阅读说明：本技术 改性有机聚硅氧烷及其制备方法和应用 (Modified organopolysiloxane and preparation method and application thereof ) 是由 严锦河 陈春江 赵洁 张鹏硕 曹鹤 刘秋艳 任海涛 李献起 刘盛楠 王宝喜 胡质 于 2020-08-04 设计创作，主要内容包括：本发明公开了一种改性有机聚硅氧烷及其制备方法和应用,将端含氢硅油、七甲基三硅氧烷分别与烯丙基聚氧烷基环氧聚醚在铂催化剂的作用下,合成端环氧聚醚改性硅油中间体M和N,然后将端环氧聚醚改性硅油中间体与氨基硅树脂按比例混合后,在促进剂作用下,反应生成树脂化的改性有机聚硅氧烷,产物分子构建于树脂化结构中,因此具有良好的化学稳定性,同时有效降低了反应的活化能,提高反应速率,提高了反应的正向合成率及产物的转化率。本发明所制备改性有机硅聚硅氧烷可以赋予织物优良的舒适效果,且耐洗性好,化学稳定性优良。(The invention discloses a modified organopolysiloxane and a preparation method and application thereof, wherein hydrogen-terminated silicone oil and heptamethyltrisiloxane are respectively mixed with allyl polyoxyalkyl epoxy polyether under the action of a platinum catalyst to synthesize epoxy polyether modified silicone oil intermediates M and N, then the epoxy polyether modified silicone oil intermediates are mixed with amino silicone resin in proportion and reacted under the action of an accelerant to generate resinified modified organopolysiloxane, and product molecules are constructed in a resinified structure, so that the modified organopolysiloxane has good chemical stability, the activation energy of the reaction is effectively reduced, the reaction rate is improved, and the forward synthesis rate of the reaction and the conversion rate of the product are improved. The modified organic silicon polysiloxane prepared by the invention can endow the fabric with excellent comfort effect, good washing fastness and excellent chemical stability.)

1. A modified organopolysiloxane characterized by having a structural formula represented by formula (1),

r has a structure represented by formula (2):

R¹is-CH₃Or a structure represented by formula (3):

2. the modified organopolysiloxane according to claim 1, wherein R is²Is composed of

3. A process for producing the modified organopolysiloxane according to claim 1 or 2, which comprises the steps of:

A. preparation of epoxy-terminated polyether modified silicone oil intermediate M

Dissolving terminal hydrogen-containing silicone oil with the hydrogen content of 0.01-0.08% and allyl polyalkoxy epoxy polyether in an organic solvent, adding a platinum catalyst, reacting at the temperature of 60-110 ℃ for 2-6 hours, and synthesizing a terminal epoxy polyether modified silicone oil intermediate M;

B. preparation of epoxy-terminated polyether modified silicone oil intermediate N

Dissolving heptamethyltrisiloxane and allyl polyalkoxy epoxy polyether in an organic solvent, adding a platinum catalyst, reacting at the temperature of 60-110 ℃ for 2-6 hours, and synthesizing an epoxy-terminated polyether modified silicone oil intermediate N;

C. preparation of modified organopolysiloxanes

Uniformly mixing the epoxy-terminated polyether modified silicone oil intermediate M, the epoxy-terminated polyether modified silicone oil intermediate N and the amino silicone resin, adding an accelerant, and carrying out amination reaction at the reaction temperature of 50-120 ℃ for 4-10 hours to obtain a modified organopolysiloxane product;

the molar ratio of the epoxy-terminated polyether modified silicone oil intermediate M to the epoxy-terminated polyether modified silicone oil intermediate N is 1: 0.5-4, and the molar ratio of the sum of the epoxy groups in the epoxy-terminated polyether modified silicone oil intermediate M and N to the amino group in the amino silicone resin is 1: 0.5-2.

