CN117003942A - Copolymer for paper product treatment, treatment method and product - Google Patents

Copolymer for paper product treatment, treatment method and product Download PDF

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Publication number
CN117003942A
CN117003942A CN202310653780.9A CN202310653780A CN117003942A CN 117003942 A CN117003942 A CN 117003942A CN 202310653780 A CN202310653780 A CN 202310653780A CN 117003942 A CN117003942 A CN 117003942A
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alkyl
equal
formula
group
osi
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蒋凌飞
李焦丽
孔祥晶
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Beijing Mapu New Materials Co ltd
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Beijing Mapu New Materials Co ltd
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Priority to CN202310653780.9A priority Critical patent/CN117003942A/en
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J3/00—Manufacture of articles by pressing wet fibre pulp, or papier-mâché, between moulds
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present application relates to a copolymer for paper product treatment, a composition comprising the copolymer and a treated product thereof. The copolymer comprises repeating units derived from monomer I and repeating units derived from monomer II. The monomers are defined as the specification. The copolymer or compositions comprising the copolymer can treat a wide variety of articles, such as paper products, at a wide range of pH values (acidic, neutral and basic), particularly basic sizing or coating environments, and impart oil and water repellency to the article.

Description

Copolymer for paper product treatment, treatment method and product
Technical Field
The present application relates to a copolymer for paper product treatment, a composition comprising the copolymer and a treated product such as a paper product.
Technical Field
The paper product is treated to render its surface water and oil repellent so that the oil and fat food can be packaged. There are two methods which are commonly used at present for treating paper products, namely, film coating treatment is carried out on the surface of the paper products, which is equivalent to film coating on the surface of the paper products, but the paper prepared by the method cannot be recycled, and the recycling property is poor. The other method is to coat the surface of the paper product, but the coating amount is generally higher, and a film is formed, so that the properties of air permeability, appearance and the like of the paper product are changed. While paper products are treated, it is often desirable to impart water and oil repellency while not changing their appearance or basic properties.
The organosilicon polymer is a compound widely used, and is widely used due to excellent performance, high inertia and good safety, the patent CN100300612 describes an organosiloxane polymer which can be used for processing paper products, so that the paper products have water and oil repellent functions, but the polymer is based on a coating method, the coating needs film forming, and the process is complex.
CN 114573767B describes a silicone polymer which can be used in the treatment of paper products, which is a cationic polymer, suitable only in neutral and acidic environments, but which may fail in alkaline environments. The requirements of modern papermaking processes, the manufacture of paper in alkaline environments, are also very common processes, so it is very important to ensure that paper treatment chemicals can preserve their properties in alkaline environments, especially in sizing environments with higher pH.
Thus, there is a need to develop a polymer suitable for use in a wider range of pH values.
Disclosure of Invention
The object of the present application is to provide a copolymer for paper product treatment and a composition comprising the copolymer, which can treat paper products in a wider range of pH values (acidic, neutral and alkaline), especially alkaline sizing or coating environments, and impart oil and water repellent properties without altering the basic properties of the paper product.
In a first aspect, the present application provides a copolymer for water and oil repellent treatment of paper products comprising repeat units derived from monomer I and repeat units derived from monomer II,
a) The structural general formula of the monomer I is shown in the formula I:
M-Z or Z-M-Z
I is a kind of
Wherein M contains a polymerizable functional group;
z is selected from the structures shown in the following,
in Z, R 3 Each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 20 Alkoxy or R of (A) 4 -O-R 5 -a group, R 4 Is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 5 Is C 1 -C 20 An alkylene group of 1.ltoreq.a.ltoreq.200;
Y 1 and Y 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Or an alkylaryl group of the formula (1):
R 7 each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 8 Each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 20 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 10 Is C 1 -C 20 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 shown in the formula II:
CH 2 ＝C(R 1 )-G-(R 2 O) q -R 3 II
in formula II, R 1 Represents a hydrogen atom or a methyl group, R 2 Each independently is C 1 -C 6 Is an alkylene group, q is an integer from 1 to 50; r is R 3 Represents a hydrogen atom or C 1 -C 20 Alkyl of (a);
wherein G is selected from the group shown in G-1 and G-2,
-C(O)-O-B-
G-1
-C(O)-N(R 4 )-B-
G-2
R 4 represents a hydrogen atom or a methyl group, B being absent or C 1 -C 20 Alkylene groups of (a).
The inventors of the present application have unexpectedly found that the use of the copolymers obtained by polymerization of monomers I and II described above allows the treatment of paper products in a wider range of pH values (acidic, neutral and alkaline), especially alkaline sizing or coating environments, and imparts excellent oil and water repellency properties to the paper products without altering the basic properties of the paper products.
In some embodiments, in formula II, R 2 Is C 2 -C 4 Alkylene groups of (a). In some embodiments, in formula II, q is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, or 49. In some embodiments, in formula II, q is an integer from 1 to 20.
In some embodiments, in formula II, R 3 Is a hydrogen atom or C 1 -C 10 Alkyl radicals of (2), e.g. hydrogen atoms, C 1 -C 3 Alkyl or C of (2) 4 -C 6 Is a hydrocarbon group.
In some embodiments, B is absent or C in the groups shown in G-1 and G-2 1 -C 10 Alkylene of (C) 1 -C 3 Alkylene or C of (2) 4 -C 6 Alkylene groups of (a).
In some embodiments, monomer II 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, or methoxypolyethylene glycol (meth) acrylate.
In some embodiments, the polymerizable functional group in M is selected from groups containing carbon-carbon double bonds.
