CN117264120A - Modified saccharide substance, treating agent, preparation method and application thereof - Google Patents

Modified saccharide substance, treating agent, preparation method and application thereof Download PDF

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Publication number
CN117264120A
CN117264120A CN202310988994.1A CN202310988994A CN117264120A CN 117264120 A CN117264120 A CN 117264120A CN 202310988994 A CN202310988994 A CN 202310988994A CN 117264120 A CN117264120 A CN 117264120A
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equal
alkyl
group
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蒋凌飞
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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    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Abstract

The application relates to a modified saccharide substance, a treating agent, a preparation method and application thereof. The modified saccharide provided by the application comprises a saccharide and an organosilicon polymer, wherein the saccharide is connected with the organosilicon polymer through a chemical bond, the organosilicon polymer comprises a structural unit generated by a monomer I, and the definition of the monomer I is as shown in the specification. The modified saccharide substance and the treating agent containing the modified saccharide substance can be used in a wider pH environment to treat various articles, so that the oil-repellent and water-repellent properties of the surfaces of the articles are endowed.

Description

Modified saccharide substance, treating agent, preparation method and application thereof
Technical Field
The application relates to a modified saccharide substance, a treating agent, a preparation method and application thereof.
Technical Field
The surfaces of paper, fiber fabrics, etc. are treated to be water-repellent and oil-repellent, so that they have some special application functions, such as paper being applicable to packaging of grease foods, fiber fabrics being excellent in preventing various stains, improving the neatness of clothing, etc. For a long time, in order to obtain such a water-repellent and oil-repellent function, fluorides are generally used for the treatment of paper, fiber fabrics and the like, and can make the surface of an article water-repellent and oil-repellent without changing the appearance of the article.
However, in recent years, as the international society has increased attention to polyfluoroalkyl compounds (PFAS), month 3 of 2023, the european union chemical administration (ECHA) has opened public consultations concerning the increased restrictions on PFAS manufacture, release and use proposals in REACH restrictions (REACH appendix XIVII) submitted to ECHA in denmark, germany, the netherlands, norway and sweden, with the aim of giving the interested parties the opportunity to take PFAS REACH restrictions for regulatory comments, and after the public consultation has ended. The ECHA's Committee for Risk Assessment (RAC) and socioeconomic analysis Committee (SEAC) will evaluate proposed restrictions and develop comments based on consultation comments, ultimately being governed by the European Committee's decision whether to incorporate PFAS into restrictions.
In view of the above, new non-fluorine compounds have been proposed to replace existing fluorine-containing finishes.
Patent CN100300612 describes a copolymer of an organosiloxane which can be used for the treatment of paper, making the paper water-repellent and oil-repellent, but this copolymer is based on a coating method which requires film formation and is relatively complex in process.
CN 114573768B describes a silicone copolymer which can be used for the treatment of articles, which is a cationic copolymer, and which has certain limitations in application, in particular in alkaline environments, with the possibility of failure.
Alkaline environments, particularly those with higher pH, are more common in modern industrial applications, such as the modern paper industry, where alkaline papermaking is the dominant process. Such as in leather kneading, alkaline environments are more prevalent. For stone treatment, the main component of marble is calcium carbonate, which reacts with acid, so it is important to ensure that the chemical remains functional in alkaline condition. Therefore, there is a need to develop a treatment agent suitable for a wider range of pH values.
Disclosure of Invention
The purpose of the present application is to provide a modified saccharide capable of polymerizing in water, which can be used in a wider pH environment, and which can treat various articles to impart oil-repellent and water-repellent properties to the surfaces of the articles, and a treating agent comprising the modified saccharide.
In a first aspect, the present application provides a modified saccharide, which includes a saccharide and an organosilicon polymer, where the saccharide is connected to the organosilicon polymer through a chemical bond, and the organosilicon polymer includes a structural unit generated by a monomer I, where the structural general formula of the monomer I is shown in 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 selectFrom 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 some embodiments, the silicone polymer is grafted onto the saccharide.
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 selected from C 1 -C 20 Alkylene group, C 6 -C 20 Arylene groups of (a) and combinations thereof;
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 Is a hydrocarbon group.
