阅读说明：本技术 改性聚硅氧烷及其制备方法和作为聚氨酯软泡用匀泡剂的用途 (Modified polysiloxane, preparation method thereof and application of modified polysiloxane as foam stabilizer for polyurethane flexible foam ) 是由 高源� 张聪颖 马伟 曹骏 封玲珑 邱化敏 杨继朋 刘志峰 于 2020-05-12 设计创作，主要内容包括：本发明提供了一种改性聚硅氧烷及其制备方法和聚氨酯软泡用匀泡剂的用途。在主链的聚硅氧烷链段中嵌入碳链结构,同时对端位的惰性甲基结构进行一定的取代修饰。增强了主链与聚氨酯发泡油相物料的相容性,增强了其在液液界面的定向吸附,降低其表面张力。在其侧链进行大分子聚醚链节的修饰,增强了聚合物的增溶效果,同时增强了其乳化效果。该方法制备的匀泡剂,可使得软质聚氨酯泡沫各原料间的相容性更好,在发泡、成核、凝胶、固泡等阶段有较好的稳定性和匀泡性,能够满足聚氨酯软泡用的性能要求,且制备的泡沫可达到国外水平。(The invention provides modified polysiloxane, a preparation method thereof and application of a foam stabilizer for polyurethane flexible foam. Carbon chain structures are embedded in polysiloxane chain segments of the main chain, and meanwhile, certain substitution modification is carried out on the inert methyl structures at the end positions. The compatibility of the main chain and the polyurethane foaming oil phase material is enhanced, the directional adsorption of the polyurethane foaming oil phase material on a liquid-liquid interface is enhanced, and the surface tension of the polyurethane foaming oil phase material is reduced. The side chain is modified by macromolecular polyether chain link, so that the solubilization effect of the polymer is enhanced, and the emulsification effect of the polymer is enhanced. The foam stabilizer prepared by the method can ensure that the compatibility among all raw materials of the soft polyurethane foam is better, has better stability and foam stabilizing performance in the stages of foaming, nucleation, gelation, foam fixation and the like, can meet the performance requirements for the soft polyurethane foam, and the prepared foam can reach the foreign level.)

1. A modified polysiloxane compound of formula (1):

wherein m is 1 to 10, preferably 2 to 6; n is 5 to 100, preferably 10 to 50;

r is- (CH)₂)_q-a divalent radical of straight carbon chain structure wherein q is from 4 to 8, preferably from 4 to 6;

R₁is p-toluene-1-butenyl, 2-toluene-1-allyl;

R₂is polyether allyl CH₂＝CH-CH-(CH₂-CH₂-O)_x-(CH₂-CH(CH₃)-O)_y-H

Wherein x is 20-40 and y is 20-60.

2. A method for producing the modified polysiloxane compound of formula (1) according to claim 1, comprising the steps of:

c. putting the compound shown in the formula (2) into a reaction kettle, heating to 80-110 ℃, preferably 82-90 ℃ in an inert gas atmosphere such as nitrogen protection, and according to the total hydrogen content of the compound shown in the formula (2): the molar ratio of the allyl polyether is 1: 1.01-2, preferably 1: 1.05-1.2, the allyl polyether uniformly mixed with a certain amount of a Kanst catalyst and/or chloroplatinic acid is slowly dripped into a reaction kettle, the temperature of the reaction kettle rises due to exothermic reaction, and after the dripping is finished and the reaction temperature of a system does not rise any more, the heat preservation is continued at a certain temperature (for example, 100-130 ℃, preferably 110-120 ℃) to obtain the polymer of the formula (1);

wherein m is 1 to 10, preferably 2 to 6; n is 5 to 100, preferably 10 to 50;

r is- (CH)₂)_q-a divalent radical of straight carbon chain structure wherein q is from 4 to 8, preferably from 4 to 6;

R₁is p-toluene-1-butenyl, 2-toluene-1-allyl.