In some embodiments, in formula I, M is as shown in formula I-1:
CH 2 ＝C(R 1 )-X-B-
I-1
in the formula I-1, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl of (a); b is C 1 -C 20 Is used for the preparation of an alkylene group,
x is selected from the group shown as X-1 and X-2,
-C(O)-O-
X-1
-C(O)-N(R 2 )-
X-2
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl of (a);
in some embodiments, in formula I-1, R 1 Selected from hydrogen atoms or C 1 -C 10 Alkyl groups of (2), e.g. C 1 -C 3 Alkyl, C of (2) 4 -C 6 Alkyl or C of (2) 8 -C 10 Is a hydrocarbon group. In some embodiments, in formula I-1, B is C 1 -C 10 Alkylene of (C) 1 -C 3 Alkylene group, C 4 -C 6 Alkylene or C of (2) 8 -C 10 Alkylene groups of (a).
In some embodiments, X-1 and X-2 areIn the radicals, R 2 Selected from hydrogen atoms or C 1 -C 10 Alkyl groups of (2), e.g. C 1 -C 3 Alkyl, C of (2) 4 -C 6 Alkyl or C of (2) 8 -C 10 Is a hydrocarbon group.
In some embodiments, in formula I-1, R 1 Selected from a hydrogen atom or a methyl group; b is C 1 -C 6 An alkylene group of (a); x, R 2 Selected from hydrogen atoms or methyl groups.
In some embodiments, in formula I, M is as shown in formula I-2:
CH 2 ＝C(R 1 )-W-B-
I-2
in the formula I-2, R 1 Selected from hydrogen atoms or C 1 -C 20 An alkyl group;
w is selected from the group shown in W-1, W-2, W-3 and W-4,
-O-C(O)-N(R 2 )- W-2
-O-C(O)-O- W-3
-O-C(O)-O-D-N(R 2 )- W-4
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl, D is C 1 -C 20 An alkylene group of (a); when W is selected from W-1, B is absent or C 1 -C 20 When W is selected from W-2, W-3,W-4, B is C 1 -C 20 Alkylene groups of (a).
In some embodiments, in formula I-2, R 1 Selected from hydrogen atoms or C 1 -C 10 Alkyl groups of (2), e.g. C 1 -C 3 Alkyl, C of (2) 4 -C 6 Alkyl or C of (2) 8 -C 10 Is a hydrocarbon group. In some embodiments, in formula I-2, B is C 1 -C 10 Alkylene of (C) 1 -C 3 Alkylene group, C 4 -C 6 Alkylene or C of (2) 8 -C 10 Alkylene groups of (a).
In some implementationsIn embodiments, in formula I-2, R 2 Selected from hydrogen atoms or C 1 -C 10 Alkyl groups of (2), e.g. C 1 -C 3 Alkyl, C of (2) 4 -C 6 Alkyl or C of (2) 8 -C 10 Is a hydrocarbon group. In some embodiments, in formula I-2, D is C 1 -C 10 Alkylene of (C) 1 -C 3 Alkylene group, C 4 -C 6 Alkylene or C of (2) 8 -C 10 Alkylene groups of (a).
In some embodiments, in formula I-2, R 1 And R is 2 Selected from hydrogen atoms or methyl groups, B and D being C 1 -C 6 Alkylene groups of (a).
In some embodiments, when W is selected from W-1, B is absent or C 1 -C 10 Alkylene of (C) 1 -C 3 Alkylene group, C 4 -C 6 Alkylene or C of (2) 8 -C 10 Alkylene groups of (a).
In some embodiments, when W is selected from W-2, W-3,W-4, B is C 1 -C 10 Alkylene of (C) 1 -C 3 Alkylene group, C 4 -C 6 Alkylene or C of (2) 8 -C 10 Alkylene groups of (a).
In some embodiments, in formula I, M is as shown in formula I-3:
in the formula I-3, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl, B is independently C 1 -C 20 Alkylene groups of (a).
In some embodiments, in formula I-3, R 1 Selected from hydrogen atoms or C 1 -C 10 Alkyl groups of (2), e.g. C 1 -C 3 Alkyl, C of (2) 4 -C 6 Alkyl or C of (2) 8 -C 10 Is a hydrocarbon group. In some embodiments, in formula I-3, B is C 1 -C 10 Alkylene of (C) 1 -C 3 Alkylene group, C 4 -C 6 Alkylene or C of (2) 8 -C 10 Alkylene groups of (a).
In some embodiments, in formula I-3, R 1 Selected from hydrogen atoms or methyl groups.
In some embodiments, in Z, R 3 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 10 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 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, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 8 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 10 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 10 Is C 1 -C 10 And b is more than or equal to 0 and less than or equal to 100.
In some embodiments, in Z, R 3 Each independently is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl of (C) 7 -C 10 Alkylaryl, C 1 -C 6 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl groups of (a)，R 5 Is C 1 -C 6 An alkylene group of 1.ltoreq.a.ltoreq.30; r is R 7 Each independently is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl groups of (a); r is R 8 Each independently is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl of (C) 7 -C 10 Alkylaryl, C 1 -C 6 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl group R of (2) 10 Is C 1 -C 16 The alkylene group of (2) is more than or equal to 0 and less than or equal to 30.
In some embodiments, a is an integer from 1 to 80, an integer from 1 to 30, an integer from 1 to 20, or an integer from 1 to 10.
In some embodiments, b is 0. In some embodiments, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5.
In some embodiments, each Z is independently selected from one or more of the following structures i-1 to i-6:
r is each independently selected from C 1 -C 10 Alkyl, C 6 -C 10 Aryl, C 7 -C 12 Aralkyl or C of (C) 7 -alkylaryl of C12;
m+1 is less than or equal to 1 and less than or equal to 60, preferably m+1 is less than or equal to 1 and less than or equal to 30; p is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; q is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; x is not less than 1 and not more than 9, preferably not less than 1 and not more than 7, and each x can be the same or different.
In some embodiments, R is C 1 -C 3 For example methyl.
