阅读说明：本技术 一种有机硅聚醚共聚物及其制备方法与应用 (Organic silicon polyether copolymer and preparation method and application thereof ) 是由 唐雄峰 王震翔 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种有机硅聚醚共聚物及其制备方法与应用,属于泡沫稳定剂领域。其结构式为m＝10-80,n＝1-10,p＝1-10,m+n+p＝12-100；R和R-3选自甲基、R-1或R-2,R-1为-CH-2CH-2CH-2O(CH-2CH-2O)-x(CH-2CHCH-3O)-yR-4,x＝10-30,y＝0-10,x+y＝10-40；R-2为-CH-2CH-2CH-2O(CH-2CH-2O)-(x1)(CH-2CHCH-3O)-(y1)G,x1＝10-30,y1＝0-10,x1+y1＝10-40；G为具有或或的聚苄醚；R-4＝-OH或C1-C4烷基。该有机硅聚醚共聚物可高效改善芳香族聚酯多元醇与各组分相容性及储存稳定性,提高聚氨酯泡沫性能。(The invention discloses an organic silicon polyether copolymer and a preparation method and application thereof, belonging to the field of foam stabilizers. The structural formula is m-10-80, n-1-10, p-1-10, m + n + p-12-100; r and R 3 Selected from methyl, R 1 Or R 2 ，R 1 is-CH 2 CH 2 CH 2 O(CH 2 CH 2 O) x (CH 2 CHCH 3 O) y R 4 ，x＝10‑30，y＝0‑10，x+y＝10‑40；R 2 is-CH 2 CH 2 CH 2 O(CH 2 CH 2 O) x1 (CH 2 CHCH 3 O) y1 G, x 1-10, y 1-0-10, x1+ y 1-10-40; g is a group having Or Or The benzyl ether of (a); r 4 -OH or C1-C4 alkyl. The organic silicon polyether copolymer can effectively improve the compatibility and the storage stability of the aromatic polyester polyol and each component, and improve the performance of polyurethane foam.)

1. The organic silicon polyether copolymer is characterized in that the structural formula of the organic silicon polyether copolymer is shown in the specification

Wherein m has a value of 10-80, n has a value of 1-10, p has a value of 1-10, and m + n + p has a value of 12-100;

r and R₃Are respectively independentThe three sites are selected from methyl and R₁Or R₂；

R₁is-CH₂CH₂CH₂O(CH₂CH₂O)_x(CH₂CHCH₃O)_yR₄，x＝10-30，y＝0-10，x+y＝10-40；

R₂is-CH₂CH₂CH₂O(CH₂CH₂O)_x1(CH₂CHCH₃O)_y1G, x 1-10, y 1-0-10, x1+ y 1-10-40; g is of the formula The benzyl ether of (a);

R₄-OH or C1-C4 alkyl.

2. The method of preparing the silicone polyether copolymer of claim 1, comprising the steps of: the preparation is carried out according to the structure of the organic silicon polyether copolymer.

3. The preparation method according to claim 2, characterized in that polydimethyl-methylhydrogensiloxane, allyl polyether alkene with a terminal of benzyl ether and allyl polyether with a terminal of hydroxyl or alkyl are reacted in the presence of a first catalyst and a cocatalyst to obtain the silicone polyether copolymer;

the first catalyst is a chloroplatinic acid catalyst, and the cocatalyst comprises at least one of N, N-dimethylaniline, N-dimethylformamide, isooctanol, triethylamine, ethylenediamine and triphenylphosphine;

preferably, the amount of the cocatalyst is 3-80ppm of the total mass of the reaction raw materials of the silicone polyether copolymer.

4. The method of claim 3, wherein the reaction is carried out at 80-130 ℃ for 2-8 hours.

5. The method according to claim 3, wherein the polydimethylsiloxane is prepared by a method comprising: reacting octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethyldihydrodisiloxane in the presence of a second catalyst;

the second catalyst comprises at least one of acid clay, sulfuric acid, and trifluoromethanesulfonic acid;

preferably, the second catalyst is sulfuric acid;

preferably, the amount of the second catalyst is 0.5 to 5 wt% of the total amount of the reaction raw materials of the polydimethylsiloxane.