3. The method of claim 2, wherein the compound of formula (2) is prepared by:

b. the compound of formula (3) is reacted with tetramethylcyclotetrasiloxane in the ratio of 1: 0.8 to 5, preferably 1:1 to 4, is added into a reaction kettle, dehydration is carried out under the protection of inert gas such as nitrogen, then a catalyst is added, reaction is carried out at a certain temperature, neutralization and filtration are carried out to obtain the compound of the formula (2),

wherein n is 5 to 100, preferably 10 to 50;

r is- (CH)₂)_q-a divalent radical of straight carbon chain structure wherein q is from 4 to 8, preferably from 4 to 6;

R₁is p-toluene-1-butenyl, 2-toluene-1-allyl.

4. The method of claim 3, wherein the compound of formula (3) is prepared by:

a. putting the hydrogen-terminated silicone oil into a reaction kettle, dehydrating in the protection of inert gas such as nitrogen, and then, at a certain temperature, according to the total hydrogen content of the hydrogen-terminated silicone oil: diene: the mol ratio of the p-1-butenyl toluene and/or the 1-allyl-2-toluene is 1.5-3: 1: 1.5-3; preferably 1.8 to 2.2: 1: 1.8-2.2, more preferably about 2:1:2, adding compound diene, p-1-butenyl toluene and/or 1-allyl-2-toluene, uniformly stirring, adding a certain amount of Kanst catalyst and/or chloroplatinic acid, then quickly raising the reaction temperature, and when the reaction temperature is not raised any more, keeping the temperature at a certain temperature to obtain the compound represented by the formula (3).

5. The process according to claim 2, wherein in step c, the amount of the kate catalyst and/or chloroplatinic acid is 0.5 to 10ppm, preferably 1 to 5ppm, based on the total weight of the compound of formula (2) and allyl polyether;

before adding the Kanst catalyst and/or chloroplatinic acid, the reaction system is heated to 80-110 ℃ and the temperature is kept at 110-130 ℃.

6. The process according to claim 3, wherein in step b, the catalyst is one or more of concentrated sulfuric acid, trifluoromethanesulfonic acid, acidic ion exchange resins, preferably trifluoromethanesulfonic acid; and/or

The amount of the catalyst is 0.1 to 2 percent based on the total weight of the compound represented by the formula (3) and the tetramethylcyclotetrasiloxane;

the reaction temperature is 40-75 ℃, preferably 50-65 ℃.

7. The process according to claim 4, wherein in step a, the diene is one or more of butadiene, pentadiene, hexadiene, heptadiene, octadiene, preferably butadiene; and/or

Wherein the p-1-butenyl toluene and/or 1-allyl-2-toluene is p-1-butenyl toluene.

8. The method as claimed in claim 4, wherein, in step a, the reaction temperature is 70-120 ℃, preferably 80-110 ℃, and the system heat preservation temperature is 105-125 ℃, preferably 110-120 ℃; and/or

In step a, the amount of the Kanst catalyst and/or chloroplatinic acid is 0.5 to 50ppm, preferably about 1 to 5ppm, based on the total mass of the hydrogen-terminated silicone oil, the diene, the p-1-butenyl toluene and/or the 1-allyl-2-toluene.

9. Use of a compound represented by the formula (1) according to claim 1 as a modified polysiloxane foam stabilizer for polyurethane flexible foams.

Technical Field

The invention relates to the field of organosilicon foam stabilizer for polyurethane foam, in particular to modified polysiloxane, a preparation method thereof and application of the foam stabilizer for polyurethane soft foam.

Background

The polyurethane soft foam silicone oil is also called foam homogenizing agent, foam stabilizer or foam stabilizer, is a modified polysiloxane surfactant, and is an important auxiliary agent in the polyurethane foaming process. The foaming process is that various materials are subjected to chemical reaction in a very short time, and the materials are changed into colloid from liquid and then into high polymer, and undergo at least 5 processes of reaction, foaming, foam stabilization, foam fixation and the like. The foam stabilizer ensures that various reactions in the polyurethane foaming process are smoothly carried out, supports the foam body, and avoids the undesirable phenomena of foam collapse, air hole thickening, foam cracking and the like.