In some embodiments, Z is selected from
One or more of the following;
r is each independently selected from C 1 -C 10 Alkyl, C 6 -C 10 Aryl, C 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a);
me represents methyl, ph represents phenyl; m+1 is less than or equal to 1 and less than or equal to 60, preferably m+1 is less than or equal to 1 and less than or equal to 30; p is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; q is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; x is not less than 1 and not more than 9, preferably not less than 1 and not more than 7, and each x can be the same or different.
In some embodiments, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.
In some embodiments, x is 1, 2, 3, 4, 5, 6, or 7.
In some embodiments, monomer I is selected from
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝CHC(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-CH 2 -Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )[O-[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 ] 2 ，0≤n≤25；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 ，1≤n≤25；
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 ，1≤n≤25；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 3 ，1≤n≤25；
CH 2 ＝CH-ph-Si(OSi(CH 3 ) 3 ) 3 (ph represents
CH 2 ＝CH-ph-(CH 2 ) 2 Si(OSi(CH 3 ) 3 ) 3 (ph represents
CH 2 ＝CH-ph-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl, ph represents1≤n≤25；
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl),
1≤n≤25；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents butyl), n is more than or equal to 1 and less than or equal to 25;
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents butyl),
1≤n≤25；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ] 2 ；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ] 2 ；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 represents butyl), n is more than or equal to 1 and less than or equal to 25;
CH 2 ＝C(CH 3 )-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 Represents butyl),
1≤n≤25。
in some embodiments, monomer I comprises silicon monomer I-A and/or silicon monomer I-B;
the general formula of the silicon monomer I-A is the same as formula I, and also satisfies Y when a is 1 1 And/or Y 2 Is of the formula (1), at least one Y when a is greater than 1 and less than or equal to 200 1 Is a structure of formula (1) and/or at least one Y 2 Is a structure of formula (1);
the general formula of the silicon monomer I-B is the same as the formula I, and Y is also satisfied 1 And Y 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl and C of (C) 7 -C 12 Alkylaryl groups of (a).
In some embodiments, the silicon monomer I-A has the formula I-A:
M-Z 1 or Z is 1 -M-Z 1
Formula I-A
Wherein M contains a polymerizable functional group;
Z 1 selected from the group consisting of the structures shown in the following,
Z 1 wherein R is 3 Each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Is an alkylaryl group of (C)Radical, C 1 -C 20 Alkoxy or R of (A) 4 -O-R 5 -a group, R 4 Is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 5 Is C 1 -C 20 An alkylene group of 1.ltoreq.a.ltoreq.200;
Y 1 and Y 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 And the structure of formula (1) below, provided that when a is 1, Y 1 And/or Y 2 Is of the formula (1), at least one Y when a is greater than 1 and less than or equal to 200 1 Is a structure of formula (1) and/or at least one Y 2 Is a structure of formula (1):
R 7 each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 8 Each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 20 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 10 Is C 1 -C 20 The alkylene group of (2) is more than or equal to 0 and less than or equal to 200.
In the present application, the definition of M in formula I-A is the same as that of M in formula I.
In some embodiments, Z 1 Wherein R is 3 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 10 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 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, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 8 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 10 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 10 Is C 1 -C 10 And/or 0.ltoreq.b.ltoreq.80.
According to some embodiments of the application, Z 1 Wherein R is 3 Each independently is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl of (C) 7 -C 10 Alkylaryl, C 1 -C 6 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl group R of (2) 5 Is C 1 -C 6 An alkylene group of 1.ltoreq.a.ltoreq.30; r is R 7 Each independently is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl groups of (a); r is R 8 Each independently is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl of (C) 7 -C 10 Alkylaryl, C 1 -C 6 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl group R of (2) 10 Is C 1 -C 16 The alkylene group of (2) is more than or equal to 0 and less than or equal to 30.
In some embodiments, in formula I-A, a is an integer from 1 to 80, an integer from 1 to 30, an integer from 1 to 20, or an integer from 1 to 10.
In some embodiments, b is 0 in formula I-A. In some embodiments, in formula I-A, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5.
In some embodiments, Z 1 One or more selected from the following structures i-3 to i-6:
r is each independently selected from C 1 -C 10 Alkyl, C 6 -C 10 Aryl, C 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a);
m+1 is less than or equal to 1 and less than or equal to 60, preferably m+1 is less than or equal to 1 and less than or equal to 30; p is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; q is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; x is not less than 1 and not more than 9, preferably not less than 1 and not more than 7, and each x can be the same or different.
In some embodiments, R is C 1 -C 3 For example methyl.
In some preferred embodiments, Z 1 Selected from the following structures:
one or more of the following;
me represents methyl, 1.ltoreq.m+1.ltoreq.60, preferably 1.ltoreq.m+1.ltoreq.30; p is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; q is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; x is not less than 1 and not more than 9, preferably not less than 1 and not more than 7, and each x can be the same or different.
In some embodiments, silicon monomer I-A is selected from
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝CHC(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-CH 2 -Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )[O-[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 ] 2 ，0≤n≤25；
CH 2 ＝CH-ph-Si(OSi(CH 3 ) 3 ) 3 (ph represents
CH 2 ＝CH-ph-(CH 2 ) 2 Si(OSi(CH 3 ) 3 ) 3 (ph represents
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ] 2 ；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ] 2 ；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 Represents butyl), n is more than or equal to 1 and less than or equal to 25;
CH 2 ＝C(CH 3 )-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 represents butyl),
1≤n≤25。
in some embodiments, the silicon monomer I-B has the formula I-B:
M-Z 2 or Z is 2 -M-Z 2
Formula I-B
Wherein M contains a polymerizable functional group;
Z 2 selected from the group consisting of the structures shown in the following,
Z 2 in (1), Y 1 And Y 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl and C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 3 Each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 20 Alkoxy or R of (A) 4 -O-R 5 -a group, R 4 Is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 5 Is C 1 -C 20 Is not less than 1 and not more than 200.
