CN110894267A - Fluorine-silicon graft copolymer, surface treating agent and application - Google Patents
Fluorine-silicon graft copolymer, surface treating agent and application Download PDFInfo
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- CN110894267A CN110894267A CN201911185237.0A CN201911185237A CN110894267A CN 110894267 A CN110894267 A CN 110894267A CN 201911185237 A CN201911185237 A CN 201911185237A CN 110894267 A CN110894267 A CN 110894267A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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Abstract
The invention belongs to the field of polymers containing fluorine and silicon, and particularly discloses a fluorine-silicon graft copolymer, a surface treating agent containing the fluorine-silicon graft copolymer and application of the surface treating agent. The fluorine-silicon graft copolymer is prepared by graft copolymerization of fluorine-silicon monomer, fluorine-free (methyl) acrylate monomer, active hydrogen-containing monomer and organic siloxane. According to the fluorine-silicon graft copolymer provided by the invention, proper fluorine-containing monomers and organic silicon monomers are selected, and the fluorine-containing and silicon-containing monomers are inserted into the main chain of acrylic resin or grafted as a side group through a one-step graft polymerization reaction to generate a dendritic network structure, so that the advantages of organic silicon and organic fluorine compounds are combined, and the excellent water-proof and oil-proof effects are achieved.
Description
Technical Field
The invention relates to a polymer containing fluorine and silicon, in particular to a fluorine and silicon graft copolymer, and also relates to a surface treating agent containing the fluorine and silicon graft copolymer and application of the surface treating agent.
Background
The fluorine-containing water-and-oil repellent product which is industrially matured at present is mainly a fluorine-containing monomer polymer (product C8) based on a perfluorooctyl compound, but the perfluorooctyl compound easily generates byproducts such as PFOA (perfluorooctanoic acid and salts thereof) and PFOS (perfluorooctane sulfonyl compound) which have difficult degradability, in-vivo accumulation and carcinogenicity during polymerization, so that relevant standards are developed in various countries around the world to limit the sale and use of fluorine-containing products such as PFOS.
Research shows that the perfluoro C6 alkyl product has no C8 alkyl component, so that no PFOS and its derivative and no PFOA produced, and is one important alternative path of perfluoro octyl water and oil repellent product. However, the perfluoro C6 alkyl water-and oil-repellent agent has a large difference in water-and oil-repellency from the C8 product, and has poor water-and oil-repellency. Chinese patent publication No. CN103788316B discloses a fluorine-containing block copolymer synthesized by a block copolymerization method, which has excellent waterproof performance, but the water-and oil-repellent treatment process thereof needs to be heated to 170 ℃ for baking and crosslinking, which is very likely to cause yellowing of cloth, and high-temperature treatment also inevitably causes high energy consumption.
In addition, the conventional water-repellent and oil-repellent finishing agent has two common preparation methods, namely an emulsion polymerization method and a solution polymerization method. The emulsion polymerization needs to add a surfactant and a cosolvent, the layering phenomenon can occur due to improper control conditions, the storage stability of the product is poor, and high-temperature baking and crosslinking are needed when the fabric is treated, so that the yellowing of the fabric is easily caused, and the high-temperature treatment also inevitably causes the problem of high energy consumption. The solution polymerization does not need a surfactant, the storage is stable, the layered precipitation generally does not occur after the reaction is finished, the secondary treatment is not needed during the use, and the excellent water and oil resistance of the fabric can be obtained only by spraying or soaking the solution type water and oil repellent finishing agent on the fabric and then naturally airing the fabric. Which is not possessed by the water-repellent and oil-repellent finishing agent produced by emulsion polymerization. Based on the characteristics of the solution type water-repellent and oil-repellent finishing agent, the solution type water-repellent and oil-repellent finishing agent can be prepared into spraying type household goods, and consumers can independently treat various household articles according to the demands and wishes, so that the household articles have water-proof and oil-proof properties.
Considering that the existing C8 solvent-based water-repellent and oil-repellent finishing agent product has safety and environmental problems, the C6 solvent-based water-repellent and oil-repellent finishing agent substitute product has poor water-proof and oil-proof performance, and the characteristics of high performance and convenient use of the solution-type water-repellent and oil-repellent finishing agent are that the emulsion-type product cannot substitute, therefore, the development of a novel, environment-friendly, safe and high-performance solution-type water-repellent and oil-repellent finishing agent is very necessary.
Disclosure of Invention
The invention mainly solves the technical problem of providing a fluorine-silicon graft copolymer, and also provides a surface treating agent containing the fluorine-silicon graft copolymer and application of the surface treating agent.