6. The method according to claim 5, wherein the polydimethylsiloxane is carried out at 25-90 ℃ for 3-24 hours.

7. The method according to claim 3, wherein the method for preparing the allyl polyether alkene having a terminal polybenzyl ether comprises: reacting allyl polyether with terminal hydroxyl with bromo-poly benzyl ether in the presence of a third catalyst and a solvent;

the third catalyst is sodium hydride, and the solvent is tetrahydrofuran;

preferably, the amount of the third catalyst is 0.1-0.5 wt% of the total amount of the raw materials for the reaction of the allyl polyether alkene with the end of the benzyl ether;

preferably, the solvent is used in an amount of 50 to 200 wt% based on the total amount of the starting materials for the reaction of the allyl polyether alkene terminated with the benzyl ether.

8. The method according to claim 7, wherein the preparation of the allyl polyether alkene having a terminal poly (benzyl ether) is performed at 20-50 ℃ for 5-50 h.

9. Use of the silicone polyether copolymer of claim 1 in the production of a polyurethane foam.

10. A polyurethane foam characterized by reaction raw materials comprising the silicone polyether copolymer according to claim 1;

preferably, the reaction raw material of the polyurethane foam further comprises aromatic polyester polyol, and 1-5 parts of the silicone polyether copolymer is used for every 100 parts of the aromatic polyester polyol by mass parts;

more preferably, 2 to 3 parts of the silicone polyether copolymer is used per 100 parts of the aromatic polyester polyol.

Technical Field

The invention relates to the technical field of foam stabilizers, and particularly relates to an organic silicon polyether copolymer and a preparation method and application thereof.

Background

The organosilicon polyether copolymer is a comb-shaped copolymer with siloxane as a main chain and polyether as a side chain, wherein the siloxane is used as a hydrophobic group, so that the product has low surface tension and excellent chemical stability, electrical insulation, ageing resistance and other properties; the polyether is used as a hydrophilic group, so that the product has good surface activity. The change of the type, the quantity and the position of the side chain grafted polyether can effectively adjust the hydrophily and lipophilicity of the copolymer, thereby obtaining different performances such as foam stabilization, defoaming, lubrication, emulsification and the like. Since the silicone polyether copolymer has the above-mentioned unique properties, the silicone polyether copolymer is widely used in the preparation process of polyurethane foam as a foam stabilizer.

Polyurethane foam is an important synthetic material, and has the advantages of porosity, small relative density, high specific strength, excellent physical and mechanical properties, acoustic properties, electrical properties and chemical resistance. Polyurethane foam is prepared by chemically reacting various raw materials (such as isocyanate, polyol, foaming agent, etc.) in a short time, and changing from liquid to colloid and then to high polymer, and undergoing complicated processes such as foaming, gelling, etc. In the whole chemical reaction process, the foam can be uniformly foamed and stable under the action of the foam stabilizer, so that the foam with uniform foam holes is prepared. The foam stabilizer mainly has the following functions: (1) and (4) emulsifying. The foaming raw materials are emulsified and uniformly mixed, so that the foaming reaction and the crosslinking reaction are smoothly carried out. (2) Nucleation and stabilization of the foam. The foam stabilizer can reduce the surface tension of the material, and the mixed air is easy to form a bubble core during stirring; in the foaming process, the foam stabilizer enables the thinned cell walls to be stable and uniformly distributed by reducing the stress in the cell walls. (3) Closed/open pore action. The foam stabilizer in the rigid polyurethane foam can obtain a foam body with uniform and fine foam cells and a closed cell rate higher than 95 percent by reducing the surface tension of a foaming system, so that a foam product has a good heat insulation effect and sufficient mechanical strength. The foam stabilizer in the soft polyurethane foam can eliminate the defects of foam cracking, closed cells and the like by controlling the opening time of the foam, and endow the foam with good air permeability and comfort performance.

The polyurethane foam can be made into flexible, semi-rigid and rigid polyurethane foams according to different raw materials (isocyanate, polyalcohol and foaming agent) and the change of formula. Based on the important function of the foam stabilizer, the organic silicon polyether copolymers with different structures are developed to be used as the foam stabilizer aiming at different polyurethane foaming plastics. In the preparation of rigid polyurethane foams, the polyols used include: polyether polyols, polyester polyols, biobased polyols, and the like. Because the structures of the different types of polyols for the rigid polyurethane foam are obviously different, the development of various polyurethane foam stabilizers with different structures for the rigid polyurethane foam preparation in order to adapt to the structural change of the polyols becomes a research trend.

In the rigid polyurethane foam polyol, polyester polyol, particularly aromatic polyester polyol, contains benzene rings, so that the heat resistance of the foam can be improved, the flame retardance can be improved, the polyurethane foam can be widely used for sandwich foam boards and building spraying, and the polyester polyol foam has the basic properties of polyether polyol rigid foam, and has the characteristics of fine foam, good toughness, excellent flame retardance and the like. However, the aromatic polyester polyol contains a benzene ring structure, and compared with polyether polyol, the aromatic polyester polyol has poor compatibility with components such as a foaming agent and the like, and is easy to have the phenomena of uneven mixing, poor storage stability, easy delamination and the like, so that the quality of prepared polyurethane foam is influenced. Therefore, there is a need to develop a new silicone polyether copolymer and a preparation method thereof to solve the compatibility problem existing at present.