In the present application, the definition of M in formula I-B is the same as that of M in formula I.
In some embodiments, Z 2 In (1), Y 1 And Y 2 Identical or different, each independently selected from C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl and C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 3 Each independently selected from C 1 -C 10 Alkyl, C of (2) 6 -C 12 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 10 Alkoxy or R of (A) 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl, C of (2) 6 -C 12 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 5 Is C 1 -C 10 Alkylene groups of (a).
According to some embodiments of the invention, Z 2 In the formula, a is more than or equal to 1 and less than or equal to 80. According to some embodiments of the invention, Z 2 In the formula, a is more than or equal to 1 and less than or equal to 30. According to some embodiments of the invention, Z 2 In the formula, a is more than or equal to 1 and less than or equal to 20. According to some embodiments of the invention, Z 2 In the formula, a is more than or equal to 1 and less than or equal to 10.
In some embodiments, Z 2 In (1), Y 1 And Y 2 Identical or different, each independently selected from C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl and C of (C) 7 -C 10 Alkylaryl groups of (a); r is R 3 Each independently selected from C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl of (C) 7 -C 10 Alkylaryl, C 1 -C 6 Alkoxy or R of (A) 4 -O-R 5 -a group, R 4 Is C 1 -C 6 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 10 Aralkyl or C of (C) 7 -C 10 Alkylaryl group R of (2) 5 Is C 1 -C 6 Alkylene groups of (a).
In some embodiments, Z 2 One or more selected from the following structures i-1 to i-2:
r is each independently selected from C 1 -C 10 Alkyl, C 6 -C 10 Aryl, C 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a);
m+1 is less than or equal to 1 and less than or equal to 60, preferably m+1 is less than or equal to 1 and less than or equal to 30; x is more than or equal to 1 and less than or equal to 9, preferably x is more than or equal to 1 and less than or equal to 7.
Z 2 The following structure is preferred:
one or more of the following;
me represents methyl, ph represents phenyl; m+1 is less than or equal to 1 and less than or equal to 60, preferably m+1 is less than or equal to 1 and less than or equal to 30; x is more than or equal to 1 and less than or equal to 9, preferably x is more than or equal to 1 and less than or equal to 7.
In some embodiments, silicon monomer I-B is selected from
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl), n is more than or equal to 1 and less than or equal to 25;
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 ，1≤n≤25；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 3 ，1≤n≤25；
CH 2 ＝CH-ph-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9
(C 4 H 9 represents butyl, ph represents1≤n≤25；
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl),
1≤n≤25；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents butyl), n is more than or equal to 1 and less than or equal to 25;
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents butyl),
1≤n≤25。
in some embodiments, monomer I produces repeating units in a mass content of 30 to 90%. In some embodiments, monomer I produces repeating units in a mass content of 40 to 85%. In some embodiments, monomer I produces repeating units in an amount of 50 to 80% by mass. In some embodiments, monomer I produces repeating units in a mass content of 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or a range of any two compositions thereof.
In some embodiments, monomer II produces repeating units in an amount of 5 to 65% by mass. In some embodiments, monomer II produces repeating units in an amount of 10 to 50% by mass. In some embodiments, monomer II produces repeating units in a mass content of 15 to 45%. In some embodiments, monomer II produces repeating units in a mass content of 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range of any two of these compositions.
In some embodiments, the proportion of repeating units produced by silicon monomer I-a in the total amount of repeating units produced by silicon monomer I-a to repeating units produced by silicon monomer I-B is 1% to 100%,5% to 100%,10% to 100%, or 50% to 100%, e.g., 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, e.g., 1%, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or any two thereof. The total amount of repeating units produced by silicon monomer I-A and repeating units produced by silicon monomer I-B, i.e., the total amount of repeating units produced by monomer I.
In some embodiments, the copolymers of the present application do not include repeat units derived from monomer IV, wherein monomer IV 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, or dipropylaminopropyl (meth) acrylamide.
In some embodiments, the structural formula of monomer IV is as shown in formula IV:
CH 2 ＝C(R 1 )-P-B-N(R 3 R 4 ) IV
in the formula IV, P is selected from groups shown as P-1 and P-2,
-C(O)-O-
P-1
-C(O)-N(R 2 )-
P-2
b is C 1 -C 20 An alkylene group of (a); r is R 1 And R is 2 Each independently is a hydrogen atom or C 1 -C 20 An alkyl group; r is R 3 And R is 4 Each independently is a hydrogen atom, C 1 -C 18 Alkyl, hydroxyethyl or benzyl, or R 3 And R is 4 And combine with the nitrogen atom to form morpholino, piperidino, or pyrrolidino.
In some embodiments, the weight average molecular weight of the copolymer is 1000 to 200 ten thousand, for example 5000 to 150 ten thousand.
In a second aspect, the present application provides a composition comprising the copolymer of the first aspect of the claims and a solvent comprising water and/or an organic solvent,
in some embodiments, 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.
In a third aspect, the present application provides a method of the composition of the second aspect, comprising the steps of:
(1) Monomers (including monomers I and II) are polymerized in an organic solvent to obtain a copolymer solution.
In some embodiments, the amount of monomer I is in a range of 30 to 90%, preferably 40 to 85%, more preferably 50 to 80%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or any two of these, by mass, of the total amount of monomers.
In some embodiments, monomer II is used in an amount of 5 to 65%, preferably 10 to 50%, more preferably 15 to 45%, such as 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or any two of these ranges of composition by mass of the total amount of monomers.
