CN111961208B

CN111961208B - Emulsion polymerization method for preparing block silicone oil

Info

Publication number: CN111961208B
Application number: CN202010811282.9A
Authority: CN
Inventors: 沈昌宇; 张生岗; 陈焜
Original assignee: HANGZHOU MEIGAO HUAYI CHEMICAL CO Ltd
Current assignee: HANGZHOU MEIGAO HUAYI CHEMICAL CO Ltd
Priority date: 2020-08-13
Filing date: 2020-08-13
Publication date: 2022-03-11
Anticipated expiration: 2040-08-13
Also published as: CN111961208A

Abstract

The invention relates to an emulsion polymerization method for preparing block silicone oil. Polyether amine reacts with 1,1,3, 3-tetramethyl-1, 3-di [3- (epoxy ethyl methoxy) propyl ] disiloxane to obtain a polyether amine-siloxane intermediate, and then the polyether amine-siloxane intermediate and octamethylcyclotetrasiloxane (D4) are synthesized into block silicone oil through an emulsion polymerization method. Compared with the traditional solvent method and the bulk polymerization method, the emulsion polymerization method completes the synthesis and emulsification of crude oil in one step, not only solves the problem of the compatibility of polyether amine and polysiloxane molecular chains, but also solves the problem of the use of solvents in the synthesis and emulsification processes, and avoids the safety and environmental protection problems caused by solvent volatilization in workshop production and actual use.

Description

Emulsion polymerization method for preparing block silicone oil

Technical Field

The invention relates to the field of printing and dyeing auxiliaries, in particular to an emulsion polymerization method for preparing block silicone oil.

Background

The silicone emulsion is prepared by emulsifying bulk polymerized silicone oil such as methyl silicone oil, hydroxy silicone oil, amino modified silicone oil, etc. into emulsion by mechanical emulsification method. For stability reasons, block silicone oil emulsions synthesized by solvent processes have been developed. In recent years, due to frequent safety accidents of chemical enterprises and printing and dyeing enterprises, people pay more attention to the safety production and use problems of chemicals, especially the control of a solvent in an organic silicon emulsion in an after-finishing auxiliary agent. Because the polarity difference between the polyether amine and the polyorganosiloxane chain segment is large, a homogeneous reaction is difficult to form in the reaction process, only organic solvents such as isopropanol and the like can be added to ensure the normal reaction, and particularly, the use amount of the solvent is higher for self-emulsifying block silicone oil. In order to reduce the use of solvent, patent CN107522866A discloses a preparation method of solvent-free block silicone oil, which uses polyetheramine and epoxy double-end-cap as raw materials to prepare an amino polyether coupling agent, and then polymerizes with D4 under alkaline conditions. The polymerization method belongs to a bulk polymerization method of organic silicon, a solvent can not be used in the reaction process, but an emulsion still needs to be prepared through an emulsification step after the preparation of crude oil, and when the viscosity of the crude oil is higher, a small amount of solvent still needs to be added to reduce the viscosity during emulsification. The emulsion polymerization method belongs to an environment-friendly new technology for preparing organic silicon emulsion, and the organic silicon ring body is directly polymerized under the condition of taking water as a medium to obtain the polyorganosiloxane, and a solvent is not required to be used in the reaction process. Emulsion polymerization has been developed to date, and many researchers have prepared stable amino-modified silicone oil emulsion by the method and applied to the textile field, but the research on preparing block silicone oil by emulsion polymerization is still blank.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide an emulsion polymerization method for preparing block silicone oil, which adopts an emulsion polymerization method to prepare the block silicone oil, realizes no solvation of the block silicone oil and achieves the aim of clean production.