4. The method for preparing modified organopolysiloxane according to claim 3, wherein the molecular weight of allyl polyoxyalkyl epoxy polyether is 300 to 1500, and the structural formula is:

5. the method for preparing modified organopolysiloxane according to claim 3, wherein the organic solvent is isopropanol, t-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or diethylene glycol monoethyl ether, and the amount of the organic solvent added is 10-300% of the weight of the terminal hydrogen-containing silicone oil.

6. The method for preparing modified organopolysiloxane according to claim 3, wherein the molar ratio of Si-H bond in the terminal hydrogen-containing silicone oil to allyl group in the allyl polyalkoxy epoxy polyether in step A is 1: 0.5-2.

7. The method according to claim 3, wherein the molar ratio of heptamethyltrisiloxane to allylpolyoxyalkyl epoxy polyether in step B is 1: 0.5-2.

8. The method for producing a modified organopolysiloxane according to claim 3, wherein the platinum catalyst is chloroplatinic acid or a platinum complex.

9. The method according to claim 3, wherein the aminosilicone is gamma-diethylenetriamine propyl modified silicone, a mixture of N-cyclohexyl-gamma-aminopropyl and gamma-piperazinyl propyl modified silicone, N-dimethylaminopropyl-aminopropyl and gamma-piperazinyl propyl modified silicone, N- (beta-aminoethyl) -gamma-aminopropyl and gamma-piperazinyl propyl modified silicone, or 3-aminopropyl and N-2- (aminoethyl) -3-aminopropyl modified silicone.

10. The method for producing a modified organopolysiloxane according to claim 3, wherein the aminosilicone resin is produced by:

adding 10-50 parts by mass of absolute ethyl alcohol, 10-20 parts by mass of hydrochloric acid with the concentration of 36-37%, 10-50 parts by mass of deionized water and 2-10 parts by mass of hexamethyldisiloxane into a reactor, and stirring for 0.5-1.5 hours at the temperature of 20-50 ℃;

dropwise adding 1-20 parts of a resinification crosslinking agent and 1-20 parts of an aminosilane coupling agent mixed solution, and after dropwise adding, continuously stirring and reacting for 1-3 hours at the temperature of 30-70 ℃;

adding 20-100 parts of hexamethyldisiloxane as an extracting agent for extraction, washing an organic phase to be neutral by using deionized water, and removing the extracting agent and low-boiling-point substances by reduced pressure distillation to obtain amino silicone resin;

wherein the resinified crosslinking agent is tetraethoxysilane, methyl orthosilicate, silicon tetrachloride or mono-methyl trichlorosilane; the aminosilane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, diethylaminomethyltriethoxysilane, gamma-piperazinylpropylmethyldimethoxysilane, N-cyclohexyl-gamma-aminopropylmethyldimethoxysilane, gamma-diethylenetriaminopropylmethyldimethoxysilane or N-dimethylaminopropyl-aminopropylmethyldimethoxysilane.

11. The method according to claim 3, wherein the accelerator in the step C is a tertiary amine compound, the tertiary amine compound is triethanolamine, N-dimethyl-1, 3-propanediamine, tetramethylhexamethylenediamine or tetramethylpropanediamine, and the amount of the tertiary amine compound added is 0.1 to 10% by mass based on the aminosilicone resin.

12. Use of a modified organopolysiloxane according to claim 1 or 2 for the preparation of a textile finish.

Technical Field

The invention belongs to the technical field of organic silicon materials, and particularly relates to modified organopolysiloxane and a preparation method and application thereof.

Background

The fabric softener made of organic silicon is a softener with wide application and good effect on textiles, and the friction between fabric fibers can be effectively reduced because the surface of a silicone oil molecule is uniformly covered by methyl. The modified silicone oil represented by amino silicone oil is the most representative silicone softener variety in the market at present, has excellent performances of smoothness, softness, hydrophobicity, heat resistance, chemical corrosion resistance and the like, has low raw material cost, is non-toxic and pollution-free, and is an important auxiliary agent in the textile industry. In recent years, with the improvement of living standard of people, the requirement on the hand feeling of textiles is higher and higher, the traditional amino silicone oil cannot meet the use requirement, and in order to meet the requirement of high-grade finishing of various fabrics, organic silicon workers research that other active groups such as amide groups, ester groups, cyano groups, carboxyl groups, epoxy groups and the like are introduced into organic silicon molecules to prepare textile finishing agents, so that new characteristics can be endowed to the fabrics. Such as: the introduction of amide group is suitable for antifouling finishing, and the flexibility is greatly improved; the introduced cyano has good oil resistance; after organic fluorine modification, the water repellent oil has the advantages of oil repellency, water repellency, stain resistance, static resistance and the like.

The organic silicon resin is polyorganosiloxane with a highly crosslinked network structure, and the organic silicon resin and modified organic silicon resin products are widely applied to the fields of silicon rubber, paint, sealant and the like due to the characteristics of excellent thermal stability, electric insulation, weather resistance, water resistance, salt mist resistance, mould resistance and the like. However, there are few reports of the use of silicone resins in textile finishes.

Disclosure of Invention

The present invention addresses the above-mentioned technical problems.

In order to achieve the above purpose, the invention is realized by the following technical scheme:

the first aspect of the present invention provides a modified organopolysiloxane having a structural formula represented by formula (1),

r has a structure represented by formula (2):

R¹is-CH₃Or a structure represented by formula (3):

compared with the prior art, the modified organopolysiloxane has the beneficial effects that: the modified organic silicon polysiloxane molecule prepared by the invention is constructed in a resinification structure, has good chemical stability, and introduces polyether group into the silicon resin structure, thereby improving the water solubility of the silicon resin.

Further, R²Is composed ofR³is-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-NH-CH₂-CH₂-NH-CH₂-CH₂-or-CH₂-CH₂-CH₂-NH-CH₂-CH₂One of-EO is-CH 2-CH 2-O-and PO isa is an integer of 0 to 27, b is an integer of 0 to 36, and at least one of a and b is not 0, c is an integer of 1 to 70.

The second aspect of the present invention provides a method for preparing the above modified organopolysiloxane, comprising the steps of:

A. preparation of epoxy-terminated polyether modified silicone oil intermediate M

Dissolving terminal hydrogen-containing silicone oil with the hydrogen content of 0.01-0.08% and allyl polyalkoxy epoxy polyether in an organic solvent, adding a platinum catalyst, reacting at the temperature of 60-110 ℃ for 2-6 hours, and synthesizing a terminal epoxy polyether modified silicone oil intermediate M;

B. preparation of epoxy-terminated polyether modified silicone oil intermediate N

Dissolving heptamethyltrisiloxane and allyl polyalkoxy epoxy polyether in an organic solvent, adding a platinum catalyst, reacting at the temperature of 60-110 ℃ for 2-6 hours, and synthesizing an epoxy-terminated polyether modified silicone oil intermediate N;

C. preparation of modified organopolysiloxanes

Uniformly mixing the epoxy-terminated polyether modified silicone oil intermediate M, the epoxy-terminated polyether modified silicone oil intermediate N and the amino silicone resin, adding an accelerant, and carrying out amination reaction at the reaction temperature of 50-120 ℃ for 4-10 hours to obtain a modified organopolysiloxane product;

the molar ratio of the epoxy-terminated polyether modified silicone oil intermediate M to the epoxy-terminated polyether modified silicone oil intermediate N is 1: 0.5-4, and the molar ratio of the sum of the epoxy groups in the epoxy-terminated polyether modified silicone oil intermediate M and N to the amino group in the amino silicone resin is 1: 0.5-2.