In some embodiments, the amount of silicon monomer I-a is in a range of 1% to 100%,5% to 100%,10% to 100%,50% to 98%, e.g., 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, e.g., 1%, 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or any two thereof, by mass, of the total amount of silicon monomer I-a and silicon monomer I-B.
The manufacturing method may further include the steps of:
(2) Adding water to the copolymer solution for dispersion, and then removing the organic solvent, or removing the organic solvent first and then adding water for dispersion.
In a fourth aspect, the present application provides the use of a copolymer according to the first aspect or a composition according to the second aspect or a composition prepared by a method according to the third aspect in paper products, fabrics, leather, non-wovens, asbestos, fur, concrete, natural stone or plastics.
In a fifth aspect, the present application provides a water-and oil-repellent product comprising a product and the copolymer of the first aspect or the composition of the second aspect or the composition prepared by the method of the third aspect, the product being a paper product, a fibrous fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone or plastic.
In some embodiments, the copolymer of the first aspect or the composition of the second aspect or the composition prepared by the method of the third aspect is adhered to the surface and/or the interior of the product.
In a sixth aspect, the present application provides a method of treating a product comprising contacting the product with a copolymer according to the first aspect or a composition according to the second aspect or a composition prepared by a method according to the third aspect, the product being a paper product, a fibrous fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone or plastic.
In some embodiments, the contacting is achieved by a surface sizing or coating process.
In the present application, examples of paper products include, but are not limited to, paper carriers such as paper cups, paper bowls, paper trays, and the like. In some embodiments, the paper product comprises paper, paper box, or pulp molded products.
ADVANTAGEOUS EFFECTS OF INVENTION
The copolymer and the composition produced by the copolymer can be conveniently dissolved or dispersed in water or solvent, and can be applied to the treatment of paper products, fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, natural stone or plastics in acidic, alkaline and neutral environments, and the treatment modes comprise surface sizing, coating and the like, and can endow the surface of the product with oil and water repellent properties after the treatment.
The specific embodiment is as follows:
the present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. These examples are only for the purpose of illustrating the application and are not to be construed as limiting the application in any way. The actual scope of the application is set forth in the following claims.
In the present application, unless otherwise indicated, terms used have ordinary meanings known to those skilled in the art.
In the present application, the term "alkyl" refers to a straight chain alkyl or branched alkyl group, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, and the like.
In the present application, the term "alkylene" refers to a straight chain alkylene or branched chain alkylene, non-limiting examples of which include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, -CHCH 3 CH 2 -、-CHCH 3 CH 2 CH 2 -、CH 2 CH 3 CHCH 2 -and the like.
In the present application, "%" means mass% unless otherwise specified.
1. Polymerization process
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 application, it is preferable that after polymerization (e.g., solution polymerization or emulsion polymerization), water is added to remove the solvent to obtain an aqueous dispersion; the aqueous dispersion may also be obtained by removing the solvent and then adding 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-methylpropanenitrile), etc.
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.
The process for producing the treating agent of the present invention comprises the following steps:
(1) Proportionally placing the monomers I and II into an organic solvent, and adding an initiator to polymerize;
(2) After the polymerization is completed, water is added for dispersion, and the organic solvent is removed, or the organic solvent is removed first and then water is added for dispersion, as needed.
2. Test method
Paper product processing and testing method
The paper products that can be treated include tissue, cardboard, boxboard, pulp molding, etc., from a unit area (meter 2 ) Up to 300 grams of paper box, alsoIs a unit area (meter) 2 ) Kraft paper up to 80 grams, from a unit area (meter 2 ) Up to 30 grams of tissue paper to a unit area (meter 2 ) Up to 200 g of paper-plastic product, can be processed.
The paper product may be chemically bleached pulp or unbleached pulp, crushed wood pulp, chemimechanical pulp, mechanical pulp, etc., and may have added thereto resin components such as polyamide, polyolefin, polyvinyl alcohol, etc. The paper product processing method comprises the following steps:
(1) Examples of surface sizing treatments:
test paper preparation: paper product 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 product making process, the addition amount is 1% 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 for sizing adopts Y+L corn oxidized starch produced by Jiangxi macro chemical industry company, and the concentration is 5%. Firstly heating the starch solution to above 90 ℃ for gelatinization, testing the pH value of the sizing solution to be 8.5-8.9 after gelatinization is completed, and then adding the synthesized composition, wherein the concentration of the composition in the starch solution is 1-15% by weight. The temperature of the starch solution is controlled to be not lower than 70 ℃, the paper product is subjected to surface sizing treatment, the liquid absorption amount is over 70%, and then the paper product is subjected to drying treatment, so that the treated paper product is obtained.
(2) Surface coating example:
manufacturing of test paper products: paper product weight 230 g/m 2
The paper product 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 product with the weight of 230 g/m 2 Is a paperboard of (a) a paperboard.
CoatingThe starch is coated starch AS-28 produced by Guangxi Ming Yangyang Biochemical company. The concentration of starch is 20%, water is added into the starch and heated to more than 90 ℃ for gelatinization, the pH value of the coating liquid is tested to be 8.4-8.7 after gelatinization is completed, and then the synthesized composition is added, wherein the concentration of the composition in the starch solution is 1-15% (mass concentration). Controlling the temperature of starch not lower than 50 ℃, coating the starch on the top layer of the paperboard by using a paper product coating machine, wherein the coating weight is 3-8 g/m 2 。
Evaluation of oil repellency and Water repellency
Evaluation of oil repellency test
Thermal oil resistance test
The treated paper product was made into a container capable of holding liquid, hot oil (salad oil, peanut oil or rapeseed oil) at 85 ℃ was poured into the paper container, observed for 20 minutes, and rated for penetration.