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, a formulaIn 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, in formula I-1, B is C 6 -C 15 Arylene groups of (2), e.g. C 6 -C 9 Arylene of (C) 10 -C 12 Arylene or C of (2) 13 -C 15 Arylene group of (a).
In some embodiments, R in the groups represented by X-1 and X-2 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 selected from C 1 -C 20 Alkylene group, C 6 -C 20 Arylene groups of (a) and combinations thereof.
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 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, when W is selected from W-2, W-3,W-4, B is C 6 -C 15 Arylene groups of (2), e.g. C 6 -C 9 Arylene of (C) 10 -C 12 Arylene or C of (2) 13 -C 15 Arylene group 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 selected from C 1 -C 20 Alkylene group, C 6 -C 20 Arylene groups of (a) and combinations thereof.
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, B is C 6 -C 15 Arylene groups of (2), e.g. C 6 -C 9 Arylene of (C) 10 -C 12 Arylene or C of (2) 13 -C 15 Arylene group 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 of the otherIs 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 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, 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 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.
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 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 (a)、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.
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 group of (C),C 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 invention, 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 。
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.
The definition of M in formulas 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 represents
)，1≤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), 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(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；
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 silicone polymer further comprises structural units derived from monomer III, which is a monomer having an anion-donating group and a polymerizable unsaturated group, the anion-donating group being a carboxyl group or a sulfonic acid group.
In some embodiments, the polymerizable unsaturated group in monomer III is selected from groups containing carbon-carbon double bonds.
In some embodiments, monomer III is selected from (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamido tert-butylsulfonic acid, or salts thereof.
In some embodiments, the carbohydrate is selected from one or more of starches, cellulosics, galactomannans, xanthans, alginates, pectins, chitosans, gum arabic, carrageenan, agar, and gellan gums.
In some embodiments, the carbohydrate has a weight average molecular weight of 1000 to 65000.
In some embodiments, the carbohydrate is selected from the group consisting of starches selected from one or more of starches, modified starches, degraded starches, and modified degraded starches.
The starches herein may be obtained from all starch types, for example from potato, corn, wheat, rice, tapioca, sorghum or waxy starches having more than 80%, preferably more than 95% amylopectin, for example waxy maize starch or waxy potato starch. The starch may be modified anionically or/and cationically, esterified, etherified and/or crosslinked.
In some embodiments, the modified starch is selected from one or more of a cationic modified starch, an anionic modified starch, and a nonionic modified starch.
In some embodiments, the molecular weight Mw of the starch is suitably in the range of 1000-65000 daltons, and if the molecular weight is too large, it may be obtained by degradation or modification of the starch, the molar mass Mw of the degraded starch preferably being in the range of 2500-35000.
In some embodiments, the ratio of cationic or anionic groups in the modified starch is specified by the Degree of Substitution (DS), for example, from 0.005 to 1.0, preferably from 0.01 to 0.4.
Conventional cationized starches are for example prepared by quaternization of natural starches, such as potato, wheat, maize, rice or tapioca starch, with at least one quaternizing agent.
According to some embodiments of the polymers of the present application, the carbohydrate substance is preferably a starch, in particular a modified degraded starch, a starch having a Mw molecular weight in the range of 1000-65000.
In some embodiments, monomer I produces structural units in an amount by mass in the silicone polymer ranging from 5% to 100%, for example 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, or any two of these. In some embodiments, monomer I produces structural units in an amount of 30% to 75% by mass of the silicone polymer. In some embodiments, monomer I produces structural units in the silicone polymer at a mass content of 40% to 60%.
In some embodiments, the mass content of the saccharide in the modified saccharide is in the range of 5% -90%, e.g., 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, or any two of them. In some embodiments, the mass of the carbohydrate is from 20% to 70% of the mass of the modified carbohydrate. In some embodiments, the mass content of the carbohydrate substance in the modified carbohydrate substance is 30% -60% by mass.
In some embodiments, monomer III produces structural units in an amount by mass in the silicone polymer ranging from 0.5% to 30%, for example 1%, 3%, 5%, 7%, 10%, 11%, 13%, 15%, 17%, 20%, 21%, 23%, 25%, 27% or any two of these. In some embodiments, monomer III produces structural units in an amount of 3% to 20% by mass of the silicone polymer. In some embodiments, monomer III produces structural units in an amount of 5% to 15% by mass of the silicone polymer.