At present, the hard foam and semi-hard foam polyurethane foam homogenizing agents are widely researched in China, and the product performance of the foam homogenizing agents also reaches or even replaces the same products abroad; because the Mc (molecular weight between cross-linking points in the large molecules of the three-dimensional structure) of the hard foam polyether is 400-700, the Mc of the semi-hard foam is 700-2500, while the Mc of the soft foam is 2500-20000. Therefore, in the field of flexible foam, the foam stabilizer has very high requirements on the stability, the directional adsorption force, the solubilizing property and the compatibility of the foam stabilizer, and the foam stabilizer cannot be achieved by the common rigid foam polyurethane foam stabilizer, so the market of the foam stabilizer is monopolized by foreign companies all the time. Aiming at the current situation, a preparation method of an organic silicon foam stabilizer special for polyurethane flexible foam is developed to solve the problem in practical application.

Currently, polyether modified polysiloxane is widely used in the research field of foam stabilizer. Patent 1: CN200810021954 foam stabilizer for high-resilience foam of polyurethane in high MDI system mainly researches two polyether modified polysiloxanes with different polymerization degrees and molecular weights, which is characterized in that the polyether modified polysiloxanes are composed of two components A and B, wherein the weight percentage of A is 50-80%, the weight percentage of B is 20-50%, the principle is similar to the preparation of two emulsifiers with different HLB values, and the emulsifying property is improved by compounding. Patent 2: CN201310296323, a preparation method of a polyether modified polysiloxane foam stabilizer, on the basis of the above patent, increases the end capping rate of polyether, eliminates the residue of hydroxyl, and improves the stability of the foam stabilizer; the narrow distribution of the molecular weight of the modified polyether is improved (the wide molecular weight distribution can cause the instability of the polyether component), and the foam homogenizing effect of the foam homogenizing agent is further improved. As in patent 3: CN201810919492 "general polyurethane foam homogenizing agent and preparation method thereof", is also realized by designing special molecular weight and proportion of low hydrogen silicone oil and allyl polyether, and controlling conversion rate of reaction between Si-H and C ═ C in allyl polyether.

In all the above patents, the proportional molecular weight or polymerization degree of polyether is designed and adjusted, and polyether is hydrophilic group, which has more solubilizing effect, and no consideration is given to modification and modification of silicone, and compatibility of silicone and raw materials is not enhanced, oil phase raw materials of polyurethane soft foam are mostly TDI, MDI and modified MDI, and these raw materials are all carbon chain structures with benzene rings, while lipophilic main chain of general foam stabilizer is Si-O-Si structure, and compatibility with oil phase is general. Therefore, the lipophilic group of the common foam stabilizer is a pure organosilicon link, the compatibility of the common foam stabilizer with the raw oil phase is common, the common foam stabilizer cannot be well directionally adsorbed on a liquid-liquid interface of an oil phase and a water phase, and the emulsification effect is greatly reduced. The foaming process of the soft foam is different from the ordinary hard foam physical foaming, especially a large amount of insoluble substituted urea is generated in the foaming process of the soft foam, the molecular weight of the soft foam is large, and if the compatibility of the foam homogenizing agent and the substituted urea is insufficient, the cell walls can be broken, and the cell framework can be rapidly collapsed.

Disclosure of Invention

The invention aims to overcome the defects and provides a modified polysiloxane foam stabilizer for polyurethane flexible foam and a preparation method thereof. According to the principle of similar and compatible emulsifying agents, a linear carbon chain structure is embedded into a polysiloxane main chain with a certain polymerization degree, a terminal methyl inert group is replaced by a carbon chain structure group with a structure similar to TDI, compatibility of lipophilic chain links is enhanced, compatibility of organic silicon chain links with modified main chains and terminals is stronger with toluene diisocyanate when raw materials are mixed, and therefore directional adsorption capacity of a foam homogenizing agent in a liquid-liquid system is enhanced.