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
(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 50cm 2 At this time, the volume of water should be reduced correspondingly 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. To prevent water leakage, a layer of elastic but non-water-absorbing material is added to the turnover cylinder cover and the flat-pressing baseThe width of the rubber pad or gasket, the metal press roller should be (200+/-0.5) mm, the mass should be (10+/-0.5) kg, and the surface should be smooth.
The treated paper product sample was cut into 10 pieces (5 pieces on the front and back) of square (125.+ -.5) mm or round (125.+ -.5) mm 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: c-cobb value;
g 2-weight of the sample after water absorption;
g 1-weight of the sample before water absorption;
F—100cm 2 area under test.
3. Examples and comparative examples
Abbreviations for chemicals see table 1:
table 1 codes and chemical formulas of the respective substances
Example 1
Ext> Aext> 1000ext> mlext> fourext> -ext> neckedext> flaskext> equippedext> withext> aext> refluxext> condenserext>,ext> aext> nitrogenext> inletext> tubeext>,ext> aext> thermometerext> andext> aext> stirrerext> wasext> chargedext> withext> 75ext> gext> ofext> Siext> -ext> Bext> 3ext>,ext> 60ext> gext> ofext> PEGext> -ext> Aext> andext> 135ext> gext> ofext> methylext> ethylext> ketoneext> (ext> MEKext> hereinafterext>)ext>,ext> nitrogenext> wasext> introducedext> forext> 30ext> minutesext>,ext> theext> temperatureext> wasext> slowlyext> raisedext> toext> 60℃andext> 1.4ext> gext> ofext> text> -ext> butylext> peroxypivalateext> asext> aext> peroxideext> initiatorext> wasext> addedext> theretoext>,ext> andext> theext> reactionext> temperatureext> wasext> controlledext> atext> 60℃toext> reactext> forext> 20ext> hoursext> toext> obtainext> aboutext> 270ext> gext> ofext> aext> polymerext> solutionext> havingext> aext> solidsext> contentext> ofext> aboutext> 50ext>%ext>.ext>
540 g of water was added, and the mixture was stirred at 60℃for 1 hour or more, and MEK in the solution was distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 20%.
Examples 2 to 8
As in example 1, except that Si-B3 was replaced with a monomer I having a different structure as follows, si-NB3 (example 2), si-ph-B3 (example 3), si-OCN-B3 (example 4), si-OCO-B3 (example 5), si-B2 (example 6), si-N2-B2 (example 7), si-5 (average molecular weight 500) were used, respectively (example 8).
Example 9
A1000 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with 75 g of Si-B3, 60 g of HEMA and 135 g of methyl ethyl ketone (hereinafter referred to as MEK), nitrogen was introduced for 30 minutes, the temperature was slowly raised to 60℃and 1.4 g of t-butyl peroxypivalate as a peroxide initiator was added thereto, and the reaction temperature was controlled at 60℃to react for 20 hours to obtain about 270 g of a polymer solution having a solid content of about 50%.
540 g of water was added, and the mixture was stirred at 60℃for 1 hour or more, and MEK in the solution was distilled off under reduced pressure to obtain an aqueous dispersion having a solid content of 20%.
Performance testing
Test of several articles using the aqueous dispersion synthesized in the examples as a treatment agent:
1) Testing of paper products: selecting 50 g/m 2 Is treated by surface sizing. The starch for sizing adopts Y+L corn oxidized starch produced by Jiangxi macro chemical company, and the pH value of sizing solution is measured to be 8.7. The concentrations of the treatments were 5wt%,4wt%,3wt%, respectively, and the hot oil resistance and Cobb water absorption values were tested.
2) Testing of paper products: 230 g/m 2 Is treated by coating. The coating starch was coating starch AS-28 produced by Guangxi Ming Biochemical company, and the pH of the coating solution was measured to be 8.5. The concentrations of the treatments were 5wt%,4wt%,3wt%, respectively, and the hot oil resistance and Cobb water absorption values were tested.
Table 2 example test performance table
As can be seen from Table 2, the compositions obtained in examples 1 to 9 show excellent oil and water repellency after the treatment of paper by surface sizing or coating under alkaline conditions.
Comparative example 1
Ext> Aext> 1000ext> mlext> fourext> -ext> neckedext> flaskext> equippedext> withext> aext> refluxext> condenserext>,ext> aext> nitrogenext> inletext> tubeext>,ext> aext> thermometerext> andext> aext> stirrerext> wasext> chargedext> withext> 75ext> gext> ofext> Siext> -ext> Bext> 3ext>,ext> 40ext> gext> ofext> DNext>,ext> 20ext> gext> ofext> PEGext> -ext> Aext> andext> 135ext> gext> ofext> methylext> ethylext> ketoneext> (ext> hereinafterext> referredext> toext> asext> MEKext>)ext>,ext> nitrogenext> wasext> introducedext> forext> 30ext> minutesext>,ext> theext> temperatureext> wasext> slowlyext> raisedext> toext> 60℃andext> 1.4ext> gext> ofext> text> -ext> butylext> peroxypivalateext> asext> aext> peroxideext> initiatorext> wasext> addedext> theretoext>,ext> andext> theext> reactionext> wasext> carriedext> outext> atext> 60℃forext> 20ext> hoursext> underext> controlext> ofext> theext> reactionext> temperatureext> toext> obtainext> aboutext> 270ext> gext> ofext> aext> polymerext> solutionext> havingext> aext> solidext> contentext> ofext> aboutext> 50ext>%ext>.ext>
525 g of water and 15 g of glacial acetic acid are added, stirred at 60℃for more than 1 hour and the MEK in the solution is distilled off under reduced pressure to give an aqueous dispersion with a solids content of 20%.
Comparative examples 2 to 8
As in comparative example 1, except that Si-B3 was replaced with a monomer I having a different structure as follows, si-NB3 (comparative example 2), si-ph-B3 (comparative example 3), si-OCN-B3 (comparative example 4), si-OCO-B3 (comparative example 5), si-B2 (comparative example 6), si-N2-B2 (comparative example 7), si-5 (average molecular weight 500) were used, respectively (comparative example 8).