In order to achieve the purpose, the invention adopts the following technical scheme:

1. an emulsion polymerization method for preparing block silicone oil is characterized by comprising the following steps:

1) preparation of polyetheramine-siloxane intermediate:

adding 30-40 parts of 1,1,3, 3-tetramethyl-1, 3-bis [3- (epoxy ethyl methoxy) propyl ] disiloxane and 20-400 parts of polyetheramine into a reaction container, heating to 60-100 ℃, preserving heat for 2-6 hours, cooling to 40-50 ℃, discharging to obtain a polyetheramine-siloxane intermediate;

2) preparing the block silicone oil by an emulsion polymerization method:

adding 2-4 parts of nonionic emulsifier, 2-6 parts of cationic emulsifier and 50-70 parts of water into a reaction container, stirring for 10-30 min until the materials are completely dissolved, adding 20-40 parts of octamethylcyclotetrasiloxane, stirring for 30-60 min, pouring into a high-pressure homogenizer, homogenizing twice under the pressure of 50-500 kg to obtain a pre-emulsion, adding the homogenized pre-emulsion into the reaction container, starting stirring, adding 0.5-2 parts of alkaline catalyst, heating to 60-90 ℃, carrying out heat preservation reaction for 4-8 h, adding 1-4 parts of polyetheramine-siloxane intermediate, continuing to react for 1-2 h, cooling to 40-50 ℃, adding 2-4 parts of glacial acetic acid for neutralization to obtain block silicone oil.

Preferably, the polyether amine is one of double-end amino polyoxyethylene polyoxypropylene ether and double-end amino polyoxyethylene polyoxypropylene ether with the number average molecular weight of 200-2000;

the nonionic emulsifier is two of lauryl alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and stearyl alcohol polyoxyethylene ether with polyoxyethylene unit number of 5-35;

the cationic emulsifier is one of dodecyl benzyl ammonium chloride, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride and docosyl trimethyl ammonium chloride;

the alkaline catalyst is one of sodium hydroxide and potassium hydroxide.

The number of polyoxyethylene units is abbreviated as EO, and the octamethylcyclotetrasiloxane is abbreviated as D4.

Due to the application of the technical scheme, the invention has the following advantages:

the invention is different from amino silicone oil emulsion of bulk polymerization, block silicone oil emulsion of solvent method and block silicone oil emulsion of solvent-free bulk polymerization. Solvent is not needed in the reaction process, the polyether amine-organic siloxane intermediate can react with the polyorganosiloxane on the surface of the emulsion particles in a water dispersion medium, and-Si-O-Si-bonds in the molecular structure of the polyether amine-organic siloxane are broken under alkaline catalysis to generate-Si-O^-The active group reacts with a product obtained after the ring opening of D4, and the product is low-molecular hydroxyl-terminated polysiloxane; introducing amino and polyether chain segments into a polyorganosiloxane molecular chain to obtain the block-type polyorganosiloxane. The method simultaneously carries out synthesis and emulsification, not only solves the problem of compatibility of polyether amine and a polysiloxane molecular chain, but also avoids the problem of more solvents in the synthesis and emulsification processes of block silicone oil, and effectively promotes the safe, environment-friendly and clean production of chemical and printing and dyeing enterprises.

Detailed Description

The invention is further described below by means of specific embodiments.

Example 1:

1) preparing a polyetheramine-siloxane intermediate;

adding 36 parts of 1,1,3, 3-tetramethyl-1, 3-bis [3- (epoxy ethyl methoxy) propyl ] disiloxane and 46 parts of polyetheramine (D230, data molecular weight 230, double-end amino polyoxypropylene ether) into a reaction vessel, heating to 70 ℃, preserving heat for 4 hours, cooling to 50 ℃, and discharging;

2) preparing block silicone oil by an emulsion polymerization method;

adding 2 parts of laurinol polyoxyethylene ether (EO ═ 5), 2 parts of laurinol polyoxyethylene ether (EO ═ 25), 3 parts of hexadecyl trimethyl ammonium chloride and 65 parts of water into a reaction vessel, stirring for 30min until the materials are completely dissolved, adding 25 parts of octamethylcyclotetrasiloxane (D4), stirring for 60min, pouring into a high-pressure homogenizer, homogenizing twice under the pressure of 200kg to obtain a pre-emulsion, adding the well-homogenized pre-emulsion into the reaction vessel, starting stirring, adding 1 part of sodium hydroxide, heating to 70 ℃, carrying out heat preservation reaction for 6h, adding 1 part of polyetheramine-siloxane intermediate, continuing to react for 2h, cooling to 50 ℃, and adding 2 parts of glacial acetic acid for neutralization. The results of the emulsion appearance and physical property tests are shown in Table 1.