In view of this, the invention is particularly proposed.

Disclosure of Invention

One of the objects of the present invention consists in providing a silicone polyether copolymer to solve the above technical problems.

The second object of the present invention is to provide a method for preparing the above silicone polyether copolymer.

The invention also provides the application of the organic silicon polyether copolymer, namely the application of the organic silicon polyether copolymer in preparing polyurethane foam.

The fourth object of the present invention is to provide a polyurethane foam, the reaction raw material of which contains the above silicone polyether copolymer.

The application can be realized as follows:

in a first aspect, the present application provides a silicone polyether copolymer having the structural formula:

wherein m has a value of 10-80, n has a value of 1-10, p has a value of 1-10, and m + n + p has a value of 12-100.

R and R₃Each independently selected from methyl and R₁Or R₂，R₁is-CH₂CH₂CH₂O(CH₂CH₂O)_x(CH₂CHCH₃O)_yR₄，x＝10-30，y＝0-10，x+y＝10-40；R₂is-CH₂CH₂CH₂O(CH₂CH₂O)_x1(CH₂CHCH₃O)_y1G, x 1-10, y 1-0-10, x1+ y 1-10-40; g is of the formula The benzyl ether of (1).

R₄-OH or C1-C4 alkyl.

In a second aspect, the present application provides a method of preparing a silicone polyether copolymer as in the previous embodiments, comprising the steps of: the preparation is carried out according to the structure of the organic silicon polyether copolymer.

In an alternative embodiment, the polydimethyl-methylhydrogensiloxane, the allyl polyether alkene terminated with the polybenzyl ether, and the allyl polyether terminated with the hydroxyl or alkyl group are reacted in the presence of a first catalyst and a co-catalyst to obtain the silicone polyether copolymer.

The first catalyst is a chloroplatinic acid catalyst, and the cocatalyst comprises at least one of N, N-dimethylaniline, N-dimethylformamide, isooctanol, triethylamine, ethylenediamine and triphenylphosphine.

In an alternative embodiment, the amount of co-catalyst is 3 to 80ppm of the total mass of the reaction raw materials of the silicone polyether copolymer.

In an alternative embodiment, the reaction is carried out at 80-130 ℃ for 2-8 h.

In an alternative embodiment, a method of preparing a polydimethylsiloxane comprises: reacting octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethyldihydrodisiloxane in the presence of a second catalyst.

The second catalyst includes at least one of acid clay, sulfuric acid, and trifluoromethanesulfonic acid.

In an alternative embodiment, the second catalyst is sulfuric acid.

In an alternative embodiment, the second catalyst is used in an amount of 0.5 to 5 wt% based on the total amount of the reaction raw materials of the polydimethyl-methylsiloxane.

In an alternative embodiment, the preparation of the polydimethyl-methylsiloxane is carried out at 25-90 ℃ for 3-24 h.

In an alternative embodiment, a method of preparing an allyl polyether alkene terminated with a polybenzyl ether comprises: reacting the allyl polyether with terminal hydroxyl with bromo-poly benzyl ether in the presence of a third catalyst and a solvent.

The third catalyst is sodium hydride and the solvent is tetrahydrofuran.

In an alternative embodiment, the third catalyst is used in an amount of 0.1 to 0.5 wt% based on the total amount of the reaction starting materials for the allyl polyether alkene terminated with the benzyl ether.

In an alternative embodiment, the solvent is used in an amount of 50 to 200 wt% based on the total amount of the starting materials for the reaction of the allyl polyether alkene terminated with the benzyl ether.

In an alternative embodiment, the preparation of the allyl polyether alkene terminated with the benzyl ether is carried out at 20-50 ℃ for 5-50 h.

In a third aspect, the present application provides the use of a silicone polyether copolymer as in the previous embodiments in the production of a polyurethane foam.

In a fourth aspect, the present application provides a polyurethane foam whose reaction raw materials contain the silicone polyether copolymer according to the previous embodiment.

In an alternative embodiment, the reaction raw material of the polyurethane foam further comprises aromatic polyester polyol, and 1-5 parts of the silicone polyether copolymer is used per 100 parts of the aromatic polyester polyol by mass.