In a second aspect, the present application provides a treatment agent comprising a modified carbohydrate substance according to the first aspect, optionally an emulsifier, and an aqueous medium.
In some embodiments, the aqueous medium comprises water and optionally an organic solvent. In some embodiments, the aqueous medium is preferably water. In some embodiments, the aqueous medium includes water and an organic solvent. The organic solvent is not particularly limited, and any organic solvent that can be mixed with water is suitable for use in the present application, and examples of the organic solvent include acetone, methyl ethyl ketone, ethyl acetate, ethanol, isopropyl alcohol, butyl diglycol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and the like. The ratio of water to the organic solvent is not particularly limited.
In some embodiments, the emulsifier is selected from one or more of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.
In some embodiments, the emulsifier is selected from the group consisting of the reaction products of long chain monohydric alcohols (C10-C22 alkanols) with 4 to 50 moles of ethylene oxide and/or propylene oxide per mole of alcohol, or ethoxylated phenols or alkoxylated alcohols esterified with sulfuric acid, which are typically used in a form neutralized with a base.
In some embodiments, the emulsifier is selected from sodium alkanesulfonate, sodium alkyl sulfate, sodium dodecylbenzenesulfonate, sulfosuccinates, alkyl quaternary ammonium salts, alkyl benzyl ammonium salts (e.g., dimethyl C12-C18 alkyl benzyl ammonium chloride), primary, secondary or tertiary fatty amine salts, quaternary amino amine compounds, alkyl pyridinium salts, alkyl oxazolium salts.
In a third aspect, the present application provides a method for producing the treating agent according to the second aspect, which comprises subjecting a monomer to a polymerization reaction in the presence of a saccharide and an initiator.
In some embodiments, the method of making comprises the steps of:
(1) Mixing a saccharide with water to obtain a first mixture;
(2) The polymerization is carried out by adding monomer, initiator, optional organic solvent, optional emulsifier and optional molecular weight regulator to the first mixture.
According to some embodiments of the present application, a method of preparing a treatment agent comprises the steps of:
adding saccharide and water into a reactor, heating to a certain temperature, dispersing or dissolving saccharide in water, gradually dropwise adding or completely adding polymerizable monomer I and/or monomer III into the reactor, and simultaneously dropwise adding an initiator to initiate polymerization to obtain the treating agent.
In a fourth aspect, the present application provides the use of a modified carbohydrate according to the first aspect or a treatment according to the second aspect or a treatment prepared by a method according to the third aspect in a fibrous web, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper products or plastics.
In a fourth aspect, the present application provides a water and oil repellent product comprising a product of a fibrous fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper products or plastics and a modified carbohydrate according to the first aspect or a treatment according to the second aspect or a treatment prepared by a method according to the third aspect.
In some embodiments, the modified carbohydrate according to the first aspect or the treatment according to the second aspect or the treatment prepared by the method according to the third aspect is attached to the surface and/or the interior of the product.
In a fifth aspect, the present application provides a method of treating a product comprising contacting the product with a modified carbohydrate material according to the first aspect or a treating agent according to the second aspect or a treating agent prepared by a method according to the third aspect, the product being a fibrous fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper product or plastic.
In some embodiments, the contacting is achieved by an internal addition process, a surface sizing process, a surface coating process, a soaking treatment process.
In the present application, the fiber fabric includes animal or plant natural fibers such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., semisynthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, carbon fibers, asbestos fibers, etc., or mixed fiber fabrics thereof.
ADVANTAGEOUS EFFECTS OF INVENTION
The modified saccharide substance and the treating agent comprising the modified saccharide substance can be used for treating various articles such as paper products, fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, stone or plastics and the like and endowing the surfaces of the articles with the functions of water repellency and oil repellency.
The specific embodiment is as follows:
in order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the following examples. These examples are only for the purpose of explaining the present application and are not intended to constitute any limitation to the present application. The actual scope of the application is set forth in the following claims.