In order to solve the technical problems, the invention adopts a technical scheme that: a fluorine-silicon graft copolymer comprises the following raw materials:
(1) the fluorine-silicon monomer is shown as a formula (I), and the fluorine-silicon monomer is a fluorine-silicon monomer containing a plurality of terminal double bonds:
A-O-Rf-B-CH2-O-M-Si-(N-CH＝CH2)3formula (I)
In the formula (I), A is C substituted by 1 or more fluorine atoms1～16A linear alkyl group;
rf represents- (C)4F8O)a-(C3F6O)b-(C2F4O)c-(CF2O)d-, wherein a, b, c and d each independently represent an integer of 0 to 200, and the sum of a, b, c and d is at least 1;
b is C substituted by 1 or more fluorine atoms1～6A linear alkylene chain of (a);
m, N are each independently selected from C1～6A straight alkylene chain of (A) or (C)2～6A branched alkylene chain of (a);
(2) a fluorine-free (meth) acrylate monomer,
(3) a monomer containing active hydrogen and a monomer containing active hydrogen,
(4) an organosiloxane.
Further preferably, in the formula (I), A is C substituted by 3 to 7 fluorine atoms1～3A linear alkyl group; a. the sum of b, c and d is 4-40; b is C substituted by 2-6 fluorine atoms1～3A linear alkylene chain of (a); m, N are each independently selected from C1～3A linear alkylene chain of (a);
for example, the fluorosilicone monomer may be optionally selected from the following compounds:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2CH2-CH＝CH2)3
CF3O-(C4F8O)10-(C3F6O)10-(CF2O)10-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C2F4O)20-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(CF2O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)2-(C3F6O)2-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
as a preferred embodiment, the fluorine-free (meth) acrylate monomer is represented by formula (II):
wherein, X1Is a hydrogen atom or a methyl group;
X2is C1～C22Linear hydrocarbon group of (2), or C3～C22With branched hydrocarbon radicals or C3～C22The ring is an aromatic ring or an aliphatic ring.
Specifically, the fluorine-free (meth) acrylate monomer is optionally selected from one or more of methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate.
In the present invention, isobornyl (meth) acrylate means isobornyl methacrylate and/or isobornyl acrylate. It is to be inferred that the other groups containing a methyl group in parentheses have the same meaning. For example, n-butyl (meth) acrylate refers to n-butyl methacrylate and/or n-butyl acrylate.
As a preferred embodiment, the active hydrogen-containing monomer is a (meth) acrylic monomer containing at least one of a hydroxyl group, an amino group, and a mercapto group, or a double bond-containing hydroxyl group, amino group, and mercapto group-based monomer, or a diol, diamine, and dimercapto-based monomer, or a monomer containing any two of a hydroxyl group, an amino group, and a mercapto group;
preferably, the active hydrogen-containing monomer is optionally selected from one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, N-methylolacrylamide, N-hydroxyethyl acrylamide, N-vinylpyrrolidone, diacetone acrylamide, ethylene glycol, ethylene diamine, propylene diamine, hexamethylene diamine, p-phenylene diamine, thiophenol, hydroxylamine, primary amino mercaptan, secondary amino mercaptan, mercaptoethanol.
In a preferred embodiment, the organosiloxane is organosiloxane which contains at least one of amino, sulfydryl and double bonds and can be polymerized with acrylate;
preferably, the organic siloxane is one or more selected from vinyl trimethoxy silane, vinyl triethoxy silane, amino propyl triethoxy silane, mercaptopropyl trimethoxy silane, methacryloxypropyl trimethyl silane, vinyl silicone oil and hydrogen-containing silicone oil.
As a more preferred embodiment, the fluorosilicone graft copolymer comprises the following raw materials:
wherein the fluorine-silicon monomer is selected from the following compounds:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2CH2-CH＝CH2)3
CF3O-(C4F8O)10-(C3F6O)10-(CF2O)10-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C2F4O)20-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(CF2O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)2-(C3F6O)2-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3；
further preferred is
CF3CF2O-(CF2O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3；
The fluorine-free (methyl) acrylate monomer is octadecyl acrylate and/or isobornyl methacrylate; further preferred is stearyl acrylate;
the active hydrogen-containing monomer is methacrylic acid-3-chloro-2-hydroxypropyl ester and/or mercaptoethanol;
the organosiloxane is vinyl trimethoxy silane and/or methacryloxypropyl trimethyl silane.
