阅读说明：本技术 一种含硅的织物用无氟疏水易去污剂水溶性共聚物及其共聚方法 (Fluorine-free hydrophobic easy-detergent water-soluble copolymer for silicon-containing fabric and copolymerization method thereof ) 是由 徐秀峰 于 2019-10-31 设计创作，主要内容包括：本发明公开了一种含硅的织物用无氟疏水易去污剂水溶性共聚物及其共聚方法,其含有以下组分,带共轭双键的亲水性单体,包含N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、或者是由通式CH<Sub>2</Sub>＝CX<Sup>1</Sup>C(C＝O)-O-(RO)<Sub>n</Sub>-X<Sup>2</Sup>和CH<Sub>2</Sub>＝CX<Sup>1</Sup>C(C＝O)-O-(RO)<Sub>n</Sub>-C(＝O)CX<Sup>1</Sup>＝CH<Sub>2</Sub>表示的氧亚烷基(甲基)丙烯酸酯或氧亚烷基二(甲基)丙烯酸酯中的至少一种,其中X1是氢原子或甲基,X2是氢原子或者饱和或不饱和的C1-C22烃基,R是C2-C6亚烷基,且n是1-10的整数。该含硅的织物用无氟疏水易去污剂水溶性共聚物利用聚硅氧烷链段的柔软特性,改善经防水防油剂处理的织物手感。(The invention discloses a water-soluble copolymer of fluorine-free hydrophobic soil release agent for silicon-containing fabric and a copolymerization method thereof, wherein the water-soluble copolymer comprises a hydrophilic monomer with conjugated double bonds, and the hydrophilic monomer comprises N-vinyl pyrrolidone, N-vinyl caprolactam or a general formula of CH 2 ＝CX 1 C(C＝O)‑O‑(RO) n ‑X 2 And CH 2 ＝CX 1 C(C＝O)‑O‑(RO) n ‑C(＝O)CX 1 ＝CH 2 Of oxyalkylene (meth) acrylate or oxyalkylene di (meth) acrylate represented byAt least one, wherein X1 is a hydrogen atom or a methyl group, X2 is a hydrogen atom or a saturated or unsaturated C1-C22 hydrocarbon group, R is a C2-C6 alkylene group, and n is an integer of 1 to 10. The fluorine-free hydrophobic soil release agent-facilitating water-soluble copolymer for the silicon-containing fabric utilizes the soft characteristic of a polysiloxane chain segment to improve the hand feeling of the fabric treated by the waterproof and oil-proof agent.)

1. A fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics, which is characterized in that: which comprises the following components in percentage by weight,

hydrophilic monomers with conjugated double bonds, containing N-vinylpyrrolidone, N-vinylcaprolactam or of the formula CH₂＝CX¹C(C＝O)-O-(RO)_n-X²And CH₂＝CX¹C(C＝O)-O-(RO)_n-C(＝O)CX¹＝CH₂At least one of oxyalkylene (meth) acrylates or oxyalkylene di (meth) acrylates represented by (i) wherein X1 is a hydrogen atom or a methyl group, X2 is a hydrogen atom or a saturated or unsaturated C1-C22 hydrocarbon group, R is a C2-C6 alkylene group, and n is an integer of 1 to 10;

from the general formula CH₂＝CX¹C(C＝O)-O-R¹-Si(X²)(X³)X⁴A terminal methylpolysiloxane alkyl acrylate of the formula, wherein X¹Is a hydrogen atom or a methyl group, R¹Is C2-C6 alkylene, X²，X³，X⁴Represented by the general formula- (O-Si (CH)₃)₂)_nCH₃N is an integer of 0 to 6, X²，X³，X⁴May be the same or different groups;

the functional monomer is one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl acrylamide, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-isobutoxy acrylamide, hydroxyoctyl acrylate, isocyanato acrylate, acetoacetoxyethyl methacrylate and glycidyl methacrylate.

2. The fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics according to claim 1, characterized in that: the anti-rust paint also comprises the following components,

chain transfer agents including one or more of alkyl mercaptans (dodecyl mercaptan, octadecyl mercaptan, octyl mercaptan, etc.) aminoethanethiol, mercaptoethanol, thioglycolic acid, and 2-mercaptopropionic acid Zhang-Kong;

oil-soluble initiators, peroxides or azo compounds.

3. The fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics according to claim 2, characterized in that: the perhydride is one or more of benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tert-butyl peroxypivalate, and the azo compound is one or more of 2, 2-azobisisobutyronitrile, 4, 4-azobis (4-cyanovaleric acid) and azodicarbonamide.