Unless otherwise indicated herein, the terms used herein have their ordinary meanings as known to those skilled in the art.
In this 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 chainAlkylene groups, 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 percent unless otherwise specified.
1. The polymerization method comprises the following steps:
According to the present application, a treating agent comprising a modified saccharide is obtained by subjecting an olefin-containing unsaturated monomer to free radical emulsion polymerization in the presence of at least one redox initiator and a saccharide polymer, wherein
(a) 5-80% of monomer I, monomers containing M-Z and/or Z-M-Z structures,
(b) From 5% to 80% of at least one carbohydrate, preferably a starch, having a Mw of 1000-65000;
(c) From 5% to 10% of monomers III containing polymerizable double bond structures and hydrophilic functional groups such as acrylic acid and the like;
wherein the sum of I+saccharide+III is 100%.
The preferred modified carbohydrate substances or treatments use the following components:
the carbohydrate is preferably starch, which can be obtained from all starch types, for example from potato, corn, wheat, rice, tapioca, sorghum or waxy starch having more than 80%, preferably more than 95%, amylopectin, for example waxy corn starch or waxy potato starch. The starch may be modified anionically or/and cationically, esterified, etherified and/or crosslinked. Nonionic, anionic or cationic starches are preferred.
The molecular weight Mw of the starch is suitably in the range of 1000 to 65000 daltons, and if the molecular weight is too great, it may be obtained by degradation or modification of the starch, the molar mass Mw of the degraded starch preferably being in the range of 2500 to 35000.
In substituted starches, the ratio of cationic or anionic groups is dictated by the Degree of Substitution (DS). The degree of substitution is, for example, 0.005 to 1.0, preferably 0.01 to 0.4.
All starches can be used. Conventional cationized starches are for example prepared by quaternization of natural starches, such as potato, wheat, maize, rice or tapioca starch, with at least one quaternizing agent. The degradation of the starch is preferably carried out before the polymerization of the monomers, but can also be carried out during the polymerization of the monomers. Degradation may be carried out by oxidation, heat, acidolysis or enzymolysis. The degradation of the starch is preferably carried out enzymatically and/or oxidatively in the apparatus in which the polymerization is to be carried out or in a separate step directly before the start of the emulsion polymerization. In the polymerization, a single degraded starch or a mixture of two or more degraded starches may be used. In a monomer reaction mixture containing several components, the starch is present in an amount of 5-90%, preferably 20-70%.
According to the present application, redox initiators are used for initiating the polymerization reaction, said initiators preferably stabilizing water-soluble redox systems containing a graft linkage, for example comprising hydrogen peroxide and heavy metal salts, or comprising hydrogen peroxide and sulfur dioxide, or comprising hydrogen peroxide and sodium metabisulfite. Other suitable redox systems are the following combinations: tert-butyl hydroperoxide/sulfur dioxide, potassium or sodium persulfate/sodium bisulfite, ammonium persulfate/sodium bisulfite, or ammonium persulfate/iron (II) sulfate. Preferably, a combination of hydrogen peroxide with a heavy metal salt such as iron (II) sulfate is used. Typically, the redox system additionally contains other reducing agents, such as ascorbic acid, formaldehyde sulfoxylate, hydrogen sulfite or sodium dithionite. In addition, other reducing agents such as ascorbic acid, sodium formaldehyde sulfoxylate, sodium hydrogen sulfite or sodium dithionite are included. Since the polymerization of the monomers takes place in the presence of starch and the starch also acts as a reducing agent, it is generally not necessary to use additional reducing agents simultaneously. The redox initiator is used in an amount of, for example, 0.05 to 10%, preferably 0.1 to 5%, based on the monomers.
The emulsion polymerization of monomers I and/or monomers III is carried out in an aqueous medium in the presence of a starch having a molar mass Mw of from 1000 to 65000. The monomers may be polymerized by emulsion polymerization, following the feed procedure. Preferably, the aqueous solution of degraded starch and heavy metal salt is first added and the monomers are added, either continuously or batchwise, alone or as a mixture, to the oxidatively active component of the redox initiator, preferably hydrogen peroxide.
The addition may be performed uniformly or non-uniformly during metering, i.e. varying the metering rate.
The polymerization is generally carried out under nitrogen protection, during which the respective combinations should be ensured to be thoroughly mixed, so that the reaction mixture is preferably under stirring during the entire duration of the polymerization and any subsequent post-polymerization.
The polymerization is generally carried out at a temperature of from 30℃to 100℃and preferably from 50℃to 110 ℃. Pressure reactors for continuous polymerization in stirred tank cascades or flow tubes may also be used.
To enhance the dispersing effect, conventional ionic, nonionic or zwitterionic emulsifiers may be added to the polymerization batch. If appropriate, only conventional emulsifiers are used, in amounts of from 0 to 3%, preferably from 0.02% to 2%, based on the total amount of monomers used. Examples of conventional emulsifiers are the reaction products of long-chain monohydric alcohols (C10-C22-alkanols) with 4 to 50 mol of ethylene oxide and/or propylene oxide per mol of alcohol, or ethoxylated phenols or alkoxylated alcohols esterified with sulfuric acid, which are generally used in a form neutralized with a base. Other conventional emulsifiers are, for example, sodium alkanesulfonates, sodium alkylsulfates, sodium dodecylbenzenesulfonates, sulfosuccinates, alkyl quaternary ammonium salts, alkyl benzyl ammonium salts (e.g.dimethyl C12-C18-alkyl benzyl ammonium chloride), primary, secondary or tertiary fatty amine salts, quaternary amino amine compounds, alkylpyridinium salts, alkyl oxazolium salts.
During emulsion polymerization, the monomers may be metered directly into the initial mixture, or may be added to the polymerization batch in the form of an aqueous emulsion or microemulsion. For this purpose, the monomers are emulsified in water with the abovementioned conventional emulsifiers.
The polymerization is carried out at a pH of from 2 to 9, preferably in the weakly acidic range of from 3 to 5.5. The pH may be adjusted to the desired value prior to or during polymerization with conventional acids such as hydrochloric acid, sulfuric acid or acetic acid or with bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia, ammonium carbonate, etc. The dispersion is preferably adjusted to a pH of from 5 to 7 with sodium hydroxide solution, potassium hydroxide solution or ammonia after the polymerization has ended.
In order to remove as much of the remaining monomer as possible from the treatment agent, postpolymerization is advantageously carried out. For this purpose, after the end of the main polymerization, an initiator selected from the group consisting of hydrogen peroxide, peroxides, hydroperoxides and/or azo compounds is added to the treatment agent, it being possible to use a combination of the initiator with a suitable reducing agent, for example ascorbic acid or sodium hydrogen sulfite. Preferably, oil-soluble initiators which are poorly soluble in water are used, for example conventional organic peroxides, such as dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide or dicyclohexyl peroxydicarbonate.
For the postpolymerization, the reaction mixture is heated, for example, to a temperature corresponding to the temperature of the main polymerization or to a temperature 20℃higher, preferably 10℃higher. When the polymerization initiator has been consumed or the monomer conversion is, for example, at least 98%, preferably at least 99.5%, the main polymerization is completed. T-butyl peroxide is preferred for the post-polymerization. Post-polymerization is carried out, for example, at from 35℃to 100℃and generally from 45℃to 95 ℃.
After the polymerization is completed, a complexing agent for the heavy metal ions may be added to the treating agent in an amount such that all the heavy metal ions are bound in a complexing manner.
The modified carbohydrate-containing treatment agent is, for example, 5% to 50%, preferably 15% to 40% in solids content.