Preferably, the mass ratio of the fluorine-silicon monomer to the fluorine-free (methyl) acrylate monomer to the active hydrogen-containing monomer to the organic siloxane is (9-40): (2-20): (0.5-5): (0.5 to 5);
more preferably, the mass ratio of the fluorine-silicon monomer, the fluorine-free (methyl) acrylate monomer, the active hydrogen-containing monomer and the organic siloxane is (12-33): (6-20): (0.5-4): (0.5 to 4).
The invention also provides a surface treating agent, which comprises the fluorine-silicon graft copolymer.
Further, the surface treatment agent further comprises a solvent.
In a preferred embodiment, the solvent is at least one selected from the group consisting of ethyl acetate, butyl acetate, n-hexane, n-heptane, petroleum ether, hexafluoropropylene trimer, perfluorohexanone, and hydrofluoroether, and may be one or a mixed solvent of two or more thereof.
The surface treatment agent can be applied to water-and oil-repellent treatment.
Further, the surface treatment agent can be applied to water-and oil-repellent treatment of fiber products, nonwoven fabrics, stone materials, concrete, leather, and the like.
The application method of the surface treating agent is to directly spray the surface treating agent on the surface of an article to be treated or soak the article to be treated by adopting the surface treating agent.
The invention provides a fluorine-silicon graft copolymer, which is prepared by the graft copolymerization of fluorine-silicon monomer, fluorine-free (methyl) acrylate monomer, active hydrogen-containing monomer and organic siloxane. The fluorine-silicon monomer is used, the characteristic of low surface energy of fluorine is utilized, when fabrics and the like are treated by the fluorine-silicon monomer, the fluorocarbon chains with extremely low surface energy are erected on the surfaces of polymer molecules like pig hair and extend to the outer side due to strong rigidity and poor flexibility, and thus, when liquid is dripped on the surfaces of the fabrics, the fluorocarbon chains are shielded by the fluorocarbon chains, and therefore, the excellent water and oil proofing effects are achieved. Research also finds that the length and stacking state of the perfluorocarbon chain are key to determine the water and oil resistance. In the prior art, the fluorine-containing monomer and the non-fluorine monomer are generally copolymerized by a one-step method, but the perfluorocarbon chain and the non-fluorine carbon chain are stacked in a crossed manner, and the water and oil proofing performance of the fluorine-containing carbon chain cannot be fully exerted. Based on the method, the fluorine-silicon monomer containing a plurality of terminal double bonds is adopted, and the fluorine-silicon monomer has a plurality of polymerization sites, and can generate a dendritic network-shaped molecular structure after reacting with the acrylate monomer, so that the method is very favorable for directing the perfluorinated side chains outwards, avoids the cross accumulation of the perfluorinated carbon chains, and enables the fluorine atoms to achieve the maximum effective utilization rate. The electron cloud of fluorine atom shields the carbon-carbon main chain well, and the perfluoroalkyl with low surface tension plays an excellent waterproof and oilproof effect while ensuring the stability of the carbon-carbon bond through the shielding protection of the fluorine atom to the main chain and the internal molecules.
Polysiloxane molecules in the fluorine-silicon graft copolymer formed by adding the organic siloxane are in a spiral structure, methyl bonded with Si is outwards arranged and rotates around the Si-O bond, so that the molecular volume is large, the cohesive energy density is low, the surface tension is small, and the polymer has excellent waterproof performance; and the bond length of Si-O bond in the organosilicon chain segment is longer than that of C-C bond, and 2 methyl shields are provided, so that the chain is very soft, and the fluorocarbon chain has low surface tension, and the main chain of silicon oxide has the characteristic of soft and soft curling, so that the silicone group is introduced by adding the organic siloxane, the respective advantages can be exerted, the function of the interpenetrating network structure of the fluorine-silicon polymer can be exerted, the polymerized fluorine-silicon graft copolymer shows more excellent performance, the defects of poor adhesion, low hardness, common strength and difficult normal temperature curing of the fluorine-silicon material can be improved, the prepared treating agent product is more widely applied, and the performance is mutually compensated and is more perfect. The addition of the organic siloxane can not only enhance the water-repellent and oil-repellent effects, but also reduce the fluorine content, namely reduce the use of fluorine, thereby saving the cost.
The fluorine-silicon polymer formed by the monomer containing active hydrogen is added, and hydroxyl contained in the base materials for processing cloth, cement or wood and the like can be crosslinked with the active hydrogen of the fluorine-silicon polymer in the form of intermolecular hydrogen bonds or covalent bonds, so that the binding force of the polymer and the base materials is improved, and the mechanical friction resistance and the washing resistance of the polymer can be enhanced.