4. A polymerization method of fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabric is characterized in that: comprises the following steps of (a) carrying out,

firstly, introducing a certain weight part of methyl ethyl ketone serving as a solvent into a reaction vessel provided with a stirrer, a thermometer, a reflux condenser tube, a dropping funnel, a nitrogen inlet and a heater according to a formula ratio; then, the general formula CH weighed according to the formula proportion is stirred₂＝CX¹C(C＝O)-O-R¹-Si(X²)(X³)X⁴The terminal methyl polysiloxane alkyl acrylate, the hydrophilic monomer with conjugated double bond, and the likeAdding an functional monomer, a chain transfer agent and an oil-soluble initiator into a reactor in sequence to obtain a mixture; further stirring the mixture at 50-80 ℃ for 8-16 hours under the protection of nitrogen to complete copolymerization, and cooling to room temperature to obtain a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure to obtain a copolymer body.

5. The method of polymerizing the fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics according to claim 4, wherein: comprises the following steps of (a) carrying out,

first, 100 parts by weight of methyl ethyl ketone as a solvent was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater; thereafter, 60 parts of CH are added under stirring₂＝C(CH₃)C(C＝O)-O-(CH₂)₃-Si(CH₂)₂(OSi(CH₂)₂)₃CH₃20 parts of N-vinyl-2-pyrrolidone, 8 parts of hydroxybutyl acrylate, 0.05 part of lauryl mercaptan and 1 part of an oil-soluble initiator 4, 4-azobis (4-cyanovaleric acid) and azodicarbonamide were added to a reactor in this order to obtain a mixture; the mixture was further stirred at 60 ℃ for 12 hours under nitrogen protection to complete copolymerization and cooled to room temperature to give a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure (1000pa/25 ℃ C.) to obtain a copolymer body.

6. The method of polymerizing the fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics according to claim 4, wherein: comprises the following steps of (a) carrying out,

first, 100 parts by weight of methyl ethyl ketone as a solvent was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater; thereafter, 60 parts of CH are added under stirring₂＝C(CH₃)C(C＝O)-O-(CH₂)₃-Si(CH₂)₂(OSi(CH₂)₂)₃CH₃20 parts of CH₂＝CHC(C＝O)-O-(CH2O)₅H, 8 parts of hydroxybutyl acrylate, 0.05 part of lauryl mercaptan and 1 part of oil-soluble initiators 4, 4-azobis (4-cyanovaleric acid) and azodicarbonamide were added to a reactor in order to obtain a mixture; the mixture was further stirred at 60 ℃ for 12 hours under nitrogen protection to complete copolymerization and cooled to room temperature to give a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure (1000pa/25 ℃ C.) to obtain a copolymer body.

7. The method of polymerizing the fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics according to claim 4, wherein: comprises the following steps of (a) carrying out,

first, 100 parts by weight of Methyl Ethyl Ketone (MEK) as a solvent was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater; thereafter, 60 parts of CH are added under stirring₂＝C(CH₃)C(C＝O)-O-(CH₂)₃-Si(OSi(CH₃)₃)₃20 parts of CH₂＝CHC(C＝O)-O-(CH2O)₅H, 8 parts of hydroxybutyl acrylate, 0.05 part of lauryl mercaptan and 1 part of oil-soluble initiators 4, 4-azobis (4-cyanovaleric acid) and azodicarbonamide were added to a reactor in order to obtain a mixture; the mixture was further stirred at 60 ℃ for 12 hours under nitrogen protection to complete copolymerization and cooled to room temperature to give a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure (1000pa/25 ℃ C.) to obtain a copolymer body.

8. An aqueous solution of a hydrophobic soil release agent, which is prepared by mixing a polymer bulk polymerized by the polymerization method of the fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabric according to any one of claims 3 to 7 with deionized water.

9. The application of a fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics is characterized in that: the detergent is used for processing fabrics and has the effect of easy decontamination.

The technical field is as follows:

the invention relates to the field of detergents, in particular to a fluorine-free hydrophobic detergent-susceptible water-soluble copolymer for silicon-containing fabrics and a copolymerization method thereof.

Background art:

soil release refers to the ability of a fabric to remove stains more easily during a subsequent washing process or wiping process after the fabric has been stained with the stains (both aqueous and oily stains). And the chemical which realizes the soil release function is called as soil release agent. Currently common soil release agents include; 1. hydrophobic and oleophobic easy-to-decontaminate emulsion containing a fluorinated polyurethane structure (high cost and general easy-to-decontaminate effect); 2. the water solution containing the fluorine acrylate structure, hydrophobic and oleophobic easy detergent (high cost, hard hand feeling and washing tolerance); 3. the polyether modified polyester structure is a hydrophilic detergent-easy aqueous solution (without hydrophobicity).