In addition, flexible polyurethane foams produce more insoluble substituted ureas during foaming, with carbon chain modified silicones being more soluble than unmodified silicones. Meanwhile, the main chain organic silicon is modified by p-1-butenyl toluene or 1-allyl-2-toluene, so that the surface tension of the main chain of the polysiloxane is reduced, the functions of groups at two ends of the copolymer are enhanced, the mutual influence and interference between long-chain hydrophobic groups and hydrophilic groups are avoided, the hydrophilic and lipophilic adjusting dimensionality of the organic silicon polyether copolymer is increased, and a larger structural space is provided for the hydrophilic and lipophilic adjustment of the organic silicon polyether copolymer.

Finally, 2000-3500 large molecular weight allyl polyether is selected to modify the modified organic silicon. The hydrophilicity of the emulsion is changed, the molecular weight is larger, the solubilization effect is better, and the emulsifying capacity is stronger.

According to one aspect of the present invention, there is provided a modified polysiloxane compound represented by the formula (1):

wherein m is 1 to 10, preferably 2 to 6; n is 5 to 100, preferably 10 to 50;

r is- (CH)₂) q-is a divalent radical of straight carbon chain structure, where q is 4 to 8, preferably 4 to 6;

R₁is p-toluene-1-butenyl, 2-toluene-1-allyl;

R₂is polyether allyl; CH (CH)₂＝CH-CH-(CH₂-CH₂-O)x-(CH₂-CH(CH₃)-O)_y-H

Wherein x is from 20 to 40, preferably from 25 to 35, and y is from 20 to 60, preferably from 30 to 50.

According to another aspect of the present invention, there is provided a method for producing a modified polysiloxane compound represented by formula (1), which comprises the steps of:

c. the compound of formula (2) is charged into a reaction vessel and heated to 80-110 ℃, preferably 82-90 ℃, for example 85 ℃, in an inert gas atmosphere, for example under nitrogen, in accordance with the total hydrogen content of the compound of formula (2): the molar ratio of the allyl polyether is 1: 1.01-2, preferably 1: 1.05-1.2, the allyl polyether uniformly mixed with a certain amount of a Kanst catalyst and/or a chloroplatinic acid catalyst is slowly dripped into a reaction kettle (for example, 1-20ml/min), the temperature of the reaction kettle rises due to an exothermic reaction, after the dripping is finished, the temperature is kept for a period of time (for example, 0.5-3 hours, preferably about 1 hour) at a certain temperature (for example, 100-130 ℃, preferably 110 and 120 ℃) after the reaction temperature of the system does not rise any more, so as to obtain the polymer of the formula (1),

wherein n, m, R and R₁The definitions of (a) are the same as those described above.

Preferably, the compound represented by formula (2) is prepared by the following steps:

b. reacting a compound represented by formula (3) with tetramethylcyclotetrasiloxane in the following ratio of 1: 0.8 to 5, preferably 1:1 to 4, into a reaction kettle, dehydrating under the protection of inert gas such as nitrogen, adding a catalyst, reacting at a certain temperature for 2 to 10 hours, preferably 4 to 6 hours, neutralizing, filtering to obtain the compound of formula (2),

wherein n, R and R₁The definitions of (a) are the same as those described above.

Preferably, the compound represented by formula (3) is prepared by the following steps:

a. adding hydrogen-terminated silicone oil into a reaction kettle, dehydrating in the protection of inert gas such as nitrogen, and adding 1000g of Si-H participating in the reaction into the reaction kettle at a certain temperature according to the total hydrogen content of the hydrogen-terminated silicone oil (for example, the total hydrogen content is 0.05 percent of the hydrogen-terminated silicone oil): diene: the mol ratio of the p-1-butenyl toluene and/or the 1-allyl-2-toluene is 1.5-3: 1: 1.5-3; preferably 1.8 to 2.2: 1: 1.8-2.2, more preferably about 2:1:2, adding the compound diene, p-1-butenyl toluene and/or 1-allyl-2-toluene, uniformly stirring, adding a certain amount of a Kanst catalyst and/or chloroplatinic acid, then quickly raising the reaction temperature, and keeping the temperature at a certain temperature for 10 minutes to 1 hour, preferably about 30 minutes, so as to obtain the compound represented by the formula (3).

The diene may be selected, for example, from one or more of butadiene, pentadiene, hexadiene, heptadiene and octadiene; butadiene is preferred.

Preferably, in step c, the catalyst may be selected from one or both of a kast catalyst and chloroplatinic acid.

Preferably, in step c, the catalyst is used in an amount of 0.5 to 20ppm, preferably 1 to 5ppm, based on the total weight of the compound represented by formula (2) and allyl polyether. In step c, preferably, before adding the Kanst catalyst, the temperature of the reaction system is increased to 80-110 ℃, and the heat preservation temperature is 110-130 ℃.

In step c, the allyl polyether used has the general formula: CH (CH)₂＝CH-CH-(CH₂-CH₂-O)_x-(CH₂-CH(CH₃)-O)_yH, wherein x is 20-40, y is 20-60, the molecular weight is determined according to the values of x and y, and the structure can be customized by using allyl polyether of Huangma chemical engineering in Zhejiang, and allyl polyether of morning chemical engineering in Yangzhou.

In step b, the catalyst is, for example, one or more of concentrated sulfuric acid, trifluoromethanesulfonic acid, and acidic ion exchange resin, preferably trifluoromethanesulfonic acid. The dosage of the catalyst is 0.1-2%, and the total weight of the compound represented by the formula (3) and the tetramethylcyclotetrasiloxane is taken as a reference. The reaction temperature is 40-75 ℃, preferably 50-65 ℃. The alkali used for neutralization may be, for example, one or both of sodium bicarbonate and calcium carbonate.

In step a, the diene is one or more of butadiene, pentadiene, hexadiene, heptadiene and octadiene; butadiene is more preferred. As the p-1-butenyltoluene and/or 1-allyl-2-toluene, p-1-butenyltoluene is preferable.

In the step a, the reaction temperature is 70-120 ℃, preferably 80-110 ℃, and the system heat preservation temperature is 105-125 ℃, preferably 110-120 ℃.

In step a, the amount of the Kanst catalyst and/or chloroplatinic acid is 0.5 to 20ppm, preferably about 1 to 5ppm, based on the total mass of the hydrogen-terminated silicone oil, the diene, the p-1-butenyl toluene and/or the 1-allyl-2-toluene.

The molecular weight range of the hydrogen-terminated silicone oil can be 4500-5500, the viscosity is preferably 50cp +/-5, the volatile content is preferably less than 1%, and trade names can be used: the hydrogen-terminated silicone oil can be prepared into products (with hydrogen content of 0.5% -0.007%, can be prepared) according to specific requirements, for example, the hydrogen-terminated silicone oil produced by Jiangxi Lanxing fire silicone, Zhejiang Runzhe silicone new material Co., Ltd, Zhejiang Xinanmai chart silicone and Zhejiang Hengheng synthetic silicone can be used.

The invention further provides application of the compound shown in the formula (1) as a modified polysiloxane foam stabilizer for polyurethane flexible foam.

Advantageous effects

Compared with the existing modified organic silicon foam stabilizer for soft foam, the foam stabilizer of the invention is characterized in that: the polymer represented by the formula (1) increases a carbon chain structure in the silicone chain of the main chain, and enhances the compatibility of the main chain with an oil phase compared with the conventional silicone chain; compared with the conventional trimethyl-terminated organosilicon, the polymer represented by the formula 1 has the terminal methyl inert group replaced by a carbon chain structural group with a structure similar to TDI, so that the functions of the two end groups of the copolymer are enhanced, the mutual influence and interference between a long-chain hydrophobic group and a hydrophilic group are avoided, the hydrophilic and lipophilic adjusting dimensionality of the organosilicon polyether copolymer is increased, and a larger structural space is provided for the hydrophilic and lipophilic adjustment of the organosilicon polyether copolymer. The compatibility of oleophylic chain links is enhanced, and the compatibility of organic silicon chain links with modified main chains and end positions and toluene diisocyanate is stronger when the raw materials are mixed, so that the directional adsorption capacity of the foam stabilizer in a liquid-liquid system is enhanced.

In addition, 2000-3500 large molecular weight allyl hyperbranched polyether is selected to modify the modified organic silicon. The hydrophilicity of the emulsion is changed, the molecular weight is larger, the solubilization effect is better, and the emulsifying capacity is stronger. The polymer prepared by the method can meet the higher performance requirement of the foam stabilizer for soft foam, and the emulsification and foam stabilizer has more excellent emulsification and foam stabilizing effects.

Detailed Description

The following examples are given to further illustrate the preparation of the present invention and should not be construed as limiting the scope of the invention to the embodiments set forth herein. Parts are parts by mass unless otherwise specified.

Example 1

600 parts of terminal hydrogen-containing silicone oil (terminal hydrogen-containing silicone oil, constant industry silicone limited of manufacturers) with the hydrogen content of 0.1361% and the degree of polymerization 20 is put into a 1L reaction kettle, heated to 120 ℃ in nitrogen protection for water removal, cooled to 80 ℃, and subjected to reaction according to the total hydrogen content of the terminal hydrogen-containing silicone oil (600 parts x 0.1361% ═ 0.8166 mol): hexadiene: adding 33 parts of hexadiene and 119 parts of p-1-butenyl toluene at a molar ratio of (2:1:2) to the p-1-butenyl toluene at 80 ℃, uniformly mixing, adding 0.002 part of a Kaster catalyst (3ppm) (the Kaster catalyst is purchased from PL-56 manufacturer of Shanghai Silibao high New materials Co., Ltd.), rapidly increasing the system temperature, and keeping the temperature at 110 ℃ for 30min to obtain a polymer (3) with a molecular weight of 3600 (determined according to the GPC relative molecular weight).

In this reactor, the polymerization temperature was adjusted as per polymer (3): the molar ratio of tetramethylcyclotetrasiloxane is (1: 3) 100 parts of tetramethylcyclotetrasiloxane are added. 1.7 parts of trifluoromethanesulfonic acid as a catalyst was added, and after 6 hours of reaction at 50 ℃, neutralization and filtration were carried out to obtain polymer (2) having a molecular weight of 4082 and a hydrogen content of 0.0614% (determination of the hydrosilylation content by PGC and infrared).

100 parts of the polymer (2) are added into a 1L reaction kettle, heated to 80 ℃ under the protection of nitrogen, and the hydrogen content of the polymer (2): the molar ratio of the polyether is (1: 1.1), the structure of the slow dropwise adding is CH₂＝CH-CH-(CH₂-CH₂-O)₃₀-(CH₂-CH(CH₃)-O)₂₀813 parts of allyl polyether (containing 0.005 part of Kaster catalyst, trade name: allyl polyether, manufacturer: morning chemical Co., Ltd., Yangzhou, structure customization), the temperature of the reaction system rises, and after the dropwise addition, the temperature of the system does not rise any more and is kept at 110 ℃ for 1 hour, so that the polymer represented by the above formula (1) is obtained (the reaction progress is monitored by the change of the amount of hydrosilicon according to infrared characteristics).