In the water and oil repellent treatment, alkoxy of a fluorine-silicon compound and hydroxyl are combined with active groups on a substrate such as fibers, a cross-linked network is formed by combining the alkoxy groups and the hydroxyl with hydrogen bonds of the fibers, and an organic compound network layer can be formed on the surface of a treated object, so that the aim of improving water and oil resistance is fulfilled. Therefore, the fluorine-silicon grafted copolymer provided by the invention selects proper fluorine-containing monomers and organic silicon monomers, and the fluorine-containing and silicon-containing monomers are inserted into the main chain of acrylic resin or grafted as a side group through a one-step graft polymerization reaction to generate a dendritic network structure, so that the advantages of organic silicon and organic fluorine compounds are combined, and the excellent water-proof and oil-proof effects are achieved.
The fluorine-silicon graft copolymer provided by the invention can endow the surface of an article with enough water and oil resistance, and particularly does not contain toxic byproducts such as PFOS, PFOA and the like which have harm to human bodies and the environment, so that the environmental and safety problems of the product are effectively reduced.
In addition, the solvent type waterproof and oil-proof agent is prepared by selecting the common low-toxicity and cheap solvent such as ethyl acetate, butyl acetate and the like as the solvent for reaction, so that the advantages of the solution type water-repellent and oil-repellent finishing agent can be exerted. For example, the coating type household product can be prepared, consumers can independently treat various household articles according to the demands and the wishes, and the coating type household product has the advantages of convenience in use and high efficiency.
Detailed Description
The technical solution of the present invention will be explained in detail below.
The fluorine-silicon graft copolymer provided by the invention is prepared from the following raw materials:
(1) a fluorine-silicon monomer,
(2) a fluorine-free (meth) acrylate monomer,
(3) a monomer containing active hydrogen and a monomer containing active hydrogen,
(4) an organosiloxane;
graft copolymerization.
Specifically, the fluorine-silicon acrylate-based fluorine-free (methyl) acrylate-based fluorine-silicon acrylate-based.
For example, the composition ratio of the reaction materials can be as follows by mass percent:
9 to 40 percent of fluorine silicon monomer,
2 to 20 percent of fluorine-free (methyl) acrylate monomer,
0.5 to 5 percent of monomer containing active hydrogen,
0.5 to 5 percent of organic siloxane,
0.1 to 3 percent of initiator,
30 to 85 percent of solvent.
The more optimized range can be as follows according to the mass percentage content:
12 to 33 percent of fluorine silicon monomer,
6 to 20 percent of fluorine-free (methyl) acrylate monomer,
0.5 to 4 percent of monomer containing active hydrogen,
0.5 to 4 percent of organic siloxane,
0.1 to 1 percent of initiator,
60 to 80 percent of solvent.
As the initiator, there can be used an organic peroxide initiator such as benzoyl peroxide, t-butyl peroxypivalate or the like, or an azo initiator such as azobisisobutyronitrile, azobisisoheptonitrile or the like.
The reaction solvent is a conventional solvent, and may be, for example, ethyl acetate, butyl acetate, n-hexane, n-heptane, petroleum ether, hexafluoropropylene trimer, perfluorohexanone, hydrofluoroether, etc., and may be one of them or a mixed solvent of two or more of them.
The preparation of the fluorine-silicon monomer is realized by the following steps:
firstly, reacting perfluoropolyether acyl fluoride with methanol to obtain perfluoropolyether methyl ester;
then, hydrolyzing the perfluoropolyether methyl ester under the conditions of an alkaline catalyst and a solvent to obtain perfluoropolyether methanol;
then, reacting the perfluoropolyether methanol with allyl bromide to obtain allyl perfluoropolyether;
carrying out hydrosilylation reaction on allyl perfluoropolyether and trichlorosilane, taking triacetoxy methylsilane as a water removing agent and platinum as a catalyst for the reaction, and obtaining a perfluoropolyether modified substance with chlorosilane at the tail end after the reaction is finished;
and then reacting the prepared perfluoropolyether modified substance with chlorosilane at the tail end with allyl magnesium bromide to obtain the fluorosilicone monomer.