The invention content is as follows:

the technical problem to be solved by the invention is to provide a fluorine-free hydrophobic soil release agent-prone water-soluble copolymer for silicon-containing fabrics, which utilizes the soft characteristic of a polysiloxane chain segment to improve the hand feeling of fabrics treated by a waterproof and oil-proof agent, wherein the fluorine-free hydrophobic soil release agent-prone water-soluble copolymer for silicon-containing fabrics utilizes the hydrophobicity of a silicon-containing group to enhance the inversion effect (flip-flop effect) -which means that a polymer coexisting with a hydrophobic group and a hydrophilic group, when the surface is contacted with air, the hydrophobic group stretches and the hydrophilic group curls to embody the hydrophobicity, and when the surface is contacted with water, the hydrophilic group stretches and the hydrophobic group curls to embody the hydrophilicity, so that stains can be taken away from the surface of the fabrics through the water; the characteristic that the silicon-containing groups reduce the friction coefficient of the fiber is utilized, the friction impact of water on the fabric treated by the detergent is reduced when the fabric is washed by water, and the water washing resistance is further improved.

The technical proposal of the invention is to provide a fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for silicon-containing fabrics, which comprises the following components,

hydrophilic monomers with conjugated double bonds, containing N-vinylpyrrolidone, N-vinylcaprolactam or of the formula CH₂＝CX¹C(C＝O)-O-(RO)_n-X²And CH₂＝CX¹C(C＝O)-O-(RO)_n-C(＝O)CX¹＝CH₂At least one of oxyalkylene (meth) acrylates or oxyalkylene di (meth) acrylates represented by (i) wherein X1 is a hydrogen atom or a methyl group, X2 is a hydrogen atom or a saturated or unsaturated C1-C22 hydrocarbon group, R is a C2-C6 alkylene group, and n is an integer of 1 to 10;

from the general formula CH₂＝CX¹C(C＝O)-O-R¹-Si(X²)(X³)X⁴A terminal methylpolysiloxane alkyl acrylate of the formula, wherein X¹Is a hydrogen atom or a methyl group, R¹Is C2-C6 alkylene, X²，X³，X⁴Represented by the general formula- (O-Si (CH)₃)₂)_nCH₃N is an integer of 0 to 6, X²，X³，X⁴May be the same or different groups;

the functional monomer is one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl acrylamide, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-isobutoxy acrylamide, hydroxyoctyl acrylate, isocyanato acrylate, acetoacetoxyethyl methacrylate and glycidyl methacrylate.

Preferably, the chain transfer agent comprises one or more of alkyl mercaptan (dodecyl mercaptan, octadecyl mercaptan, octyl mercaptan, etc.), aminoethanethiol, mercaptoethanol, thioglycolic acid, and 2-mercaptopropionic acid;

oil-soluble initiators, peroxides or azo compounds.

Wherein, the perhydride is one or more of benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tert-butyl peroxypivalate, and the azo compound is one or more of 2, 2-azo-bis-isobutyronitrile, 4, 4-azo-bis (4-cyano-valeric acid) and azodicarbonamide.

The invention also provides a polymerization method of the fluorine-free hydrophobic soil release agent-susceptible water-soluble copolymer for the silicon-containing fabric, which comprises the following steps,

firstly, a certain weight part of Methyl Ethyl Ketone (MEK) is taken as a solvent to be introduced into a reaction vessel which is provided with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet and a heater according to the formula proportion; then, the general formula CH weighed according to the formula proportion is stirred₂＝CX¹C(C＝O)-O-R¹-Si(X²)(X³)X⁴Terminal methyl polysiloxane alkyl acrylic acidAdding ester, hydrophilic monomer with conjugated double bond, functional monomer, chain transfer agent and oil-soluble initiator into a reactor in sequence to obtain a mixture; further stirring the mixture at 50-80 ℃ for 8-16 hours under the protection of nitrogen to complete copolymerization, and cooling to room temperature to obtain a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure to obtain a copolymer body.

On the basis, a certain amount of deionized water is added to obtain a hydrophobic detergent-easy aqueous solution with corresponding effective content.