Example 2

600 parts of terminal hydrogen-containing silicone oil (Hengyun silicone Co., Ltd.) with the terminal hydrogen content of 0.0904% and the degree of polymerization of 30 is put into a 1L reaction kettle, heated to 120 ℃ under the protection of nitrogen gas for dehydration, cooled to 90 ℃, and added according to the total hydrogen content of the terminal hydrogen-containing silicone oil: hexadiene: adding 20 parts of hexadiene and 71 parts of p-1-butenyl toluene at a molar ratio of (1.8:1:1.8) of the p-1-butenyl toluene at 90 ℃, uniformly mixing, adding 5ppm0.003 part of a Kanster catalyst, rapidly increasing the system temperature, and preserving the temperature at 110 ℃ for 30min after the temperature is not increased any more to obtain a polymer (3) with the molecular weight of 5082 (determined according to viscosity and GPC).

In this reactor, the polymerization temperature was adjusted as per polymer (3): the molar ratio of tetramethylcyclotetrasiloxane is (1: 2) 99 parts of tetramethylcyclotetrasiloxane are added. 1.6 parts of trifluoromethanesulfonic acid as a catalyst was added, and after 6 hours of reaction at 50 ℃, neutralization and filtration were carried out to obtain polymer (2) having a molecular weight of 5322 and a hydrogen content of 0.225% (determined by viscosity and infrared, respectively).

100 parts of the polymer (2) are added to a 1L reactor, heated to 90 ℃ under nitrogen protection, and the hydrogen content of the polymer (2): the molar ratio of the polyether is (1: 1.1), the structure of the slow dropwise adding is CH₂＝CH-CH-(CH₂-CH₂-O)₂₀-(CH₂-CH(CH₃)-O)₂₀514 parts of (0.003 parts of Karster catalyst) of (H) -allyl polyether (allyl polyether available from morning chemical Co., Ltd., Yangzhou) obtained by reacting the polymer of the above formula (1) (the degree of progress of the reaction was monitored by measuring the amount of silicon hydrogen by infrared spectroscopy) with the temperature of the reaction system rising and then not rising any more after the completion of the dropwise addition.

Example 3:

600 parts of terminal hydrogen-containing silicone oil (terminal hydrogen-containing silicone oil produced by Hengyucheng organosilicon Co., Ltd.) having a terminal hydrogen content of 0.0541% and a degree of polymerization of 50 was charged into a 1L reactor, heated to 120 ℃ under nitrogen protection to remove water, and then cooled to 100 ℃ according to the total hydrogen content of the terminal hydrogen-containing silicone oil: butadiene: adding 8.7 parts of butadiene and 47 parts of p-1-butenyl toluene at the molar ratio of (2:1:2) of the p-1-butenyl toluene at 100 ℃, uniformly mixing, adding 5ppm0.003 part of a Kaster catalyst, rapidly increasing the system temperature, and preserving the temperature at 120 ℃ for 30min after the temperature is not increased any more to obtain a polymer (3) with the molecular weight of 8014 (determined according to viscosity).

In this reactor, the polymerization temperature was adjusted as per polymer (3): 59 parts of tetramethylcyclotetrasiloxane are added in a molar ratio of (1: 3). Adding 1.4 parts of catalyst trifluoromethanesulfonic acid, reacting at 50 ℃ for 6 hours, neutralizing, and filtering to obtain polymer (2), wherein the molecular weight is 8732, and the hydrogen content is 0.137% (determined according to viscosity and infrared methods, respectively).

Adding 100 parts of the polymer (2) into a 1L reaction kettle, heating to 100 ℃ under the protection of nitrogen, and reacting according to the hydrogen content of the polymer (2): the molar ratio of the polyether is (1: 1.15), and the structure of the slow dropwise adding is CH₂＝CH-CH-(CH₂-CH₂-O)₃₀-(CH₂-CH(CH₃)-O)₃₀489 parts of (0.003 part of Karster catalyst) allyl polyether of-H (allyl polyether available from morning chemical Co., Ltd., Yangzhou), which increased the temperature of the reaction system, and after the completion of the dropwise addition, the temperature of the system did not increase any more, and the system was kept at 120 ℃ for 1 hour to obtain a polymer represented by the above formula (1) (the degree of progress of the reaction was monitored by the change in the amount of silicon hydrogen according to infrared characterization).