Comparative example 9
A1000 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with 75 g of Si-B3, 40 g of DN,20 g of HEMA and 135 g of methyl ethyl ketone (hereinafter referred to as MEK), nitrogen was introduced for 30 minutes, the temperature was slowly raised to 60℃and 1.4 g of t-butyl peroxypivalate as a peroxide initiator was added thereto, and the reaction temperature was controlled at 60℃to obtain about 270 g of a polymer solution having a solids content of about 50% by reacting for 20 hours.
525 g of water and 15 g of glacial acetic acid are added, stirred at 60℃for more than 1 hour and the MEK in the solution is distilled off under reduced pressure to give an aqueous dispersion with a solids content of 20%.
The performance of comparative examples 1-9 was tested according to the test method of the examples. The results are shown in Table 3.
Table 3 comparative example test performance
As can be seen from Table 3, the resulting compositions of comparative examples 1 to 9 hardly impart good water and oil repellency to paper under alkaline conditions.
It can be seen by combining tables 2 and 3 that the copolymers of the present invention and the compositions obtained therefrom also impart good oil and water repellency properties to paper under alkaline sizing conditions.
The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.

Claims (14)

1. A copolymer for water-repellent and oil-repellent treatment of paper products, which comprises a repeating unit produced by a monomer I and a repeating unit produced by a monomer II,
a) The structural general formula of the monomer I is shown in the formula I:
M-Z or Z-M-Z
I is a kind of
Wherein M contains a polymerizable functional group;
z is selected from the structures shown in the following,
in Z, R 3 Each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 20 Alkoxy or R of (A) 4 -O-R 5 -a group, R 4 Is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 5 Is C 1 -C 20 An alkylene group of 1.ltoreq.a.ltoreq.200;
Y 1 and Y 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Or an alkylaryl group of the formula (1):
R 7 each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 8 Each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 20 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 10 Is C 1 -C 20 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 shown in the formula II:
CH 2 ＝C(R 1 )-G-(R 2 O) q -R 3 II
in formula II, R 1 Represents a hydrogen atom or a methyl group, R 2 Each independently is C 1 -C 6 Alkylene of (C) is preferred 2 -C 4 Q is an integer from 1 to 50, preferably an integer from 1 to 20; r is R 3 Represents a hydrogen atom or C 1 -C 20 Alkyl radicals of (2), preferably hydrogen atoms or C 1 -C 10 More preferably a hydrogen atom, C 1 -C 3 Alkyl of (a);
wherein G is selected from the group shown in G-1 and G-2,
-C(O)-O-B-
G-1
-C(O)-N(R 4 )-B-
G-2
r4 represents a hydrogen atom or a methyl group, B is absent or C 1 -C 20 Alkylene of (2), preferably absent or C 1 -C 10 Alkylene groups of (a).
2. The copolymer of claim 1, wherein:
m is shown as a formula I-1:
CH 2 ＝C(R 1 )-X-B-
I-1
in the formula I-1, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl of (a); b is C 1 -C 20 An alkylene group of (a);
x is selected from the group shown as X-1 and X-2,
-C(O)-O-
X-1
-C(O)-N(R 2 )-
X-2
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl of (a);
and/or
M is shown as a formula I-2:
CH 2 ＝C(R 1 )-W-B-
1-2
in the formula I-2, R 1 Selected from hydrogen atoms or C 1 -C 20 An alkyl group;
w is selected from the group shown in W-1, W-2, W-3 and W-4,
-O-C(O)-N(R 2 )- W-2
-O-C(O)-O- W-3
-O-C(O)-O-D-N(R 2 )- W-4
R 2 selected from hydrogen atoms or C 1 -C 20 Alkyl, D is C 1 -C 20 An alkylene group of (a); when W is selected from W-1, B is absent or C 1 -C 20 When W is selected from W-2, W-3,W-4, B is C 1 -C 20 An alkylene group of (a);
and/or
M is shown as a formula I-3:
in the formula I-3, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl, B is independently C 1 -C 20 Alkylene groups of (a).
3. The copolymer of claim 1 or 2, excluding repeat units from monomer IV, wherein monomer IV 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, or dipropylaminopropyl (meth) acrylamide,
preferably, the structural general formula of the monomer IV is shown in formula IV:
CH 2 ＝C(R 1 )-P-B-N(R 3 R 4 ) IV
In the formula IV, P is selected from groups shown as P-1 and P-2,
-C(O)-O-
P-1
-C(O)-N(R 2 )-
P-2
b is C 1 -C 20 An alkylene group of (a); r is R 1 And R is 2 Each independently is a hydrogen atom or C 1 -C 20 An alkyl group; r is R 3 And R is 4 Each independently is a hydrogen atom, C 1 -C 18 Alkyl, hydroxyethyl or benzyl, or R 3 And R is 4 And combine with the nitrogen atom to form morpholino, piperidino, or pyrrolidino.
4. A copolymer according to any one of claims 1 to 3, characterized in that:
the mass content of the repeating units produced by the monomers I in the copolymer is 30 to 90%, preferably 40 to 80%, more preferably 45 to 70%; and/or the mass content of the repeating units derived from the monomer II in the copolymer is 5 to 65%, preferably 15 to 55%, more preferably 25 to 45%.
5. The copolymer according to claim 1 to 4,
the monomer I comprises a silicon monomer I-A and/or a silicon monomer I-B;
the general formula of the silicon monomer I-A is the same as formula I, and also satisfies Y when a is 1 1 And/or Y 2 Is of the formula (1), at least one Y when a is greater than 1 and less than or equal to 200 1 Is a structure of formula (1) and/or at least one Y 2 Is a structure of formula (1);
the general formula of the silicon monomer I-B is the same as the formula I and is also satisfiedFoot Y 1 And Y 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C of (2) 6 -C 20 Aryl, C of (2) 7 -C 12 Aralkyl and C of (C) 7 -C 12 Alkylaryl groups of (a).