As a preferable mode, first, 100 parts by weight of methyl ethyl ketone as a solvent was introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater; thereafter, 60 parts of CH are added under stirring₂＝C(CH₃)C(C＝O)-O-(CH₂)₃-Si(CH₂)₂(OSi(CH₂)₂)₃CH₃20 parts of N-vinyl-2-pyrrolidone, 8 parts of hydroxybutyl acrylate, 0.05 part of lauryl mercaptan and 1 part of an oil-soluble initiator 4, 4-azobis (4-cyanovaleric acid) and azodicarbonamide were added to a reactor in this order to obtain a mixture; the mixture was further stirred at 60 ℃ for 12 hours under nitrogen protection to complete copolymerization and cooled to room temperature to give a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure (1000pa/25 ℃ C.) to obtain a copolymer body. And finally, 208 parts of deionized water is added to obtain a hydrophobic detergent-susceptible aqueous solution with the effective content of 30%.

As still another preferable mode, first, 100 parts by weight of methyl ethyl ketone as a solvent is introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater; thereafter, 60 parts of CH are added under stirring₂＝C(CH₃)C(C＝O)-O-(CH₂)₃-Si(CH₂)₂(OSi(CH₂)₂)₃CH₃20 parts of CH₂＝CHC(C＝O)-O-(CH2O)₅H, 8 parts of hydroxybutyl acrylate, 0.05 part of lauryl mercaptan and 1 part of oil-soluble initiatorAdding a hair agent 4, 4-azobis (4-cyanovaleric acid) and azodicarbonamide to a reactor in sequence to obtain a mixture; the mixture was further stirred at 60 ℃ for 12 hours under nitrogen protection to complete copolymerization and cooled to room temperature to give a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure (1000pa/25 ℃ C.) to obtain a copolymer body. And finally, 208 parts of deionized water is added to obtain a hydrophobic detergent-susceptible aqueous solution with the effective content of 30%.

As still another preferable mode, first, 100 parts by weight of Methyl Ethyl Ketone (MEK) as a solvent is introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, a nitrogen inlet, and a heater; thereafter, 60 parts of CH are added under stirring₂＝C(CH₃)C(C＝O)-O-(CH₂)₃-Si(OSi(CH₃)₃)₃20 parts of CH₂＝CHC(C＝O)-O-(CH2O)₅H, 8 parts of hydroxybutyl acrylate, 0.05 part of lauryl mercaptan and 1 part of oil-soluble initiators 4, 4-azobis (4-cyanovaleric acid) and azodicarbonamide were added to a reactor in order to obtain a mixture; the mixture was further stirred at 60 ℃ for 12 hours under nitrogen protection to complete copolymerization and cooled to room temperature to give a copolymer solution; then, the methyl ethyl ketone solvent in the copolymer solution was removed by distillation under reduced pressure (1000pa/25 ℃ C.) to obtain a copolymer body. And finally, 208 parts of deionized water is added to obtain a hydrophobic detergent-susceptible aqueous solution with the effective content of 30%.

Furthermore, the invention also provides a hydrophobic soil release agent aqueous solution which is prepared by mixing the polymer body polymerized by the polymerization method of the fluorine-free hydrophobic soil release agent water-soluble copolymer for the silicon-containing fabric and water. The mixing proportion is adjusted according to requirements.

Furthermore, the water-soluble copolymer of the fluorine-free hydrophobic soil release agent for the silicon-containing fabric can be used for fabric processing to ensure that the fabric has a soil release effect.

Compared with the prior art, the invention has the following advantages after adopting the scheme: a novel silicon-containing fluorine-free hydrophobic easy-to-clean water-soluble copolymer solution is synthesized by using a hydrophilic monomer with a conjugated double bond and terminal methyl polysiloxane acrylate on the traditional fabric, so that the soft characteristic of a polysiloxane chain segment is utilized to improve the hand feeling of the fabric treated by the waterproof and oil-proof agent; and the hydrophobicity of the silicon-containing group is utilized to enhance the inversion effect (flip-flop effect) -which means that the polymer coexists with the hydrophobic group and the hydrophilic group, when the surface is in contact with the air, the hydrophobic group stretches and the hydrophilic group curls to embody the hydrophobicity, and when the surface is in contact with the water, the hydrophilic group stretches and the hydrophobic group curls to embody the hydrophilicity, so that the stain can be carried out from the surface of the fabric through the water; meanwhile, the characteristic that the silicon-containing groups reduce the friction coefficient of the fibers is utilized, so that the friction impact of water on the fabric treated by the detergent is reduced when the fabric is washed, and the washing resistance is further improved.

The specific implementation mode is as follows:

the invention is further illustrated with respect to specific embodiments below: