reduced pressure to give an aqueous dispersion having a solids content of 25%.
Examples 3 to 4
The procedure used in examples 3-4 was exactly the same as in example 1, but synthesis experiments were carried out using polysiloxane monomers of different molecular weights, respectively. Respectively, si-20 (molecular weight: 2000) and Si-30 (molecular weight: 3000).
Performance testing involves testing several articles with the synthesized polymers:
1) Testing of textiles: respectively selecting 100% of polyester cloth and 100% of cotton cloth, diluting the treating agent into 3% of liquid, performing padding treatment, and respectively testing water resistance, spraying experiment and oil resistance;
2) Testing of paper: two papers of 230 g/m respectively were selected 2 The cardboard is subjected to surface coating treatment, and the concentration of the treating agent is 5%; another is 50 g/m 2 Is treated by surface sizing, the concentration of the treating agent is 5%, and the TAPPI oil resistance rating and Cobb water absorption value are tested, respectively.
3) Paper tableware testing: a 1% strength stock solution was prepared and a 10 inch disc was made up by adding 2% AKD type sizing agent and 10% treating agent, weighing 20 grams. Testing with salad oil at 80deg.C for 20 min, grading and scoring according to penetration condition; test with 100deg.C boiled water for 30 min, and record passing or leaking water.
4) Testing of sandstone: diluting the treating agent of the invention into 3% liquid by using water, taking a sandstone sample to soak the liquid, taking out the sandstone sample, naturally airing the sandstone sample for 48 hours, controlling the temperature to be not lower than 25 ℃, then respectively dripping salad oil, mustard sauce and coffee on the surface of the sandstone, observing the wetting state, and grading and scoring.
The performance is summarized in table 4:
table 4 test performance comparison table
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Si | Si-5 | Si-10 | Si-20 | Si-30 |
| Polyester cloth water resistance | 3 | 3 | 3 | 2 |
| Polyester cloth spray | 90 | 90 | 90 | 80 |
| Polyester cloth oil resistance | 2 | 2 | 2 | 1 |
| Water resistance of cotton cloth | 3 | 3 | 3 | 2 |
| Cotton cloth spraying | 90 | 90 | 90 | 80 |
| Oil resistance of cotton cloth | 2 | 2 | 2 | 1 |
| 230 g paper oil repellency | 2 | 2 | 2 | 1 |
| 230 g of paper Cobb | 20 | 19 | 22 | 25 |
| 50 g paper oil repellency | 2 | 2 | 2 | 1 |
| 50 g of paper Cobb | 20 | 19 | 22 | 25 |
| Hot oil testing of dinner plate | 5 | 5 | 4 | 2 |
| Dinner plate boiled water test | By passing through | By passing through | By passing through | By passing through |
| Sandstone salad oil | 5 | 5 | 4 | 3 |
| Sandstone mustard sauce | 5 | 5 | 3 | 2 |
| Sandstone soy sauce | 5 | 5 | 4 | 2 |
| Sandstone coffee | 5 | 5 | 5 | 5 |
Examples 5 to 8
The procedure used in examples 5 to 8 is exactly the same as in example 1, but the content of monomers I varies from 30% to 80% and the content of amino-containing monomers II is adjusted accordingly. The performance is summarized in table 5:
table 5 test performance comparison table
| Example 1 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Si-5 | 77％ | 60％ | 50％ | 39％ | 27％ |
| DM | 15％ | 32％ | 42％ | 53％ | 65％ |
| HEMA | 8％ | 8％ | 8％ | 8％ | 8％ |
| Polyester cloth water resistance | 3 | 3 | 2 | 2 | 1 |
| Polyester cloth spray | 90 | 90 | 90 | 80 | 70 |
| Polyester cloth oil resistance | 2 | 1 | 1 | 0 | 0 |
| Water resistance of cotton cloth | 3 | 2 | 2 | 1 | 1 |
| Cotton cloth spraying | 90 | 90 | 80 | 80 | 70 |
| Oil resistance of cotton cloth | 2 | 1 | 1 | 0 | 0 |
| 230 g paper oil repellency | 2 | 2 | 1 | 1 | 0 |
| 230 g of paper Cobb | 20 | 21 | 23 | 26 | 30 |
| 50 g paper oil repellency | 2 | 2 | 1 | 1 | 0 |
| 50 g of paper Cobb | 20 | 21 | 23 | 26 | 30 |
| Hot oil testing of dinner plate | 5 | 4 | 3 | 2 | 2 |
| Dinner plate boiled water test | By passing through | By passing through | By passing through | Water leakage | Water leakage |
| Sandstone salad oil | 5 | 4 | 2 | 2 | 2 |
| Sandstone mustard sauce | 5 | 4 | 3 | 2 | 2 |
| Sandstone soy sauce | 5 | 4 | 3 | 2 | 2 |
| Sandstone coffee | 5 | 5 | 3 | 2 | 2 |
Examples 9 to 13
The procedure used in examples 9-13 was exactly the same as in example 1, but synthesis experiments were carried out using monomers I of different structures, respectively.
Example 9 monomer Structure CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 3 (molecular weight 500) is denoted as Si-5Me
Example 10 monomer Structure CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 8 H 17 (molecular weight 500) is denoted as Si-5Oct
Example 11 monomer Structure CH 2 ＝C(CH 3 )C(O)-(NH)-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (molecular weight 500) is designated Si-5Bu (N)
Example 12 monomer Structure is branched, CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )[(Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 ] 2 (molecular weight 500) is designated Si-5-2Bu
Example 13 monomer Structure is branched, CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )[(Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 (CH 2 ) 3 OCH 3 ] 2 (molecular weight 500) is designated Si-5-2OMe
The performance is summarized in Table 6:
table 6 test performance comparison table
| Example 1 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | |
| Si | Si-5 | Si-5Me | Si-5Oct | Si-5Bu(N) | Si-5-2Bu | Si-5-2OMe |
| Polyester cloth water resistance | 3 | 3 | 3 | 3 | 3 | 2 |
| Polyester cloth spray | 90 | 90 | 90 | 90 | 80 | 80 |
| Polyester cloth oil resistance | 2 | 2 | 2 | 2 | 2 | 2 |
| Water resistance of cotton cloth | 2 | 2 | 3 | 2 | 2 | 1 |
| Cotton cloth spraying | 90 | 90 | 90 | 90 | 90 | 80 |
| Oil resistance of cotton cloth | 2 | 2 | 2 | 2 | 2 | 1 |
| 230 g paper oil repellency | 2 | 2 | 2 | 2 | 2 | 1 |
| 230 g of paper Cobb | 20 | 20 | 21 | 22 | 24 | 25 |
| 50 g paper oil repellency | 2 | 2 | 3 | 2 | 2 | 1 |
| 50 g of paper Cobb | 20 | 21 | 19 | 19 | 23 | 25 |
| Hot oil testing of dinner plate | 5 | 5 | 5 | 5 | 5 | 4 |
| Dinner plate boiled water test | By passing through | By passing through | By passing through | By passing through | By passing through | By passing through |
| Sandstone salad oil | 5 | 3 | 5 | 5 | 3 | 3 |
| Sandstone mustard sauce | 5 | 4 | 5 | 5 | 3 | 2 |
| Sandstone soy sauce | 5 | 3 | 5 | 5 | 4 | 3 |
| Sandstone coffee | 5 | 3 | 5 | 5 | 5 | 4 |
Examples 14 to 17
Examples 14-17 are exactly the same as example 1, except that instead of HEMA, vinyl pyrrolidone (NVP), 2-butanone oxime adduct of 2-isocyanatoethyl Acrylate (ANCO), methacrylic acid (MAA), glycidyl methacrylate (AGE) are added.