Compared with the prior art, the preparation method adopting the technical scheme has the beneficial effects that:

1) according to the invention, the terminal hydrogen-containing silicone oil and the heptamethyltrisiloxane are respectively mixed with the allyl polyoxyalkyl epoxy polyether under the action of a platinum catalyst to synthesize terminal epoxy polyether modified silicone oil intermediates M and N, then the terminal epoxy polyether modified silicone oil intermediate M, N is mixed with the amino silicone resin in proportion, and then the mixture reacts under the action of an accelerant to generate the resinified modified organopolysiloxane, and the product molecules are built in a resinified structure, so that the reaction has good chemical stability.

2) The polyether group is introduced into the silicone resin structure, so that the water solubility of the silicone resin is improved, the silicone resin can be applied to the field of silicone finishing agents, and the modified silicone polysiloxane prepared by the invention can endow the fabric with excellent comfort effect, good washing fastness and excellent chemical stability.

Furthermore, the molecular weight of the allyl polyoxyalkyl epoxy polyether is 300-1500, and the structural formula is as follows:

further, the organic solvent is isopropanol, tert-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or diethylene glycol monoethyl ether, and the adding amount of the organic solvent is 10-300% of the mass of the hydrogen-terminated silicone oil.

Further, the molar ratio of Si-H bonds in the terminal hydrogen-containing silicone oil to allyl groups in the allyl polyalkoxy epoxy polyether in the step A is 1: 0.5-2.

Furthermore, the molar ratio of the heptamethyltrisiloxane to the allyl polyoxyalkyl epoxy polyether in the step B is 1: 0.5-2.

Further, the platinum catalyst is chloroplatinic acid or a platinum complex.

Further, the amino silicone resin is gamma-diethylenetriamine propyl modified silicone resin, the mixture of N-cyclohexyl-gamma-aminopropyl and gamma-piperazinyl propyl co-modified silicone resin, the mixture of N-dimethylaminopropyl-aminopropyl and gamma-piperazinyl propyl co-modified silicone resin, the mixture of N- (beta-aminoethyl) -gamma-aminopropyl and gamma-piperazinyl propyl co-modified silicone resin or the mixture of 3-aminopropyl and N-2- (aminoethyl) -3-aminopropyl co-modified silicone resin.

Further, the amino silicone resin is prepared by the following method:

adding 10-50 parts by mass of absolute ethyl alcohol, 10-20 parts by mass of hydrochloric acid with the concentration of 36-37%, 10-50 parts by mass of deionized water and 2-10 parts by mass of hexamethyldisiloxane into a reactor, and stirring for 0.5-1.5 hours at the temperature of 20-50 ℃;

dropwise adding 1-20 parts of a resinification crosslinking agent and 1-20 parts of an aminosilane coupling agent mixed solution, and after dropwise adding, continuously stirring and reacting for 1-3 hours at the temperature of 30-70 ℃;

adding 20-100 parts of hexamethyldisiloxane as an extracting agent for extraction, washing an organic phase to be neutral by using deionized water, and removing the extracting agent and low-boiling-point substances by reduced pressure distillation to obtain amino silicone resin;

wherein the resinified crosslinking agent is tetraethoxysilane, methyl orthosilicate, silicon tetrachloride or mono-methyl trichlorosilane; the aminosilane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, diethylaminomethyltriethoxysilane, gamma-piperazinylpropylmethyldimethoxysilane, N-cyclohexyl-gamma-aminopropylmethyldimethoxysilane, gamma-diethylenetriaminopropylmethyldimethoxysilane or N-dimethylaminopropyl-aminopropylmethyldimethoxysilane.

Further, in the step C, the accelerator is a tertiary amine compound, the tertiary amine compound is triethanolamine, N-dimethyl-1, 3-propane diamine, tetramethyl hexane diamine or tetramethyl propane diamine, and the addition amount of the tertiary amine compound is 0.1-10% of the mass of the amino silicone resin.

In the third aspect of the invention, the modified organopolysiloxane is applied to a fabric finishing agent to endow the fabric with excellent thick, smooth and elastic handfeel, and has a better use effect.

Detailed Description

In order that those skilled in the art will better understand the present invention, the following detailed description will be given for clear and complete description of the technical solution of the present invention.