The fluorine-silicon monomer is a fluorine-silicon monomer containing a plurality of terminal double bonds, and more preferably, the fluorine-silicon monomer is represented by formula (I):
A-O-Rf-B-CH2-O-M-Si-(N-CH＝CH2)3formula (I)
Wherein A is C substituted with 1 or more fluorine atoms1～16A linear alkyl group;
rf represents- (C)4F8O)a-(C3F6O)b-(C2F4O)c-(CF2O)d-, where a, b, c and d are each independently integers taken from 0 to 200, and the sum of a, b, c and d is at least 1;
b is C substituted by 1 or more fluorine atoms1～6A linear alkylene chain of (a);
m, N are each independently selected from C1～6A straight alkylene chain of (A) or (C)2～6A branched alkylene chain of (a);
more preferably, in the above formula (I), A is C substituted with 3 to 7 fluorine atoms1～3A linear alkyl group; a. the sum of b, c and d is 4-40; b is C substituted by 2-6 fluorine atoms1～3A linear alkylene chain of (a); m, N are each independently selected from C1～3A linear alkylene chain of (a).
For example, non-limiting examples of fluorosilicone monomers may be:
fluorine-silicon monomer 1:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 2:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 3:
CF3CF2O-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 4:
CF3CF2O-(C3F6O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 5:
CF3CF2CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 6:
CF3CF2CF2O-(C4F8O)20-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2CH2-CH＝CH2)3
fluorine-silicon monomer 7:
CF3O-(C4F8O)10-(C3F6O)10-(CF2O)10-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 8:
CF3CF2O-(C2F4O)20-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 9:
CF3CF2O-(CF2O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
fluorine-silicon monomer 10:
CF3CF2CF2O-(C4F8O)2-(C3F6O)2-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
the fluorine-free (methyl) acrylate monomer is shown as a formula (II):
wherein, X1Is a hydrogen atom or a methyl group;
X2is C1～C22Linear hydrocarbon group of (2), or C3～C22With branched hydrocarbon radicals or C3～C22The ring is an aromatic ring or an aliphatic ring.
For example, the fluorine-free (meth) acrylate monomer may be any one or more selected from methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate.
The active hydrogen-containing monomer is a (methyl) acrylic monomer containing at least one of hydroxyl, amino and sulfydryl, or a double-bond hydroxyl, amino and sulfydryl monomer, or a dihydric alcohol, diamine and sulfydryl monomer, or a monomer containing any two of hydroxyl, amino and sulfydryl; preferably, the active hydrogen-containing monomer is optionally selected from one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 3-chloro-2 hydroxypropyl methacrylate, N-methylolacrylamide, N-hydroxyethyl acrylamide, N-vinyl pyrrolidone, diacetone acrylamide, ethylene glycol, ethylene diamine, propylene diamine, hexamethylene diamine, p-phenylene diamine, thiophenol, hydroxylamine, primary amino mercaptan, secondary amino mercaptan, mercaptoethanol.
The organic siloxane is organic siloxane which contains at least one of amino, sulfydryl and double bonds and can generate polymerization reaction with acrylate; preferably, the organic siloxane is one or more selected from vinyl trimethoxy silane, vinyl triethoxy silane, amino propyl triethoxy silane, mercaptopropyl trimethoxy silane, methacryloxypropyl trimethyl silane, vinyl silicone oil and hydrogen-containing silicone oil.
The following description will be made by way of specific examples.
Example 1
Firstly, preparing a fluorine silicon monomer 2:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
the method comprises the following steps:
s1: 300g of CF3CF2O-(C4F8O)20-CF2-CH2reacting-O-C (═ O) F with 43.81g of methanol under stirring at room temperature for 24 hours, finishing the reaction, placing the reaction mixture in a separating funnel, washing with methanol for three times, and distilling a lower layer sample under reduced pressure to obtain perfluoropolyether methyl ester;
s2: a three-necked flask was charged with 100g of methyl perfluoropolyether, and 3 portions were added to a total of 6.89g of NaBH4Adding 200mL of absolute ethyl alcohol, stirring and reacting at room temperature for 24 hours under the protection of nitrogen to obtain perfluoropolyether methanol;