Example 4:

600 parts of terminal hydrogen-containing silicone oil (terminal hydrogen-containing silicone oil produced by Hengyucheng organosilicon Co., Ltd.) having a terminal hydrogen content of 0.2748% and a degree of polymerization of 10 was charged into a 1L reactor, heated to 120 ℃ under nitrogen protection to remove water, and then cooled to 100 ℃ in accordance with the total hydrogen content (600 × 0.2748% ═ 1.6488 mol): butadiene: adding 44 parts of butadiene and 240 parts of p-1-butenyl toluene at the molar ratio of (2:1:2) of the p-1-butenyl toluene at 100 ℃, uniformly mixing, adding 5ppm0.004 parts of a Kanster catalyst, rapidly increasing the temperature of the system, and preserving the temperature at 120 ℃ for 30min after the temperature is not increased any more to obtain a polymer (3) with the molecular weight of 2094 (determined according to viscosity and GPC).

In this reactor, the polymerization temperature was adjusted as per polymer (3): 101 parts of tetramethylcyclotetrasiloxane are added in a molar ratio of (1: 1) to the tetramethylcyclotetrasiloxane. Adding 1.8 parts of catalyst trifluoromethanesulfonic acid, reacting at 50 ℃ for 6 hours, neutralizing, and filtering to obtain polymer (2), wherein the molecular weight is 3054, and the hydrogen content is 0.131% (determined according to viscosity and infrared methods respectively).

100 parts of the above polymer (2) was charged in a 1L reactor under nitrogenHeating to 100 ℃ under gas protection, according to the hydrogen content (100 × 0.131% ═ 0.131mol) of the polymer (2): the molar ratio of the polyether is (1: 1.15), and the structure of the slow dropwise adding is CH₂＝CH-CH-(CH₂-CH₂-O)₄₀-(CH₂-CH(CH₃)-O)₃₀And 553 parts of (0.003 part of Karster catalyst-containing) H allyl polyether (allyl polyether available from morning chemical Co., Ltd., Yangzhou), the temperature of the reaction system rose, and after the dropwise addition was completed, the temperature of the system did not rise any more and was maintained at 120 ℃ for 1 hour to obtain a polymer represented by the above formula (1) (the degree of progress of the reaction was monitored by the change in the amount of silicon hydrogen in accordance with infrared characterization).

Performance test of the Compounds of the above examples for use as foam levelers

Remarking: TEP-330N and TPOP36-28 are polyether polyol products of Tianjin petrochemical company of China petrochemical group; WannatePM-200 is a product of Tantawanghua chemical MDI. NCO content is about 30.5-32%, and the ratio of the competitive product 1: l6863 magical chart, race 2: SD532 new stipe material, race 3: SD121 New Style materials.

Comparative results of test Performance of foam homogenizers of examples and comparative examples

Experimental data	Rise time/s	Time/s of full cup	Drawing time/s
				Example 1	10.9	33.8	76.0
Example 2	10.1	34.8	74.6
				Example 3	10.6	34.8	74.6
Example 4	10.6	34.1	73.3
				Competition 1	12.5	40.4	85.8
Competition 2	13.5	43.4	94.0
				Competition 3	13.5	42.4	95.8

The experimental environment is as follows: the temperature is 18.3 ℃ and the humidity is 17%

The higher the density, the better the foam homogenizing effect. The better the foam homogenizing effect, the shorter the starting time, the cup filling time and the wire drawing time. As can be seen from the results in the above tables, the rise time, the cup filling time, and the drawing time of the inventive examples are shorter than those of the comparative samples, and therefore, the inventive examples have a better foam leveling effect.