The above-mentioned modified saccharide-containing treating agent is used as a sizing material for paper, paperboard and cardboard. They can be used in conventional amounts as surface size and as machine size. Preferably as a surface size. The treatment agent of the present application can be processed by all methods suitable for surface sizing. The treating agent may be applied to the surface of the paper to be sized by, for example, a size press, a film press, or a gate roll coater. For application, the treating agent is generally added to the sizing press liquid in an amount of from 0.05 to 3% by weight, based on the solid matter, and depends on the desired degree of sizing of the paper to be processed. In addition, the sizing press liquid may contain other substances, such as starch, Pigment, whitening agent, increasing agent, fixing agent, anti-foam agent and retention aid. The amount of polymer applied to the surface of the paper product is, for example, 0.005-1.0/m 2 Preferably 0.01-0.5g/m 2 。
The treating agent can be used as a surface treating agent for a fiber fabric and can be applied to an object to be treated by a conventionally known method. In general, the treatment agent is diluted in water, and is applied to the surface of the object to be treated by a known method such as dip coating, spray coating, or foam, and dried. In addition, vulcanization may be applied with a suitable crosslinking agent (e.g., blocked isocyanate) if desired. Insect repellent, softener, antibacterial agent, flame retardant, antistatic agent, crease-resist agent, etc. may be added to the treatment agent of the present application. The concentration of the polymer in the treatment liquid in contact with the substrate may be from 0.01% to 10% (in particular in dip coating), for example from 0.05 to 10% by weight.
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 cartons, again per 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. Adding Guangxi Ming Yang Yangsheng in paper product making processCationic starch MC-2 starch produced by chemical company, the addition amount of which is 1 percent of the weight of the pulp board, is made into 50 grams/meter by using a fourdrinier paper machine 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 a treating agent, wherein the concentration of the treating agent in the starch solution is 1-15% by weight (the concentration of the whole treating agent, and the non-solid concentration). 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.
The coating starch is coating 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 a treating agent is added, wherein the concentration of the treating agent in the starch solution is 1% -15% (the concentration of the whole treating agent, non-solid 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
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
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. 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 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 (3) turning the cylinder right 10 s-15 s before the water absorption is finished, loosening the gland clamping device, and taking down the sample. 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 formulas of the substances
Example 1
165 g of the Ming-Yang Biochemical cationic tapioca starch RS-118 (DS value=0.045) are introduced into a flask equipped with a stirrer and with means for detecting the internal temperature. 1100 g of deionized water was added while stirring, and the mixture was heated to 85℃and stirred for 30 minutes, followed by 7.0 g of glacial acetic acid and 1.4 g of 10% ferrous sulfate heptahydrate. Then, 6.24 g of 18% hydrogen peroxide solution are metered in over 30 minutes.
Then, a mixture of 300 g of deionized water, 0.26 g of alkanesulfonate having an average chain length of C15 (40%) was started, 1.5 g of dodecylmercaptan, 210 g of Si-B3 monomer feed and metered in over 120 minutes. At the same time, 56.2 g of 18% strength hydrogen peroxide solution were added over 150 minutes.
The above mixture was post-polymerized for 30 minutes and then cooled to 50 ℃. Then 17.6 g of 10% strength tert-butyl hydroperoxide was added over 70 minutes, finally 1.1 g of 40% strength sodium ethylenediamine tetraacetate aqueous salt solution was added, the reaction mixture was cooled to 30℃and adjusted with deionized water to obtain an emulsion with a solids content of 20%, and the theoretical solids content compared with the actual measured solids content showed a monomer conversion of more than 98%.
And adding absolute ethyl alcohol into part of the obtained emulsion to demulsify, standing for 24 hours, filtering, and drying the solid obtained by filtering in a drying oven at 70 ℃ until the weight is constant to obtain a crude product. Then, acetone was used as a solvent, and the solvent was extracted in a Soxhlet extractor for 8 hours to remove a small amount of polymer not bonded to starch chemical bonds, followed by drying. The dried sample was analyzed by infrared spectroscopy (FTIR) and the results showed successful attachment of the silicone polymer to the starch via chemical bonds.
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).
And adding absolute ethyl alcohol into part of the obtained emulsion to demulsify, standing for 24 hours, filtering, and drying the solid obtained by filtering in a drying oven at 70 ℃ until the weight is constant to obtain a crude product. Then, acetone was used as a solvent, and the solvent was extracted in a Soxhlet extractor for 8 hours to remove a small amount of polymer not bonded to starch chemical bonds, followed by drying. The dried sample was analyzed by infrared spectroscopy (FTIR) and the results showed successful attachment of the silicone polymer to the starch via chemical bonds.
