阅读说明：本技术 一种采用水解内循环工艺制备有机硅树脂的方法 (Method for preparing organic silicon resin by adopting hydrolysis internal circulation process ) 是由 胡磊杰 胡孟进 于 2019-10-25 设计创作，主要内容包括：本发明属于树脂合成领域,特别涉及一种采用水解内循环工艺制备有机硅树脂的方法,本发明方法采用将水解,水洗,以及水洗分离产生的废酸水送入添加有活泼碱性物质的中和器进行中和后在进入分离器进行分离的内循环工艺,将分离后的二级循环水再次用于水解,水洗工艺,仅将分离后的含盐废水排放,该工艺大大节省了排污处理费用,又节省了原料循环水,且制得的有机硅树脂性能不受影响。(The invention belongs to the field of resin synthesis, and particularly relates to a method for preparing organic silicon resin by adopting a hydrolysis internal circulation process.)

1. A method for preparing organic silicon resin by adopting a hydrolysis internal circulation process is characterized by comprising the following steps:

(1) preparing raw materials according to a proportion;

the raw materials comprise basic organic silicon monomers, special organic silicon monomers and organic solvents;

(2) hydrolysis: fully mixing the organosilicon monomers in the step (1) in proportion, and adding the mixture into an organic solvent for co-hydrolysis;

(3) after hydrolysis, washing with water, separating by washing with water, then adding a catalyst for telomerization and polycondensation, adding a regulator to reduce the degree of gelation, and regulating the mass fraction of the silicone resin solution to 50% to obtain the silicone resin;

wherein, the waste acid water generated by hydrolysis, water washing and water washing separation in the step (2) and the step (3) adopts an internal circulation process, and secondary circulating water is used for the hydrolysis and water washing process again.

2. The method for preparing the silicone resin by adopting the hydrolysis internal circulation process as claimed in claim 1, wherein the basic silicone monomer in step (1) is: monomethyltrichlorosilane (M1), dimethyldichlorosilane (M2), monophenyltrichlorosilane (P1), diphenyldichlorosilane (P2); the special organic silicon monomer is as follows: one or more organosilicon monomer materials of organosilicon monomer containing double bond group, organosilicon monomer containing active hydrogen and silane coupling agent; the organic solvent is: cyclohexanone, butanone, ethyl acetate or butyl ethyl ether.

3. The method for preparing silicone resin by hydrolysis internal recycle process according to claim 2, wherein the silicone monomer containing double bond group is methyl vinyl dichlorosilane, the silicone monomer containing active hydrogen is methyl hydrogen dichlorosilane, the silane coupling agent is epoxy group-containing triethoxysilane, ester group-containing triethoxysilane, and amine group-containing triethoxysilane, acryl group-containing triethoxysilane.

4. The method for preparing the organic silicon resin by adopting the hydrolysis internal circulation process as claimed in claim 1, wherein in the total organic silicon monomer, the ratio of the number of the organic groups R on the silicon atoms to the number of the silicon atoms, R/Si is 1.0-1.6, the number of the phenyl groups accounts for 15-60% of the total number of R, and the mass of the special organic silicon monomer accounts for 10-40% of the total mass of the organic silicon monomer; the dosage of the organic solvent is 2-4 times of the mass of the water; the water amount is 1-2 times of the total mass of the organic silicon monomer.

5. The method for preparing the silicone resin by adopting the hydrolysis internal circulation process as claimed in claim 1, wherein the internal circulation process is as follows: and (3) feeding the waste acid water generated by hydrolysis, water washing and water washing separation into a neutralizer added with active alkaline substances for neutralization, then feeding the neutralized waste acid water into a separator for separation, and reusing the separated secondary circulating water for hydrolysis and water washing, wherein only the separated salt-containing wastewater is discharged.

6. The method for preparing the organic silicon resin by adopting the hydrolysis internal circulation process as claimed in claim 5, wherein the active alkaline substance is strong alkali inorganic base, Lewis base, hydroxylamine or strong alkali ion exchange resin.

7. The method for preparing the organic silicon resin by adopting the hydrolysis internal circulation process as claimed in claim 1, wherein the co-hydrolysis temperature is 4-10 ℃.

8. The method for preparing the organic silicon resin by adopting the hydrolysis internal circulation process as claimed in claim 1, wherein the added catalyst is a transition metal salt catalyst, and the dosage of the transition metal salt catalyst is 1 per thousand to 2 per thousand of the total mass of the organic silicon monomer; the added regulator is organosilicon oligomer with hydroxyl, epoxy or ester group, and the dosage of the organosilicon oligomer is 20-30% of the total mass of the organosilicon monomer.

Technical Field

The invention belongs to the field of resin synthesis, and particularly relates to a method for preparing organic silicon resin by adopting a hydrolysis internal circulation process.

Background

The organic silicon resin is an important member in the organic silicon material, is different from the linear structure of the organic silicon rubber and the small molecular weight of the silicon oil and the silane, is a three-dimensional net structure, and has the basic properties of the organic silicon material, such as high temperature resistance, low temperature resistance, high insulation, weather resistance, radiation resistance, chemical resistance, hydrophobicity and the like.