s3: under the protection of nitrogen, adding 50g of perfluoropolyether methanol and 1.64g of potassium tert-butoxide into a three-neck flask, adding 75mL of tert-butyl alcohol as a reaction solvent, then dropwise adding 1.33g of allyl bromide, reacting for 6h at 40 ℃, after the reaction is finished, placing the reaction mixture into a separating funnel, washing with water, extracting a lower layer sample with 200mL of trifluorotrichloroethane, taking a lower layer liquid, and carrying out rotary evaporation to obtain the allyl perfluoropolyether: CF (compact flash)3CF2O-(C4F8O)20-CF2-CH2-O-CH2-CH＝CH2；
S4: 20g of allyl perfluoropolyether, 20g of 1, 3-bis (trifluoromethyl) benzene, 0.06g of triacetoxymethylsilane and 1.36g of trichlorosilane are stirred for 30min at 5 ℃ under a nitrogen atmosphere, 0.094mL of a xylene solution containing 2% of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex is added, then the temperature is raised to 60 ℃ for reaction for 5h, and after the reaction is finished, the perfluoropolyether modified substance with chlorosilane at the tail end is obtained by reduced pressure distillation:
CF3CF2O-(C4F8O)20-CF2CH2OCH2CH2CH2SiCl3；
s5: stirring 19g of perfluoropolyether modified product of chlorosilane and 20g of 1, 3-bis (trifluoromethyl) benzene for 30min at 5 ℃ in a nitrogen atmosphere, then adding 26.4mL of 0.7mol/L diethyl ether solution of allyl magnesium bromide, stirring for 10h at room temperature, then cooling to 5 ℃, adding 5mL of methanol, heating to room temperature, filtering, washing volatile components with methanol for 3 times after reduced pressure distillation, and finally obtaining a solution containing nonvolatile fluorosilicone monomer 2 by reduced pressure distillation. The fluorine-silicon monomer 2 is:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
weighing 33g of fluorosilicone monomer 2, 19g of octadecyl acrylate, 4g of 3-chloro-2-hydroxypropyl methacrylate, 2g of vinyltrimethoxysilane, 1g of tert-butyl peroxypivalate and 130g of butyl acetate in a four-port bottle, reacting for 8 hours at 75 ℃ in a nitrogen environment, and closing nitrogen to finish the reaction to obtain the solution containing the fluorine-silicon graft copolymer.
Example 2
Weighing 33g of fluorine-silicon monomer 4, 19g of octadecyl acrylate, 4g of mercaptoethanol, 4g of vinyl trimethoxy silane, 1g of tert-butyl peroxypivalate and 130g of butyl acetate in a four-mouth bottle, reacting for 8 hours at 75 ℃ in a nitrogen environment, and closing nitrogen to finish the reaction to obtain the solution containing the fluorine-silicon graft copolymer.
Wherein, the fluorine-silicon monomer 4:
CF3CF2O-(C3F6O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
example 3
Weighing 33g of fluorosilicone monomer 8, 19g of octadecyl acrylate, 4g of 3-chloro-2-hydroxypropyl methacrylate, 2g of methacryloxypropyltrimethylsilane, 1g of tert-butyl peroxypivalate and 130g of butyl acetate in a four-port bottle, reacting for 8 hours at 75 ℃ in a nitrogen environment, and closing the nitrogen to finish the reaction to obtain the solution containing the fluorosilicone graft copolymer.
Wherein, the fluorine silicon monomer is 8:
CF3CF2O-(C2F4O)20-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
example 4
Weighing 33g of fluorosilicone monomer 9, 19g of isobornyl methacrylate, 4g of 3-chloro-2-hydroxypropyl methacrylate, 2g of vinyltrimethoxysilane, 1g of tert-butyl peroxypivalate and 130g of butyl acetate in a four-mouth bottle, reacting for 8 hours at 75 ℃ in a nitrogen environment, and closing nitrogen to finish the reaction to obtain the solution containing the fluorine-silicon graft copolymer.
Wherein, the fluorine silicon monomer 9:
CF3CF2O-(CF2O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
example 5
Weighing 33g of fluorosilicone monomer 10, 19g of isobornyl methacrylate, 4g of 3-chloro-2-hydroxypropyl methacrylate, 2g of vinyltrimethoxysilane, 1g of tert-butyl peroxypivalate and 130g of butyl acetate in a four-mouth bottle, reacting for 8 hours at 75 ℃ in a nitrogen environment, and closing nitrogen to finish the reaction to obtain the solution containing the fluorine-silicon graft copolymer.
Wherein, the fluorine silicon monomer 10:
CF3CF2CF2O-(C4F8O)2-(C3F6O)2-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
example 6
Weighing 33g of fluorosilicone monomer 8, 19g of isobornyl methacrylate, 4g of 3-chloro-2-hydroxypropyl methacrylate, 2g of vinyltrimethoxysilane, 1g of tert-butyl peroxypivalate and 130g of butyl acetate in a four-mouth bottle, reacting for 8 hours at 75 ℃ in a nitrogen environment, and closing nitrogen to finish the reaction to obtain the solution containing the fluorine-silicon graft copolymer.
Wherein, the fluorine silicon monomer is 8:
CF3CF2O-(C2F4O)20-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
the fluorosilicone monomers of examples 2-6 were prepared according to the method of fluorosilicone monomer 2 described in example 1.
Comparative example 1
Weighing CF3(CF2)5-CH2-CH2-O-(C＝O)-CH＝CH233g of isobornyl methacrylate, 19g of isobornyl methacrylate, 4g of 3-chloro-2-hydroxypropyl methacrylate, 2g of vinyltrimethoxysilane, 1g of tert-butyl peroxypivalate and 130g of butyl acetate are put in a four-mouth bottle to react for 8 hours at 75 ℃ in a nitrogen environment, and the reaction is finished by closing the nitrogen, thus obtaining the solution containing the fluorine-silicon graft copolymer.
Examples of the experiments
The products obtained in examples 1 to 6 and the product obtained in comparative example 1 were subjected to performance tests, and the fabric was treated as follows.
Firstly, processing the cloth
The finishing process of the cloth comprises the following steps: the fluorosilicone graft copolymer solutions prepared in examples 1 to 6 and comparative example 1 were diluted with ethyl acetate to give a 0.15% dilution, and the prepared dilutions were used to soak cotton cloth for 1min, and then the cotton cloth was taken out and blown with a blower for 15min to obtain test cloths.
Second, performance test
(I) testing waterproof performance
Spray water testing was performed according to AATCC-22. The spray resistance is expressed in water resistance rating. The suffix "+" attached to the data means that the performance is slightly better than the performance of the grade of the numerical characterization, and the suffix "-" means that the performance is slightly inferior to the performance of the grade of the numerical characterization. The evaluation criteria are shown in Table 1.
TABLE 1
(II) oil repellency test
The oil repellency was tested according to AATCC-TM118 by dropping a corresponding grade of oil onto the fabric and observing penetration within 30 seconds, the highest oil penetration was the oil repellency grade of the water repellent and the standard rating is given in Table 2.
TABLE 2
| Grade | Evaluation criteria |
| 1 | Medical lubricating oil |
| 2 | Mixed solution of 35 parts hexadecane and 65 parts medical lubricating oil |
| 3 | Hexadecane (Hexadecane) |
| 4 | Tetradecane |
| 5 | Dodecane |
| 6 | N-decane |
| 7 | N-octane |
| 8 | N-heptane |
The results of the performance tests on the products obtained in examples 1 to 6 and the product obtained in comparative example 1 are shown in Table 3.
TABLE 3
| Numbering | Water resistance rating | Oil repellency rating |
| Example 1 | 5 | 6 |
| Example 2 | 5 | 7 |
| Practice ofExample 3 | 5 | 5 |
| Example 4 | 5 | 5 |
| Example 5 | 4++ | 4 |
| Example 6 | 4++ | 4 |
| Comparative example 1 | 4 | 3 |
As can be seen from the data in Table 3, the products prepared by the embodiments of the invention have good water and oil proofing effects, and the comparison ratio is obviously improved. The products of examples 1 to 6 can be used as excellent water-and oil-repellent agents and can be applied to water-and oil-repellent treatments of various fiber products, nonwoven fabrics, stone materials, concrete, leather surface substrates, and the like.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (12)
1. A fluorine-silicon graft copolymer is characterized by comprising the following raw materials:
(1) a fluorosilicone monomer of formula (I):
A-O-Rf-B-CH2-O-M-Si-(N-CH＝CH2)3formula (I)
In the formula (I), A is C substituted by 1 or more fluorine atoms1～16A linear alkyl group;
rf represents- (C)4F8O)a-(C3F6O)b-(C2F4O)c-(CF2O)d-, wherein a, b, c and d each independently represent an integer of 0 to 200, and the sum of a, b, c and d is at least 1;
b is C substituted by 1 or more fluorine atoms1～6A linear alkylene chain of (a);
m, N are each independently selected from C1～6A straight alkylene chain of (A) or (C)2～6A branched alkylene chain of (a);
(2) a fluorine-free (meth) acrylate monomer,
(3) a monomer containing active hydrogen and a monomer containing active hydrogen,
(4) an organosiloxane.