Table 1 physical property test results

Example 2:

1) preparing a polyetheramine-siloxane intermediate;

adding 36 parts of 1,1,3, 3-tetramethyl-1, 3-bis [3- (epoxyethylmethoxy) propyl ] disiloxane and 60 parts of polyetheramine (D400, data molecular weight is 400, and amino-terminated polyoxypropylene ether) into a reaction vessel, heating to 80 ℃, preserving heat for 4 hours, cooling to 50 ℃, and discharging;

2) preparing block silicone oil by an emulsion polymerization method;

adding 1.5 parts of isomeric tridecanol polyoxyethylene ether (EO ═ 5), 2.5 parts of lauryl alcohol polyoxyethylene ether (EO ═ 25), 3 parts of octadecyl trimethyl ammonium chloride and 68 parts of water into a reaction vessel, stirring for 30min until the materials are completely dissolved, adding 25 parts of octamethylcyclotetrasiloxane (D4), stirring for 60min, pouring into a high-pressure homogenizer, homogenizing twice under the pressure of 300kg to obtain a pre-emulsion, adding the homogenized pre-emulsion into the reaction vessel, starting stirring, adding 1.5 parts of potassium hydroxide, heating to 80 ℃, carrying out heat preservation reaction for 4h, adding 1.5 parts of polyether amine-siloxane intermediate, continuing to react for 2h, cooling to 50 ℃, and adding 2 parts of glacial acetic acid for neutralization. The results of the emulsion appearance and physical property tests are shown in Table 2.

Table 2 results of physical property testing

Example 3:

1) preparing a polyetheramine-siloxane intermediate;

adding 36 parts of 1,1,3, 3-tetramethyl-1, 3-bis [3- (epoxyethylmethoxy) propyl ] disiloxane and 90 parts of polyetheramine (ED600, data molecular weight of 600, double-end amino polyoxyethylene polyoxypropylene ether) into a reaction vessel, heating to 90 ℃, preserving heat for 6 hours, cooling to 50 ℃, and discharging;

2) preparing emulsion polymerization type block silicone oil;

adding 1 part of isomeric tridecanol polyoxyethylene ether (EO ═ 5), 3 parts of lauryl alcohol polyoxyethylene ether (EO ═ 30), 3 parts of hexadecyl trimethyl ammonium chloride and 70 parts of water into a reaction vessel, stirring for 30min until the materials are completely dissolved, adding 25 parts of octamethylcyclotetrasiloxane (D4), stirring for 60min, pouring into a high-pressure homogenizer, homogenizing twice under the pressure of 300kg to obtain a pre-emulsion, adding the well-homogenized pre-emulsion into the reaction vessel, starting stirring, adding 1.5 parts of potassium hydroxide, heating to 80 ℃, carrying out heat preservation reaction for 4h, adding 2 parts of polyetheramine-siloxane intermediate, continuing to react for 1.5h, cooling to 50 ℃, and adding 2.5 parts of glacial acetic acid for neutralization. The results of the emulsion appearance and physical property tests are shown in Table 3.

Table 3 physical property test results

Claims

1) preparation of polyetheramine-siloxane intermediate:

2) preparing the block silicone oil by an emulsion polymerization method:

adding 2-4 parts of nonionic emulsifier, 2-6 parts of cationic emulsifier and 50-70 parts of water into a reaction container, stirring for 10-30 min until the materials are completely dissolved, adding 20-40 parts of octamethylcyclotetrasiloxane, stirring for 30-60 min, pouring into a high-pressure homogenizer, homogenizing twice under the pressure of 50-500 kg to obtain a pre-emulsion, adding the homogenized pre-emulsion into the reaction container, starting stirring, adding 0.5-2 parts of alkaline catalyst, heating to 60-90 ℃, carrying out heat preservation reaction for 4-8 h, adding 1-4 parts of polyetheramine-siloxane intermediate, continuing to react for 1-2 h, cooling to 40-50 ℃, adding 2-4 parts of glacial acetic acid for neutralization to obtain block silicone oil;

the polyether amine is one of double-end amino polyoxyethylene polyoxypropylene ether and double-end amino polyoxyethylene polyoxypropylene ether with the number average molecular weight of 200-2000;

the alkaline catalyst is one of sodium hydroxide and potassium hydroxide.