In an alternative embodiment, 2 to 3 parts of silicone polyether copolymer is used per 100 parts of aromatic polyester polyol.

The beneficial effect of this application includes:

in the organic silicon polyether copolymer containing the benzyl ether designed and synthesized by the application, the benzyl ether group is positioned at the tail end of part of polyether, so that the mutual interference between the benzyl ether group and side chain polyether is avoided, the functions of each functional group are fully exerted, and the effect of improving the compatibility of the organic silicon polyether copolymer is improved. The benzyl ether in the organic silicon polyether copolymer contains a large number of benzene rings, so that the compatibility of aromatic polyester polyol can be effectively improved, the structure of the benzyl ether has great openness, and the content of the phenyl can be adjusted according to requirements so as to meet different requirements. Meanwhile, the poly (benzyl ether) is in a dendritic structure, the viscosity of the poly (benzyl ether) is far lower than that of a linear structure copolymer with the same molecular weight, and the problems of poor mixing effect, difficult operation and the like caused by the increase of the viscosity of the copolymer due to the introduction of a high molecular weight group are solved. The benzyl ether group is positioned at the tail end of the side chain polyether, so that the steric hindrance is relatively small, and the hydrosilation reaction is easy to carry out. Based on the independence and openness of the structure of the benzyl polyether, the polyether and polysiloxane structures in the organic silicon polyether copolymer can be independently adjusted according to the application performance requirements, so that the copolymer structure has larger openness, and has good application prospects in the aspects of foam evening, wetting, leveling, emulsification and the like. Particularly, as a polyurethane foam stabilizer, the aromatic polyester polyol can effectively improve the compatibility and storage stability of the aromatic polyester polyol and each component, thereby improving the performance of polyurethane foam.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The silicone polyether copolymer provided by the present application, and the preparation method and application thereof are specifically described below.

The application provides an organic silicon polyether copolymer, and the structural formula of the organic silicon polyether copolymer is shown in the specification

Wherein m has a value of 10-80, n has a value of 1-10, p has a value of 1-10, and m + n + p has a value of 12-100.

In reference, m can take the value of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80, etc., and can also take any other value within the range of 10-80. n and p can independently take the values of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 respectively and the like.

R and R₃Each independently selected from methyl and R₁Or R₂。

Wherein R is₁is-CH₂CH₂CH₂O(CH₂CH₂O)_x(CH₂CHCH₃O)_yR₄，x＝10-30，y＝0-10，x+y＝10-40。

It should be noted that x may be 10, 12, 15, 18, 20, 22, 25, 28, 30, etc., or any other value within the range of 10-30. y can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, etc.

R₂is-CH₂CH₂CH₂O(CH₂CH₂O)_x1(CH₂CHCH₃O)_y1G，x1＝10-30，y1＝0-10，x1+y1＝10-40。

It should be noted that x1 can be 10, 12, 15, 18, 20, 22, 25, 28, 30, etc., or any other value within the range of 10-30. y1 can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, etc.

G is of the formulaThe benzyl ether of (1).

R₄-OH or C1-C4 alkyl.

In the silicone polyether copolymer containing the benzyl ether designed and synthesized by the application, the benzyl ether group is positioned at the tail end of part of polyether, so that the mutual interference between the benzyl ether group and side chain polyether is avoided, the functions of each functional group are fully exerted, and the effect of improving the compatibility of the silicone polyether copolymer is improved. The benzyl ether in the organic silicon polyether copolymer contains a large number of benzene rings, so that the compatibility of aromatic polyester polyol can be effectively improved, the structure of the benzyl ether has great openness, and the content of the phenyl can be adjusted according to requirements so as to meet different requirements. Meanwhile, the poly (benzyl ether) is in a dendritic structure, the viscosity of the poly (benzyl ether) is far lower than that of a linear structure copolymer with the same molecular weight, and the problems of poor mixing effect, difficult operation and the like caused by the increase of the viscosity of the copolymer due to the introduction of a high molecular weight group are solved. The benzyl ether group is positioned at the tail end of the side chain polyether, so that the steric hindrance is relatively small, and the hydrosilation reaction is easy to carry out. Based on the independence and openness of the structure of the benzyl polyether, the polyether and polysiloxane structures in the organic silicon polyether copolymer can be independently adjusted according to the application performance requirements, so that the copolymer structure has larger openness, and has good application prospects in the aspects of foam evening, wetting, leveling, emulsification and the like. Particularly, as a polyurethane foam stabilizer, the aromatic polyester polyol can effectively improve the compatibility and storage stability of the aromatic polyester polyol and each component, thereby improving the performance of polyurethane foam.