2. The fluorosilicone graft copolymer according to claim 1, wherein in the formula (I), A is C substituted with 3 to 7 fluorine atoms1～3A linear alkyl group; a. the sum of b, c and d is 4-40; b is C substituted by 2-6 fluorine atoms1～3A linear alkylene chain of (a); m, N are each independently selected from C1～3A linear alkylene chain of (a);
preferably, the fluorosilicone monomer is selected from the following compounds:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2CH2-CH＝CH2)3
CF3O-(C4F8O)10-(C3F6O)10-(CF2O)10-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C2F4O)20-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(CF2O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)2-(C3F6O)2-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3。
3. the fluorosilicone graft copolymer of claim 1, wherein the fluorine-free (meth) acrylate monomer is according to formula (II):
wherein, X1Is a hydrogen atom or a methyl group;
X2is C1～C22Linear hydrocarbon group of (2), or C3～C22With branched hydrocarbon radicals or C3～C22The ring is an aromatic ring or an aliphatic ring.
4. The fluorosilicone graft copolymer of claim 3, wherein the fluorine-free (meth) acrylate monomer is optionally selected from one or more of methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate.
5. The fluorosilicone graft copolymer of claim 1, wherein the active hydrogen-containing monomer is a (meth) acrylic monomer containing at least one of hydroxyl, amino and mercapto groups, or a double-bond-containing hydroxyl, amino, mercapto monomer, or a diol, diamine, dimercapto monomer, or a monomer containing any two of hydroxyl, amino and mercapto groups;
preferably, the active hydrogen-containing monomer is optionally selected from one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, N-methylolacrylamide, N-hydroxyethyl acrylamide, N-vinylpyrrolidone, diacetone acrylamide, ethylene glycol, ethylene diamine, propylene diamine, hexamethylene diamine, p-phenylene diamine, thiophenol, hydroxylamine, primary amino mercaptan, secondary amino mercaptan, mercaptoethanol.
6. The fluorosilicone graft copolymer according to claim 1, wherein the organosiloxane is an organosiloxane containing at least one of an amino group, a mercapto group, and a double bond, which is capable of undergoing a polymerization reaction with an acrylate;
preferably, the organic siloxane is one or more selected from vinyl trimethoxy silane, vinyl triethoxy silane, amino propyl triethoxy silane, mercaptopropyl trimethoxy silane, methacryloxypropyl trimethyl silane, vinyl silicone oil and hydrogen-containing silicone oil.
7. The fluorosilicone graft copolymer of claim 1, wherein the fluorosilicone monomer is selected from the group consisting of:
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C3F6O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-CF2-CH2-O-CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)20-(C3F6O)20-CF2CF2-CH2-O-CH2CH2-Si-(CH2CH2-CH＝CH2)3
CF3O-(C4F8O)10-(C3F6O)10-(CF2O)10-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(C2F4O)20-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2O-(CF2O)20-CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3
CF3CF2CF2O-(C4F8O)2-(C3F6O)2-CF2CF2-CH2-O-CH2CH2CH2-Si-(CH2-CH＝CH2)3；
the fluorine-free (methyl) acrylate monomer is octadecyl acrylate and/or isobornyl methacrylate;
the active hydrogen-containing monomer is methacrylic acid-3-chloro-2-hydroxypropyl ester and/or mercaptoethanol;
the organic siloxane is vinyl trimethoxy silane and/or methacryloxypropyl trimethyl silane.
8. The fluorosilicone graft copolymer according to any one of claims 1 to 7, wherein the mass ratio of the fluorosilicone monomer to the fluorine-free (meth) acrylate monomer to the active hydrogen-containing monomer to the organosiloxane is (9 to 40): (2-20): (0.5-5): (0.5 to 5);
preferably, the mass ratio of the fluorine-silicon monomer to the fluorine-free (methyl) acrylate monomer to the active hydrogen-containing monomer to the organic siloxane is (12-33): (6-20): (0.5-4): (0.5 to 4).
9. A surface treatment agent comprising the fluorosilicone graft copolymer according to any one of claims 1 to 8.
10. The surface treatment agent according to claim 9, characterized in that the surface treatment agent further comprises a solvent;
preferably, the solvent is at least one selected from ethyl acetate, butyl acetate, n-hexane, n-heptane, petroleum ether, hexafluoropropylene trimer, perfluorohexanone, hydrofluoroether.
11. Use of the surface treatment agent according to claim 9 or 10 in water-and oil-repellent treatment.
12. Use according to claim 11, in the water and oil repellent treatment of fibre products, non-woven fabrics, stone, concrete, leather.
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| CN112574428A (en) * | 2020-12-16 | 2021-03-30 | 济南大学 | Hyperbranched fluorine-containing silicon high-temperature-resistant release agent and application thereof |
| CN112646062A (en) * | 2020-12-18 | 2021-04-13 | 浙江理工大学 | Preparation method and application of temperature response type fabric finishing agent |
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