The prior preparation method of the organic silicon resin comprises the following processes: firstly, mixing metered organic silicon monomers with an aqueous solution containing an organic solvent, carrying out hydrolysis reaction, and washing and separating after hydrolysis is finished; then, the organic silicon resin is obtained after telomerization and concentration adjustment. Among the prior art, all can produce a large amount of waste acid water in the separation process of hydrolysising, washing to and washing, the waste acid water of discharging on the one hand can produce environmental pollution, and on the other hand carries out the manufacturing cost of the increase enterprise that aftertreatment can be great to the waste acid water of discharging.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides a novel method for preparing organic silicon resin by adopting a hydrolysis internal circulation process. The method adds a neutralization and separation process in the process of preparing the organic silicon resin, neutralizes waste acid water generated in the processes of hydrolysis, water washing and water washing separation in a neutralizer, then separates the waste acid water by a separator to form waste salt water after separation, the discharge amount of the waste salt water is greatly reduced, and the separated secondary water can be recycled.

The method for preparing the organic silicon resin by adopting the hydrolysis internal circulation process comprises the following specific process steps:

(1) preparing raw materials according to a proportion;

wherein, the raw materials for synthesizing the organic silicon resin are as follows:

basic silicone material monomer: monomethyltrichlorosilane (M1), dimethyldichlorosilane (M2), monophenyltrichlorosilane (P1), diphenyldichlorosilane (P2);

wherein, the purity of the methyl trichlorosilane is more than 99 percent;

dimethyldichlorosilane with purity of more than 99.9%;

mono-phenyl trichlorosilane, purity > 99%;

the purity of the diphenyl dichlorosilane is more than 97 percent;

special organosilicon monomer: can be as follows: one or more than one organic silicon monomer material of organic silicon monomer containing double bond group, organic silicon monomer containing active hydrogen or silane coupling agent.

Wherein, the organosilicon monomer containing double bond group can be methyl vinyl dichlorosilane;

the organosilicon monomer containing active hydrogen can be methyl hydrogen dichlorosilane;

the silane coupling agent is: epoxy-containing triethoxysilane, ester-containing triethoxysilane, and amino-and acryloyl-containing triethoxysilane.

The organic solvent is: ketone, ether or lipid solvents.

In the total organosilicon monomers, the ratio of the number of organic groups R on silicon atoms to the number of silicon atoms, R/Si is 1.0-1.6, the number of phenyl groups accounts for 15-60% of the total number of R, and the mass of the special organosilicon monomers accounts for 10-40% of the total mass of the organosilicon monomers.

The organic solvent may specifically be: cyclohexanone, butanone, ethyl acetate or butyl ether, wherein the amount of the organic solvent is 2-4 times of the mass of the water;

the water amount is 1-2 times of the total mass of the organic silicon monomer.

(2) Hydrolysis: fully mixing the organic silicon monomers in proportion, and then adding the mixture into an organic solvent for co-hydrolysis;

the cohydrolysis temperature is 4-10 ℃.

(3) And after the hydrolysis is finished, washing with water, separating by washing with water, then adding a catalyst for telomerization and polycondensation, adding a regulator to reduce the degree of gelation, and regulating the mass fraction of the silicone resin solution to 50% to obtain the silicone resin.

Wherein the added catalyst is a transition metal salt catalyst, specifically platinum chloride, cobalt naphthenate, lead acetate or zinc acetate, and the dosage of the catalyst is 1-2 per mill of the total mass of the organosilicon monomer.

The added regulator is organosilicon oligomer with hydroxyl, epoxy or ester group, and the dosage of the organosilicon oligomer is 20-30% of the total mass of the organosilicon monomer.

Wherein, the waste acid water generated by hydrolysis, washing and washing separation in the step (2) and the step (3) adopts an internal circulation process, and secondary circulating water is used for the hydrolysis and washing process again; the internal circulation process specifically comprises the following steps: feeding waste acid water generated by hydrolysis, water washing and water washing separation into a neutralizer added with active alkaline substances for neutralization, then feeding the neutralized waste acid water into a separator for separation, wherein the separated secondary circulating water is used for hydrolysis, the water washing process is adopted, and the separated salt-containing wastewater is discharged.

Wherein the active alkaline substance is strong alkali inorganic base, Lewis base, hydroxylamine or strong alkali ion exchange resin.

Has the advantages that:

(1) the method has the advantages that the waste acid water generated in the organic silicon resin production process in the prior art is completely discharged or is subjected to post-treatment, and the generated waste acid water is sent into a neutralizer added with active alkaline substances for neutralization and then is treated in the process flow of separation in a separator, so that the pollution discharge treatment cost is greatly saved, and the raw material circulating water is also saved.

(2) The organic silicon resin is prepared by the internal circulation process, the post-treatment of acid water is not needed, only a trace amount of salt-containing wastewater is generated, the requirements of energy conservation and emission reduction are met, the production cost is reduced, and the performance of the prepared organic silicon resin is not influenced.

Drawings

FIG. 1 is a flow chart of the hydrolysis internal circulation process of the present invention.

Detailed Description

The present invention will be described in detail with reference to examples.