In addition, the application also provides a preparation method of the organic silicon polyether copolymer, which comprises the following steps: the preparation is carried out according to the structure of the organic silicon polyether copolymer.

Specifically, polydimethyl-methylhydrogensiloxane, allyl polyether alkene with the end of benzyl ether and allyl polyether with the end of hydroxyl or alkyl are used as reaction raw materials to react in the presence of a first catalyst and a cocatalyst to obtain the organic silicon polyether copolymer.

In an alternative embodiment, the first catalyst is a chloroplatinic acid catalyst, and the co-catalyst comprises at least one of N, N-dimethylaniline, N-dimethylformamide, isooctanol, triethylamine, ethylenediamine, and triphenylphosphine.

In alternative embodiments, the co-catalyst is used in an amount of 3 to 80ppm, such as 3ppm, 5ppm, 10ppm, 20ppm, 50ppm, 60ppm, or 80ppm, etc., based on the total mass of the reaction raw materials of the silicone polyether copolymer.

In an alternative embodiment, the polydimethyl-methylhydrogensiloxane, the allyl polyether alkene terminated with the benzyl ether, and the allyl polyether terminated with the hydroxyl or alkyl group are reacted for 2 to 8 hours (2 hours, 5 hours, 8 hours, etc.) under the condition of 80 to 130 ℃ (such as 80 ℃, 100 ℃, 120 ℃ or 130 ℃, etc.).

The preparation method of the polydimethylsiloxane can be referred to as follows: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethyldisiloxane and tetramethyldihydrodisiloxane as reaction raw materials and reacting in the presence of a second catalyst.

In an alternative embodiment, the second catalyst may include at least one of acid clay, sulfuric acid, and trifluoromethanesulfonic acid, preferably sulfuric acid.

In alternative embodiments, the second catalyst may be used in an amount of 0.5 to 5 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, etc., of the total amount of the reaction raw materials of the polydimethylsiloxane.

In alternative embodiments, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethyldisiloxane, and tetramethyldihydrodisiloxane are reacted for 3-24 hours (e.g., 3 hours, 5 hours, 10 hours, 15 hours, 20 hours, 24 hours, etc.) at 25-90 ℃ (25 ℃, 30 ℃, 50 ℃, 70 ℃, or 90 ℃, etc.).

The preparation method of the allyl polyether alkene with the end of the benzyl ether can refer to the following steps: and (3) reacting the allyl polyether with terminal hydroxyl and bromo-poly benzyl ether as reaction raw materials in the presence of a third catalyst and a solvent.

In an alternative embodiment, the third catalyst is sodium hydride and the solvent is tetrahydrofuran.

In alternative embodiments, the third catalyst may be used in an amount of 0.1 to 0.5 wt%, such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, or 0.5 wt%, etc., of the total amount of the starting materials for the reaction of the benzyl ether terminated allyl polyether alkene.

In alternative embodiments, the solvent may be used in an amount of 50 to 200 wt%, such as 50 wt%, 100 wt%, 150 wt%, or 200 wt%, etc., of the total amount of the starting materials for the reaction of the allyl polyether alkene terminated with the benzyl ether.

In an alternative embodiment, the hydroxyl-terminated allyl polyether is reacted with brominated polybenzyl ether at 20-50 deg.C (e.g., 20 deg.C, 30 deg.C, 40 deg.C, or 50 deg.C, etc.) for 5-50h (5h, 10h, 20h, 30h, 40h, or 50h, etc.).

It should be noted that, the allyl polyether having hydroxyl or alkyl at the end can be the corresponding one, and the preparation method can be referred to the prior art, which is not described herein in detail.

Further, the application also provides the application of the organic silicon polyether copolymer in the production of polyurethane foam, for example, the organic silicon polyether copolymer is used as a foam stabilizer in the production process of polyurethane foam, and the compatibility of the aromatic polyester polyol and each component and the storage stability can be effectively improved, so that the performance of the polyurethane foam is improved.

Correspondingly, the application also provides a polyurethane foam, and the reaction raw materials of the polyurethane foam contain the organic silicon polyether copolymer.

In an alternative embodiment, the reaction raw material of the polyurethane foam further comprises aromatic polyester polyol, and 1-5 parts of the silicone polyether copolymer is used per 100 parts of the aromatic polyester polyol by mass. Preferably, 2-3 parts of silicone polyether copolymer are used per 100 parts of aromatic polyester polyol.