The performance is summarized in Table 7:
table 7 test performance comparison table
| Example 1 | Example 14 | Example 15 | Example 16 | Example 17 | |
| Functional monomer | HEMA | NVP | ANCO | MAA | AGE |
| Polyester cloth water resistance | 3 | 3 | 2 | 2 | 2 |
| Polyester cloth spray | 90 | 90 | 80 | 90 | 80 |
| Polyester cloth oil resistance | 2 | 2 | 2 | 2 | 2 |
| Water resistance of cotton cloth | 2 | 2 | 2 | 2 | 2 |
| Cotton cloth spraying | 90 | 90 | 80 | 90 | 80 |
| Oil resistance of cotton cloth | 2 | 2 | 2 | 2 | 2 |
| 230 g paper oil repellency | 2 | 2 | 1 | 2 | 2 |
| 230 g of paper Cobb | 20 | 23 | 25 | 23 | 22 |
| 50 g paper oil repellency | 2 | 2 | 1 | 2 | 2 |
| 50 g of paper Cobb | 20 | 23 | 25 | 23 | 25 |
| Hot oil testing of dinner plate | 5 | 5 | 5 | 5 | 5 |
| Dinner plate boiled water test | By passing through | By passing through | By passing through | By passing through | Water leakage |
| Sandstone salad oil | 5 | 5 | 5 | 5 | 4 |
| Sandstone mustard sauce | 5 | 5 | 5 | 5 | 5 |
| Sandstone soy sauce | 5 | 5 | 5 | 5 | 4 |
| Sandstone coffee | 5 | 5 | 4 | 5 | 5 |
Examples 18 to 21
Examples 18-21 used exactly the same procedure as example 1, but with different solvents instead of MEK, respectively: EA: ethyl acetate, ACE: acetone, EOL, ethanol, IPA, isopropanol.
The performance is summarized in Table 8:
table 8 test performance comparison table
Examples 22 to 25
Examples 22-25 used exactly the same procedure as example 1, but with a different initiator instead of t-butyl peroxypivalate (noted as TBPV), respectively, corresponding to: benzoyl peroxide (denoted BPO), azobisisobutyronitrile (denoted AIBN), azobisisovaleronitrile (denoted AMBN), dimethyl azobisisobutyrate (denoted AIBME). The properties are summarized in Table 9.
Table 9 test performance comparison table
Example 26
Into a 500ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 77 g of CH was charged 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (molecular weight: 500) (designated Si-5), 15 g of dimethylaminoethyl methacrylate CH 2 ＝C(CH 3 )C(O)-O-CH 2 CH 2 N(CH 3 ) 2 (noted as DM) 8 g of hydroxyethyl methacrylate CH 2 ＝C(CH 3 )-C(O)-O-CH 2 CH 2 OH (marked as HEMA) and 100 g of methyl ethyl ketone (marked as MEK), introducing nitrogen for 30 minutes, slowly heating to 50-60 ℃, adding 1.4 g of tert-butyl pivalate peroxide as a peroxide initiator in portions, controlling the reaction temperature to 60 ℃ and reacting for 20 hours to obtain about 200 g of polymer A solution with the solid content of about 50%.
244 g of water and 5.8 g of glacial acetic acid are added and stirred at 70℃for more than 1 hour. MEK in the polymer A solution was distilled off under reduced pressure, and 50 g of 1% hydrogen peroxide (H) 2 O 2 ) Stirring for 1 hour at the temperature of 70 ℃ to obtain an aqueous dispersion with 25% of solid after cooling the solution.
Example 27
Into a 500ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 77 g of CH was charged 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (molecular weight: 500) (designated Si-5), 15 g of N- [3- (dimethylamino) propyl group]-2-methyl-2-propenamide CH 2 ＝C(CH 3 )C(O)-NH-CH 2 CH 2 CH 2 N(CH 3 ) 2 (noted as DN), 8 g of hydroxyethyl methacrylate CH 2 ＝C(CH 3 )-C(O)-O-CH 2 CH 2 OH (HEMA) and 100 g of Methyl Ethyl Ketone (MEK), introducing nitrogen for 30 minutes, slowly heating to 50-60 ℃, and adding 1.4 g of peroxide initiator of pivalic acid peroxide in portionsThe tert-butyl ester was reacted at 60℃for 20 hours to give about 200 g of a polymer A solution having a solids content of about 50%.
295 g of water and 5.8 g of glacial acetic acid were added, and the mixture was stirred at 70℃for 1 hour or more while maintaining the temperature, and MEK in the polymer A solution was distilled off under reduced pressure to give an aqueous dispersion having a solids content of 25%.
Example 28
Into a 500ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 77 g of CH was charged 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (molecular weight 500) (designated Si-5), 15 g of N- [ 3- (dimethylamino) propyl group]-2-methyl-2-propenamide CH 2 ＝C(CH 3 )C(O)-NH-CH 2 CH 2 CH 2 N(CH 3 ) 2 (noted as DN), 8 g of hydroxyethyl methacrylate CH 2 ＝C(CH 3 )-C(O)-O-CH 2 CH 2 OH (hereinafter referred to as HEMA) and 100 g of methyl ethyl ketone (referred to as MEK), introducing nitrogen for 30 minutes, slowly heating to 50-60 ℃, adding 1.4 g of tert-butyl pivalate peroxide as a peroxide initiator in portions, controlling the reaction temperature at 60 ℃ for reacting for 20 hours, and obtaining about 200 g of polymer A solution with the solid content of about 50%.
244 g of water and 5.8 g of glacial acetic acid are added and stirred at 70℃for more than 1 hour. MEK in the polymer A solution was distilled off under reduced pressure, and 50 g of 1% hydrogen peroxide (H) 2 O 2 ) Preserving heat for more than 1 hour, and cooling the solution to obtain the aqueous dispersion with 25% of solid.
The performance is summarized in Table 10:
table 10 test performance comparison table
Example 29
Into a 500ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, 77 g of CH was charged 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (molecular weight: 500) (designated Si-5), 15 g of dimethylaminoethyl methacrylate CH 2 ＝C(CH 3 )C(O)-O-CH 2 CH 2 N(CH 3 ) 2 (noted as DM) 8 g of hydroxyethyl methacrylate CH 2 ＝C(CH 3 )-C(O)-O-CH 2 CH 2 OH (noted HEMA) and 100 grams of methyl ethyl ketone (noted MEK), dodecyl mercaptan 0.2 grams was added. Introducing nitrogen for 30 minutes, slowly heating to 50-60 ℃, adding 1.4 g of tert-butyl peroxypivalate serving as a peroxide initiator in batches, controlling the reaction temperature to 60 ℃ and reacting for 20 hours to obtain about 200 g of polymer A solution with the solid content of about 50%.
295 g of water and 5.8 g of glacial acetic acid were added, and the mixture was stirred at 70℃for 1 hour or more while maintaining the temperature, and MEK in the polymer A solution was distilled off under reduced pressure to give an aqueous dispersion having a solids content of 25%.
Examples 30 to 32
Examples 30 to 32 used exactly the same procedure as in example 29, but with a different amount and type of chain transfer agent added, dodecyl mercaptan (D12-SH) and 3-mercaptopropionic acid (DC 3-SH) were used, respectively.
The performance is summarized in Table 11:
table 11 test performance comparison table
Comparative example 1: acrylic ester copolymer emulsion
Into a 500ml reaction flask, 115.20 g of stearyl acrylate, 240 g of pure water, 33.0 g of tripropylene glycol, 6.08 g of dimethylpropyl amide stearate, 5.43 g of polyoxyethylene tridecyl (eo=18, EO represents the number of ethylene oxide units), 1.71 g of polyoxyethylene isotridecyl ether (eo=3), 2.4 g of acetic acid, and after dispersing by ultrasonic emulsification at 60℃for 15 minutes with stirring, 0.24 g of lauryl mercaptan, 0.48 g of 2, 2-azobis (2-amidinopropane) 2 hydrochloride and 9 g of water were added, and the mixture was reacted at 60℃for 5 hours to obtain an aqueous dispersion of a polymer, and the solid content was further adjusted to 30% with pure water. Performance evaluation was performed as described above.
Comparative example 2 acrylic ester and vinyl chloride copolymer emulsion
A1L autoclave was charged with 150 g of stearic acid acrylate, 360 g of pure water, 60 g of tripropylene glycol, polyoxyethylene tridecyl ether (EO=3) (HLB 8.0) =7.5 g, polyoxyethylene tridecyl ether (EO=20)
(HLB 16.3) 12.5 g, laurylthiol 1.0 g, and was dispersed by ultrasonic wave at 60℃for 15 minutes under stirring. After the autoclave was purged with nitrogen, 50 g of vinyl chloride was charged under pressure, 2.0 g of 2, 2-azobis (2-amidinopropane) 2 hydrochloride was added, and the mixture was reacted at 60℃for 3 hours to obtain an aqueous polymer dispersion (average HLB=13.2). Further, the solid content concentration was adjusted to 30% with pure water. Performance evaluation was performed as described above.
Comparative example 3: polyurethane dispersions
In a 4-neck round-bottom flask equipped with an overhead stirrer, thermocouple and condenser were added 11.6 grams of sorbitol tristearate (hydroxyl value 77.2mg KOH/g) and 4-methyl-2-pentanol (MIBK, 150 grams). The solution was refluxed for 1 hour to remove any residual moisture. After 5 hours, the solution was cooled to 50 ℃, desmourn-100100 g was added, then catalyst was added, and the solution was returned to 80 ℃ for more than one hour. Into a beaker, 300 g of water, 5.6 g of ARMEEN DM-18D, 2.8 g of TERGITOL TMN-10.8 g and 3.4 g of acetic acid were added and stirred to form a surfactant solution, and the solution obtained by the reaction was slowly added to the surfactant solution by cooling to obtain a milky emulsion. The mixture was homogeneously emulsified at 6000psi and the resulting emulsion was distilled off the solution under reduced pressure to give a polyurethane dispersion with a solids content of about 25%. Performance evaluations were performed as described above and summarized in table 12:
table 12 test performance comparison table
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Type(s) | Si-5 | Acrylic esters | Vinyl chloride-containing resin | Polyurethane dispersions |
| Polyester cloth water resistance | 3 | 2 | 2 | 2 |
| Polyester cloth spray | 90 | 90 | 90 | 90 |
| Polyester cloth oil resistance | 2 | 0 | 0 | 0 |
| Water resistance of cotton cloth | 2 | 2 | 2 | 2 |
| Cotton cloth spraying | 90 | 90 | 90 | 90 |
| Oil resistance of cotton cloth | 2 | 0 | 0 | 0 |
| 230 g paper oil repellency | 2 | 1 | 1 | 1 |
| 230 g of paper Cobb | 20 | 26 | 26 | 25 |
| 50 g paper oil repellency | 2 | 1 | 1 | 1 |
| 50 g of paper Cobb | 20 | 26 | 26 | 29 |
| Hot oil testing of dinner plate | 5 | 2 | 2 | 2 |
| Dinner plate boiled water test | By passing through | Water leakage | Water leakage | Water leakage |
| Sandstone salad oil | 5 | 3 | 3 | 2 |
| Mustard sauce | 5 | 2 | 2 | 2 |
| Soy sauce | 5 | 3 | 2 | 2 |
| Coffee machine | 5 | 3 | 3 | 3 |
From the results of the present patent examples and comparative examples, it can be seen that the comparative examples are poor in water and oil repellent effect, and particularly, there is little barrier effect against hot oil at 85 c, whereas the present patent examples have very good barrier effect against hot oil.
Claims (14)
1. A water-dispersible polymer comprising repeat units derived from monomer I, repeat units derived from monomer II, and repeat units derived from other monomers selected from at least one of monomer III, monomer IV, and monomer V;
a) The structural general formula of the monomer I is as follows:
CH 2 ＝C(R 1 )-X-Z
wherein X is selected from the group shown as X-1 and X-2,
-C(O)-O-(CH 2 )n-
X-1
-C(O)-N(R 2 )-(CH 2 )n-
X-2
R 1 and R is 2 Selected from hydrogen atoms or C 1- C 20 N is an integer from 1 to 20;
z is selected from the structures shown in the following,
in Z, R 3 Each of which is a single pieceIndependently C 1 -C 20 Alkyl of C 6 -C 20 Aryl, C of (2) 1 -C 20 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl of R 5 Is C 1 -C 10 An alkylene group of 1.ltoreq.a.ltoreq.200;
Y 1 and Y 2 Each independently is C 1 -C 20 Alkyl or C of (2) 6 -C 20 Or an aryl group of the formula:
R 7 each independently is C 1 -C 20 Alkyl or C of (2) 6 -C 20 Aryl of (a); r is R 8 Each independently is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 1 -C 20 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 10 Alkyl of R 10 Is C 1 -C 10 The alkylene of (2) is more than or equal to 0 and less than or equal to 200;
b) The structural general formula of the monomer II is as follows:
CH 2 ＝C(R 1 )-P-N(R 3 R 4 )
wherein P is selected from the group represented by P-1 and P-2,
-C(O)-O-(CH 2 )n-
P-1
-C(O)-N(R 2 )-(CH 2 )n-
P-2
wherein R is 1 And R is 2 Selected from hydrogen atoms or C 1 -C 20 Alkyl, n is an integer from 1 to 20; r is R 3 And R is 4 Each independently is C 1 -C 8 Or R is an alkyl or benzyl group 3 And R is 4 Combine and form morpholino, piperidino, or pyrrolidino together with the nitrogen atom;
c) The structural general formula of the monomer III is as follows:
CH 2 ＝C(R 1 )-G-(R 2 O) q -R 3
wherein G is selected from the group shown in G-1 and G-2,
-C(O)-O-(CH 2 )n-
G-1
-C(O)-N(R 4 )-(CH 2 )n-
G-2
wherein R is 1 Represents a hydrogen atom or a methyl group, G is selected from the group represented by G-1 or G-2, R 2 Is C 2 -C 4 Alkylene groups of 1 may contain alkylene groups having different carbon numbers, q is an integer of 1 to 50, R 3 Represents a hydrogen atom or C 1 -C 20 Alkyl of R 4 Represents a hydrogen atom or a methyl group, n is an integer of 0 to 10;
d) The monomer IV is a monomer with an anionic group and a polymerizable unsaturated group, and the anionic group is a carboxyl group or a sulfonic acid group;
e) The monomer V is selected from unsaturated group monomers containing pyrrolidone structure and polymerizable, unsaturated group monomers having blocked isocyanate groups and polymerizable, unsaturated group monomers having alkoxysilyl groups and polymerizable or unsaturated group monomers having glycidyl groups and polymerizable,
The mass content of the repeating units produced by the monomer I in the copolymer is 30-90%.
2. The polymer of claim 1, wherein:
the mass content of the repeating units generated by the monomer II in the copolymer is 5-65%; the mass content of the repeating units produced by the other monomers in the copolymer is 1-30%.
3. The polymer of claim 1, wherein:
the mass content of the repeating units generated by the monomer I in the copolymer is 40-85%; the mass content of the repeating units produced by the monomer II in the copolymer is 10-40%.