6. The copolymer according to claim 1 to 5,
in the formula I-1, R 1 Selected from hydrogen atoms or C 1 -C 10 Alkyl, preferably R 1 Selected from a hydrogen atom or a methyl group; b is C 1 -C 10 Alkylene of (C), preferably B is C 1 -C 6 An alkylene group of (a); x, R 2 Selected from hydrogen atoms or C 1 -C 10 Alkyl, preferably R 2 Selected from a hydrogen atom or a methyl group;
in the formula I-2, R 1 Selected from hydrogen atoms or C 1 -C 10 Alkyl, preferably R 1 And R is 2 Selected from hydrogen atoms or methyl groups, B and D being C 1 -C 10 Alkylene of (C), preferably B and D are C 1 -C 6 An alkylene group of (a);
in the formula I-3, R 1 Selected from hydrogen atoms or C 1 -C 10 Alkyl, preferably R 1 Selected from a hydrogen atom or a methyl group; b is C 1 -C 10 An alkylene group of (a);
in Z, R 3 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 10 Alkoxy or R 4 -O-R 5 -a group, R 4 Is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 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, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a); r is R 8 Each independently is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl of (C) 7 -C 12 Alkylaryl, C 1 -C 10 Alkoxy or R 9 -O-R 10 -a group wherein R 9 Is C 1 -C 10 Alkyl, C of (2) 6 -C 10 Aryl, C of (2) 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl group R of (2) 10 Is C 1 -C 10 And b is more than or equal to 0 and less than or equal to 100.
7. The copolymer of any one of claims 1 to 6, wherein Z is selected from the following structures: each Z is independently selected from one or more of the following structures i-1 to i-6:
z is preferably from
One or more of the following;
r is each independently selected from C 1 -C 10 Alkyl, C 6 -C 10 Aryl, C 7 -C 12 Aralkyl or C of (C) 7 -C 12 Alkylaryl groups of (a);
me represents methyl, ph represents phenyl; m+1 is less than or equal to 1 and less than or equal to 60, preferably m+1 is less than or equal to 1 and less than or equal to 30; p is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; q is more than or equal to 0 and less than or equal to 60, preferably more than or equal to 0 and less than or equal to 30; x is not less than 1 and not more than 9, preferably not less than 1 and not more than 7, and each x can be the same or different.
8. The copolymer according to any one of claim 1 to 7,
monomer I is selected from
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝CHC(O)-NH-(CH 2 ) 3 Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3 ；
CH 2 ＝CHC(O)-O-(CH 2 ) 3 Si(OSi(CH 2 CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-CH 2 -Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 Si(CH 3 )[O-[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 ] 2 ，0≤n≤25；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 ，1≤n≤25；
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 ，1≤n≤25；
CH 2 ＝C(CH 3 )C(O)-O-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 3 ，1≤n≤25；
CH 2 ＝CH-ph-Si(OSi(CH 3 ) 3 ) 3 (ph represents)；
CH 2 ＝CH-ph-(CH 2 ) 2 Si(OSi(CH 3 ) 3 ) 3 (ph represents)；
CH 2 ＝CH-ph-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl, ph represents)，1≤n≤25；
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl), n is more than or equal to 1 and less than or equal to 25;
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents butyl), n is more than or equal to 1 and less than or equal to 25
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ；
CH 2 ＝CH-O-C(O)-O-(CH 2 ) 2 -NH-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 Represents butyl),
1≤n≤25；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(OSi(CH 3 ) 3 ) 3 ] 2 ；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ] 2 ；
CH 2 ＝CH-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 represents butyl), n is more than or equal to 1 and less than or equal to 25;
CH 2 ＝C(CH 3 )-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 represents butyl), n is more than or equal to 1 and less than or equal to 25.
9. The copolymer according to any one of claim 1 to 8,
the monomer II 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 or methoxy polyethylene glycol (meth) acrylate.
10. A composition comprising the copolymer of any one of claim 1 to 9 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 and dipropylene glycol methyl ether.
11. A process for preparing the composition of claim 10, comprising the steps of:
(1) Polymerizing monomers in an organic solvent to obtain a copolymer solution;
(2) Optionally, water is added to the copolymer solution for dispersion, followed by removal of the organic solvent, or the organic solvent is removed first and then water is added for dispersion.
12. Use of the copolymer of any one of claims 1-9 or the composition of claim 10 or the composition prepared by the method of claim 11 in paper products, fabrics, leather, non-wovens, asbestos, fur, concrete, natural stone or plastics.
13. A water-and oil-repellent product comprising a product which is a paper product, a fibrous fabric, leather, nonwoven, asbestos, pelt, concrete, natural stone or plastic, and a copolymer according to any one of claims 1-9 or a composition according to claim 10 or a composition according to the method according to claim 11,
Preferably, the copolymer of any one of claims 1-9 or the composition of claim 10 or the composition prepared by the method of claim 11 is attached to the surface and/or the interior of the product.
14. A process for the treatment of a product comprising contacting the product with a copolymer according to any one of claims 1 to 9 or a composition according to claim 10 or a composition prepared by a process according to claim 11, said product being a paper product, a fibrous web, leather, non-woven fabric, asbestos, fur, concrete, natural stone or plastic,
preferably, the contacting is achieved by a surface sizing or coating process.
CN202310653780.9A 2023-06-02 2023-06-02 Copolymer for paper product treatment, treatment method and product Pending CN117003942A (en)

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Application Number Priority Date Filing Date Title
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