The organic silicon polyether copolymer is used according to the dosage, so that good emulsifying property can be embodied, and the stability and the system compatibility of the polyurethane foam are higher.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

This example provides a silicone polyether copolymer prepared in the following manner:

(1) 175.0g of octamethylcyclotetrasiloxane, 14.9g of tetramethylcyclotetrasiloxane and 10.1g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 8 hours at 30 ℃ under the action of 5g of sulfuric acid to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 71.9g of allyl polyether with a hydroxyl end and 28.1g of brominated polybenzyl ether into a reactor, and reacting for 24 hours at 25 ℃ under the action of 0.15g of sodium hydride catalyst and 80g of tetrahydrofuran solvent to obtain allyl polyether with a polybenzyl ether end;

(3) 59.6g of the above-mentioned polydimethyl-methylhydrogensiloxane and hydroxyl-terminated allyl polyether CH₂＝CHCH₂O(CH₂CH₂O)₁₀(CH₂CHCH₃O)₄H38.7g and 51.6g of the allyl polyether with the end being the polybenzyl ether are added into a reactor, and the mixture is heated to 110 ℃ for reaction for 3h under normal pressure and the existence of 6ppm of chloroplatinic acid catalyst and 12ppm of triphenylphosphine cocatalyst, so that the organosilicon polyether copolymer containing the polybenzyl ether is obtained.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₃₈-O-[Si(CH₃)R₁]_2.2-O-[Si(CH₃)R₂]_1.8-O-Si(CH₃)₃；

wherein: r₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₀(CH₂CHCH₃O)₄H；

R₂＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₅(CH₂CHCH₃O)₃G；

G has a structural formula of

Example 2

This example provides a silicone polyether copolymer prepared in the following manner:

(1) 173.6g of octamethylcyclotetrasiloxane, 17.2g of tetramethylcyclotetrasiloxane and 9.3g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 8 hours at 35 ℃ under the action of 2g of sulfuric acid to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 57.8g of allyl polyether with terminal hydroxyl and 42.2g of brominated polybenzyl ether into a reactor, and reacting for 24 hours at 25 ℃ under the action of 0.20g of sodium hydride catalyst and 100g of tetrahydrofuran solvent to obtain allyl polyether with terminal polybenzyl ether;

(3) 46.6g of the above-mentioned polydimethyl-methylhydrogensiloxane and hydroxy-terminated allyl polyether CH₂＝CHCH₂O(CH₂CH₂O)₁₃(CH₂CHCH₃O)₅H47.8g, the end of the benzyl ether allyl polyether 55.6g into the reactor, in 6ppm chloroplatinic acid catalyst and 18ppm N, N-two methyl aniline catalyst promoter conditions, normal pressure heating to 100 degrees C, reaction for 4h, containing benzyl ether silicone polyether copolymer.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₄₁-O-[Si(CH₃)R₁]₃-O-[Si(CH₃)R₂]₂-O-Si(CH₃)₃；

wherein:

R₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₃(CH₂CHCH₃O)₅H；

R₂＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₃(CH₂CHCH₃O)₅G；

g has a structural formula of

Example 3

This example provides a silicone polyether copolymer prepared in the following manner:

(1) 173.7g of octamethylcyclotetrasiloxane, 19.0g of tetramethylcyclotetrasiloxane and 7.3g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 5 hours at 75 ℃ under the action of 10g of acid clay to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 43.5g of allyl polyether with terminal hydroxyl and 56.5g of brominated polybenzyl ether into a reactor, and reacting for 36h at 30 ℃ under the action of 0.3g of sodium hydride catalyst and 150g of tetrahydrofuran solvent to obtain allyl polyether with terminal polybenzyl ether;

(3) 40.9g of the above-mentioned polydimethyl-methylhydrogensiloxane, hydroxyl-terminated allyl polyether CH₂＝CHCH₂O(CH₂CH₂O)₁₅(CH₂CHCH₃O)₃H56.2g and 52.8g of allyl polyether with the end being the polybenzyl ether are added into a reactor, and the mixture is heated to 100 ℃ under the normal pressure and reacted for 5h under the condition of 8ppm of chloroplatinic acid catalyst and 20ppm of triethylamine cocatalyst, so as to obtain the organic silicon polyether copolymer containing the polybenzyl ether.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₅₂-O-[Si(CH₃)R₁]_5.25-O-[Si(CH₃)R₂]_1.75-O-Si(CH₃)₃；

wherein:

R₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₅(CH₂CHCH₃O)₃H；

R₂＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₇(CH₂CHCH₃O)₃G；

g has a structural formula of

Example 4

This example provides a silicone polyether copolymer prepared in the following manner:

(1) 176.5g of octamethylcyclotetrasiloxane, 15.2g of tetramethylcyclotetrasiloxane and 8.2g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 8 hours at 30 ℃ under the action of 5g of sulfuric acid to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 72.2g of allyl polyether with terminal hydroxyl and 27.8g of brominated polybenzyl ether into a reactor, and reacting for 24 hours at 25 ℃ under the action of 0.15 sodium hydride catalyst and 100g of tetrahydrofuran solvent to obtain allyl polyether with terminal polybenzyl ether;

(3) 59.7g of the above-mentioned polydimethyl-methylhydrogensiloxane and terminal methylallyl polyether CH₂＝CHCH₂O(CH₂CH₂O)₁₄(CH₂CHCH₃O)₂CH₃50.6g of the above allyl polyether having a terminal of a polybenzyl ether (39.7 g) was added to a reactor, and the mixture was heated to 100 ℃ under normal pressure and a reaction was carried out for 4 hours with 8ppm of chloroplatinic acid catalyst and 25ppm of mN, N-dimethylaniline as a co-catalyst, thereby obtaining a silicone polyether copolymer containing a polybenzyl ether.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₄₇-O-[Si(CH₃)R₁]_3.25-O-[Si(CH₃)R₂]_1.75-O-Si(CH₃)₃；

wherein:

R₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₄(CH₂CHCH₃O)₂CH₃；

R₂＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₅(CH₂CHCH₃O)₃G；

wherein G has a structural formula

Example 5

This example provides a silicone polyether copolymer prepared in the following manner:

(1) 177.3g of octamethylcyclotetrasiloxane, 15.7g of tetramethylcyclotetrasiloxane and 7.1g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 8 hours at 35 ℃ under the action of 2g of sulfuric acid to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 54.9g of allyl polyether with terminal hydroxyl and 45.1g of brominated polybenzyl ether into a reactor, and reacting for 24 hours at 25 ℃ under the action of 0.2g of sodium hydride catalyst and 150g of tetrahydrofuran solvent to obtain allyl polyether with terminal polybenzyl ether;

(3) 55.3g of the above-mentioned polydimethyl-methylhydrogensiloxane and terminal methylallyl polyether CH₂＝CHCH₂O(CH₂CH₂O)₁₃(CH₂CHCH₃O)₃CH₃52.8g of the allyl polyether with the end being the polybenzyl ether and 41.9g of the allyl polyether are added into a reactor, and the mixture is heated to 100 ℃ under normal pressure and reacted for 5 hours under the conditions of 10ppm of chloroplatinic acid catalyst and 25ppm of triethylamine cocatalyst, so as to obtain the organosilicon polyether copolymer containing the polybenzyl ether.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₅₅-O-[Si(CH₃)R₁]_4.2-O-[Si(CH₃)R₂]_1.8-O-Si(CH₃)₃；

wherein:

R₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₃(CH₂CHCH₃O)₃CH₃；

R₂＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₃(CH₂CHCH₃O)₃G；

g has a structural formula of

Example 6

This example provides a silicone polyether copolymer prepared in the following manner:

(1) 177.4g of octamethylcyclotetrasiloxane, 16.9g of tetramethylcyclotetrasiloxane and 5.7g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 5 hours at 75 ℃ under the action of 10g of acid clay to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 44.6g of allyl polyether with terminal hydroxyl and 53.4g of brominated polybenzyl ether into a reactor, and reacting for 36h at 30 ℃ under the action of 0.3g of sodium hydride catalyst and 150g of tetrahydrofuran solvent to obtain allyl polyether with terminal polybenzyl ether;

(3) 43.7g of the above-mentioned polydimethyl-methylhydrogensiloxane and terminal methylallyl polyether CH₂＝CHCH₂O(CH₂CH₂O)₁₇(CH₂CHCH₃O)₅CH₃74.7g of the allyl polyether with the end being the polybenzyl ether and 31.6g of the allyl polyether are added into a reactor, and the mixture is heated to 110 ℃ under normal pressure and reacted for 5h under the conditions of 16ppm of chloroplatinic acid catalyst and 30ppm of triphenylphosphine cocatalyst, so as to obtain the organosilicon polyether copolymer containing the polybenzyl ether.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₆₈-O-[Si(CH₃)R₁]_6.8-O-[Si(CH₃)R₂]_1.2-O-Si(CH₃)₃；

wherein:

R₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₇(CH₂CHCH₃O)₅CH₃；

R₂＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₇(CH₂CHCH₃O)₅G；

g has a structural formula of

Comparative example 1

This comparative example provides a silicone polyether copolymer prepared in the following manner:

(1) 175.0g of octamethylcyclotetrasiloxane, 14.9g of tetramethylcyclotetrasiloxane and 10.1g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 8 hours at 30 ℃ under the action of 5g of sulfuric acid to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 90.9g of dimethyl-methylhydrogensiloxane and 59.1g of hydroxyl-terminated allyl polyether into a reactor, heating to 110 ℃ under normal pressure and reacting for 3h under the conditions of 6ppm of chloroplatinic acid catalyst and 12ppm of triphenylphosphine cocatalyst to obtain the organic silicon polyether copolymer.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₃₈-O-[Si(CH₃)R₁]₄-O-Si(CH₃)₃；

wherein:

R₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₀(CH₂CHCH₃O)₄H。

comparative example 2

This comparative example provides a silicone polyether copolymer prepared in the following manner:

(1) 177.3g of octamethylcyclotetrasiloxane, 15.7g of tetramethylcyclotetrasiloxane and 7.1g of hexamethyldisiloxane are added into a reactor, and the mixture is reacted for 8 hours at 35 ℃ under the action of 2g of sulfuric acid to obtain the dimethyl-methylhydrosiloxane.

(2) Adding 76.7g of polydimethyl-methylhydrogensiloxane and 73.3g of terminal methyl allyl polyether into a reactor, heating to 100 ℃ under normal pressure and reacting for 5 hours under the conditions of 10ppm of chloroplatinic acid catalyst and 25ppm of triethylamine cocatalyst to obtain the organic silicon polyether copolymer.

The structure of the organic silicon polyether copolymer after characterization and analysis is as follows:

(CH₃)₃Si-O-[Si(CH₃)₂]₅₅-O-[Si(CH₃)R₁]₆-O-Si(CH₃)₃；

wherein:

R₁＝-CH₂CH₂CH₂O(CH₂CH₂O)₁₃(CH₂CHCH₃O)₃CH₃。

test examples

The silicone polyether copolymers obtained in examples 1-6 and comparative examples 1-2 were used as polyurethane foam stabilizers for testing compatibility of rigid polyurethane polyol formulations, which are shown in Table 1, and the test results are shown in Table 2.

TABLE 1 rigid polyurethane foam formulations

Components	Parts by weight
		PS-3152	100 portions of
Phosphoric acid tris (2-chloropropyl) ester	15 portions of
		Water (W)	0.5 portion
Potassium octoate	5 portions of
		Pentamethyldiethylenetriamine	0.3 part
Polyurethane foam stabilizer	2.0 part by weight
		Cyclopentane	15-20 parts of

TABLE 2 polyester polyol formulation compatibility test results

As can be seen from table 2, the silicone polyether copolymer containing benzyl ether prepared by the present application has good emulsifying ability in the aromatic polyester polyol system. Compared with the common polyether organic silicon copolymer, the synthetic polyether organic silicon copolymer has better emulsifying property, and can ensure that the polyurethane foam has better stability and compatibility.

In conclusion, the benzyl ether group in the synthesized organic silicon polyether copolymer containing the benzyl ether is positioned at the tail end of part of polyether, so that the mutual interference between the benzyl ether group and side chain polyether is avoided, the functions of each functional group are fully exerted, and the effect of improving the compatibility of the organic silicon polyether copolymer is improved. The benzyl ether in the organic silicon polyether copolymer contains a large number of benzene rings, so that the compatibility of the aromatic polyester polyol can be effectively improved, the structure of the benzyl ether has great openness, and the content of the phenyl can be adjusted according to requirements so as to meet different requirements. Meanwhile, the poly (benzyl ether) is in a dendritic structure, the viscosity of the poly (benzyl ether) is far lower than that of a linear structure copolymer with the same molecular weight, and the problems of poor mixing effect, difficult operation and the like caused by the increase of the viscosity of the copolymer due to the introduction of a high molecular weight group are solved. The benzyl ether group is positioned at the tail end of the side chain polyether, so that the steric hindrance is relatively small, and the hydrosilation reaction is easy to carry out. Based on the independence and openness of the structure of the benzyl polyether, the polyether and polysiloxane structures in the organic silicon polyether copolymer can be independently adjusted according to the application performance requirements, so that the copolymer structure has larger openness, and has good application prospects in the aspects of foam evening, wetting, leveling, emulsification and the like. Particularly, as a polyurethane foam stabilizer, the organic silicon polyether copolymer containing the benzyl ether can effectively improve the compatibility and the storage stability of the aromatic polyester polyol and each component, thereby improving the performance of polyurethane foam.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.