4. The polymer of claim 1, wherein:
the mass content of the repeating units generated by the monomer I in the copolymer is 50-80%; and/or
The mass content of the repeating units produced by the monomer II in the copolymer is 15-35%.
5. The polymer of claim 1, wherein the polymer is a polymer of the formula,
in monomer I, R 1 And R is 2 Selected from a hydrogen atom or a methyl group; and/or
In monomer II, R 1 And R is 2 Selected from a hydrogen atom or a methyl group; and/or
In Z, R 3 Each independently is C 1 -C 10 Alkyl of C 6 -C 10 Aryl, C of (2) 1 -C 10 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl of R 5 Is C 1 -C 10 An alkylene group of 1.ltoreq.a.ltoreq.100; r is R 7 Each independently is C 1 -C 10 Alkyl or C of (2) 6 -C 10 Aryl of (a); r is R 8 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 1 -C 10 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 10 Alkyl of R 10 Is C 1 -C 10 B is more than or equal to 0 and less than or equal to 100; and/or
In monomer II, R 3 And R is 4 Are respectively and independently C 1 -C 3 Or R is an alkyl group of 3 And R is 4 And combine with the nitrogen atom to form morpholino, piperidino, or pyrrolidino.
6. The polymer of claim 1, wherein Z is selected from the following structures: ,
i-1
i-2/>
/>
ii-1
ii-2/>
iii-1
iii-2/>
iv-1
me represents methyl, ph represents phenyl, m+1 is less than or equal to 1 and less than or equal to 200, p is less than or equal to 0 and less than or equal to 200, q is less than or equal to 0 and less than or equal to 200, and x is less than or equal to 1 and less than or equal to 19.
7. The polymer of claim 6 wherein 1.ltoreq.m+1.ltoreq.100, 0.ltoreq.p.ltoreq.100, 0.ltoreq.q.ltoreq.100, 1.ltoreq.x.ltoreq.10.
8. The polymer of any one of claim 1 to 7,
the monomer II is selected from one or more of dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and dipropylaminopropyl (meth) acrylamide.
9. The polymer of any one of claim 1 to 7,
the monomer III is selected from one or more of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and methoxy polyethylene glycol (meth) acrylate;
monomer IV is selected from (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide t-butylsulfonic acid or salts thereof;
the monomer V contains pyrrolidone structure and polymerizable unsaturated group monomer, blocked isocyanate group and polymerizable unsaturated group monomer, alkoxysilyl group and polymerizable unsaturated group monomer or glycidyl group and polymerizable unsaturated group monomer;
the monomers III, IV and V produce repeating units in a mass content of 1 to 30%.
10. A composition comprising the polymer of any one of claims 1-9 and a solvent comprising water and/or an organic solvent.
11. The composition of claim 10, wherein the organic solvent is one or more of acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N-dimethylformamide, ethanol, isopropanol, N-propanol, butyl carbitol, dipropylene glycol methyl ether.
12. A process for preparing the composition of claim 10 or 11, comprising the steps of:
(1) Polymerizing monomers in an organic solvent to obtain a copolymer solution;
(2) Optionally, adding water to the copolymer solution for dispersion, and then removing the organic solvent, or removing the solvent first and then adding water for dispersion;
(3) Optionally, adding an acid to the copolymer solution to convert amino groups in the copolymer to ammonium salts;
(4) Optionally, the copolymer solution is treated with an aqueous hydrogen peroxide solution to convert the amino groups to oxynitride compounds.
13. Use of a polymer according to any one of claims 1 to 9 or a composition according to claim 10 or 11 or a composition prepared by a method according to claim 12 in a surface coating and soaking treatment process for fabrics, leather, non-wovens, asbestos, fur, concrete, natural stone, paper or plastics.
14. A product treated with a polymer according to any one of claims 1 to 9 or a composition according to claim 10 or 11 or a composition prepared by a method according to claim 12, said product being a fibrous fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper or plastic.
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