Example 9
165 g of the Ming-Yang Biochemical cationic tapioca starch RS-118 (DS value=0.045) are introduced into a flask equipped with a stirrer and with means for detecting the internal temperature. 1100 g of deionized water was added while stirring, and the mixture was heated to 85℃and stirred for 30 minutes, followed by 7.0 g of glacial acetic acid and 1.4 g of 10% ferrous sulfate heptahydrate. Then, 6.24 g of 18% hydrogen peroxide solution are metered in over 30 minutes.
Then, a feed of 300 g of deionized water, 0.26 g of an alkanesulfonate (40%) having an average chain length of C15, 1.5 g of tert-dodecyl mercaptan, 210 g of Si-B3 monomer and 20 g of MAA monomer was started and metered in over 120 minutes. At the same time, 56.2 g of 18% strength hydrogen peroxide solution were added over 150 minutes.
The above mixture was post-polymerized for 30 minutes and then cooled to 50 ℃. Then 17.6 g of 10% strength t-butyl hydroperoxide was added over 70 minutes, and finally 1.1 g of 40% strength sodium ethylenediamine tetraacetate aqueous salt solution was added, and the reaction mixture was cooled to 30℃and adjusted with deionized water to obtain an emulsion having a solids content of 20%. Comparison of the theoretical solids content with the actual measured solids content shows that the monomer conversion is greater than 98%.
And adding absolute ethyl alcohol into part of the obtained emulsion to demulsify, standing for 24 hours, filtering, and drying the solid obtained by filtering in a drying oven at 70 ℃ until the weight is constant to obtain a crude product. Then, acetone was used as a solvent, and the solvent was extracted in a Soxhlet extractor for 8 hours to remove a small amount of polymer not bonded to starch chemical bonds, followed by drying. The dried sample was analyzed by infrared spectroscopy (FTIR) and the results showed successful attachment of the silicone polymer to the starch via chemical bonds.
Performance testing
Test of several articles using the emulsions synthesized in the examples as treatment agents:
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. The specific test results are shown in Table 2.
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. The specific test results are shown in Table 2.
Table 2 test performance comparison table
As can be seen from Table 2, the treatment agents obtained in examples 1-9 showed good oil and water repellency after treatment of paper products by surface sizing or coating under alkaline conditions. From the data of example 8, it can be seen that the treatment containing the structural units derived from silicon monomer I-A has a better oil repellent effect than the treatment containing the structural units derived from silicon monomer I-B.
Comparative example 1
A four-port 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, and the reaction temperature was controlled at 60℃to react for 20 hours to obtain about 270 g of a polymer solution having a solids content of about 50%.
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
As in example 1, except that Si-B3 was replaced by vinyltriisopropoxysilane, a stable dispersion was not finally obtained, and only a gel which could not flow was obtained.
Comparative examples were tested using the same test methods as in examples 1-9, and the test results are shown in Table 3.
Table 3 comparative example test performance table
As can be seen from Table 3, the aqueous dispersions obtained in comparative examples 1-8 do not impart good water and oil repellency properties to paper products when surface sized or coated under alkaline conditions.
Comparative example 9 is a polymerization with other alkoxysilane monomers in the presence of starch, which is prone to hydrolysis and condensation, resulting in crosslinking of the polymer into a gel, failing to obtain a stable aqueous dispersion.
The technical solution of the present application is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present application fall within the protection scope of the present application.

Claims (14)

1. The modified saccharide comprises a saccharide and an organosilicon polymer, wherein the saccharide is connected with the organosilicon polymer through chemical bonds, the organosilicon polymer comprises a structural unit generated by a monomer I, and 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 Is an aralkyl of (C)Radical, 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 group of (2) is more than or equal to 0 and less than or equal to 200.
2. The modified carbohydrate substance as claimed in 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 atomsOr C 1 -C 20 Alkyl of (a); b is selected from C 1 -C 20 Alkylene group, C 6 -C 20 Arylene groups of (a) and combinations thereof;
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 represented by formula 1-2:
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 selected from C 1 -C 20 Alkylene group, C 6 -C 20 Arylene groups of (a) and combinations thereof;
and/or
M is represented by formulas 1-3:
in the formula I-3, R 1 Selected from hydrogen atoms or C 1 -C 20 Alkyl, B is independently selected from C 1 -C 20 Alkylene group, C 6 -C 20 Arylene groups of (a) and combinations thereof.
3. The modified carbohydrate as set forth in claim 1 or 2, characterized in that: the silicone polymer also includes structural units derived from monomer III, which is a monomer having an anion-donating group and a polymerizable unsaturated group, the anion-donating group being a carboxyl group or a sulfonic acid group.
4. A modified carbohydrate as claimed in any of claims 1 to 3, characterised in that: the mass content of the structural unit generated by the monomer I in the organosilicon polymer is 5-100%, preferably 30-75%, more preferably 40-60%; and/or
The mass content of the saccharide in the modified saccharide is 5-90%, preferably 20-70%, more preferably 30-60%; and/or
The mass content of the structural units produced by the monomer III in the organosilicon polymer is 0.5-30%, preferably 3-20%, more preferably 5-15%.
5. The modified carbohydrate substance as claimed in any one of claims 1 to 4, wherein: the saccharide is selected from one or more of starch, cellulose, galactomannan, xanthan gum, alginate, pectin, chitosan, gum arabic, carrageenan, agar and gellan gum;
preferably, the carbohydrate is selected from the group consisting of starches selected from one or more of starch, modified starch, degraded starch and modified degraded starch, preferably selected from one or more of cationic modified starch, anionic modified starch and nonionic modified starch;
and/or the weight average molecular weight of the saccharide is 1000-65000.
6. The modified carbohydrate substance of any of claims 1-5, wherein:
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 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).
7. The modified carbohydrate substances as claimed in any of claims 1 to 6, characterized in that,
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.
8. The modified carbohydrate substance of any of claims 1-7, 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.
9. The modified carbohydrate substances as claimed in any of claims 1 to 8, characterized in that,
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 ；
And/or
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 represents
)，1≤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), 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(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；
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;
and/or
The monomer III is selected from (methyl) acrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, (methyl) allylsulfonic acid, styrenesulfonic acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid or salts thereof.
10. A treatment agent comprising the modified carbohydrate substance of any of claims 1-9, optionally an emulsifier, and an aqueous medium, preferably the aqueous medium comprises water and optionally an organic solvent.
11. A process for preparing the treatment agent of claim 10, comprising polymerizing monomers in the presence of a saccharide and an initiator, preferably comprising the steps of:
(1) Mixing a saccharide with water to obtain a first mixture;
(2) The polymerization is carried out by adding monomer, initiator, optional organic solvent, optional emulsifier and optional molecular weight regulator to the first mixture.
12. Use of a modified carbohydrate according to any of claims 1-9 or a treating agent according to claim 10 or a treating agent prepared by a method according to claim 11 in paper products, fabrics, leather, non-wovens, asbestos, fur, concrete, stone or plastics.
13. A water-and oil-repellent product comprising a product of a paper product, a fiber fabric, leather, a nonwoven fabric, asbestos, fur, concrete, stone or plastic, and a modified saccharide according to any one of claims 1 to 9 or a treating agent according to claim 10 or a treating agent produced by the method according to claim 11,
preferably, the modified carbohydrate substances of any of claims 1 to 9 or the treatment agent of claim 10 or the treatment agent prepared by the method of claim 11 is attached to the surface and/or the interior of the product.
14. A method for treating a product comprising contacting the product with the modified saccharide of any one of claims 1 to 9 or the treating agent of claim 10 or the treating agent prepared by the method of claim 11, which is a paper product, a fiber fabric, leather, nonwoven fabric, asbestos, fur, concrete, stone or plastic,
preferably, the contacting is achieved by an internal treatment process, a surface sizing process, a surface coating process or a soaking treatment process.
CN202310988994.1A 2023-08-07 2023-08-07 Modified saccharide substance, treating agent, preparation method and application thereof Pending CN117264120A (en)

Priority Applications (1)

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CN202310988994.1A CN117264120A (en) 2023-08-07 2023-08-07 Modified saccharide substance, treating agent, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310988994.1A CN117264120A (en) 2023-08-07 2023-08-07 Modified saccharide substance, treating agent, preparation method and application thereof

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CN117264120A true CN117264120A (en) 2023-12-22

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