Organosilicon copolymer, preparation method thereof and application of organosilicon copolymer in preparation of foam stabilizer

Abstract

The invention discloses an organosilicon copolymer, a preparation method thereof and an application of the organosilicon copolymer in preparation of a foam stabilizer, and relates to the technical field of surfactants. The structural formula of the organosilicon copolymer is as follows: # imgabs0 #, wherein the structural formula of R1 is # imgabs1 #, m is 2-10, p is 1-4, q is 1-8, and m + p + q is 4-20; the structural formula of R1 is-CH2CH2CH2O, the structural formula of R2 is-CH2CH2CH2O (CH2CH2CH2CH2O) xCH3, and x is 1-7. By introducing the R1 group and the R2 group, the weather resistance, the mechanical property and the flexibility of the organosilicon copolymer are improved, the wear resistance, the folding resistance, the tensile strength and the tearing strength of the subsequent polyurethane microporous elastomer are improved, and the density and the hardness are reduced. The organosilicon copolymer provided by the invention can be widely applied to preparation of various foam stabilizers, and the polyurethane microporous elastomer prepared from the foam stabilizers has excellent performance.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, and in particular to an organosilicon copolymer and a preparation method thereof and application thereof in the preparation of a foam stabilizer. Background Art

[0002] Polyurethane materials have superior comprehensive performance and a wide range of applications. Among the many polyurethane branches, microporous elastomers are new materials between foams and elastomers. They have uniform pore size distribution and combine the advantages of foam, such as light weight, good impact resistance, and good cushioning performance, with the high strength and good wear resistance of elastomers. Therefore, they are particularly suitable as sole materials.

[0003] In recent years, there has been a trend towards lighter sole materials, however, the decrease in the density of polyurethane sole materials has created a problem of dimensional stability of molded products, which means that the bottom becomes smaller, or the surface quality of the sole material is affected due to space shrinkage.

[0004] Patent application DE2402734 discloses the preparation of integral polyurethane materials by mixing polyester alcohol-based prepolymers with polyether alcohols. The disadvantages of the polyurethane system prepared in this way are that the incompatibility of polyester alcohols and polyether alcohols, especially at low density, has an adverse effect on the mechanical properties and cannot prevent the shrinkage of the polyurethane foam.

[0005] Patent application CN1705695A discloses that the bulk density of polyurethane microporous elastomer can be improved by introducing aromatic amines and quaternary ammonium salts containing primary amines into the formula chain extender, thereby increasing the yield of the foaming agent. Although the polyurethane material prepared in this way can improve the density problem, it fails to show improvement in the shrinkage, foam surface quality and mechanical properties of the polyurethane foam.

[0006] Patent application EP1042384 discloses the preparation of low-density, dimensionally stable polyurethane materials by using a large amount of grafted polyether polyols. The disadvantage of this approach is that the mechanical properties are significantly inferior to those of polyester alcohol-based polyurethane materials. In addition, the high proportion of polyether alcohols has an adverse effect on the viscosity of the polyols.

[0007] There is currently no report that changes in the foam stabilizer structure can improve the surface quality, mechanical properties, shrinkage and other issues of polyurethane materials.

[0008] In view of this, the present invention is proposed. Summary of the invention

[0009] The object of the present invention is to provide an organosilicon copolymer and a preparation method thereof and application thereof in the preparation of a foam stabilizer.

[0010] The present invention is achieved in that:

[0011] In a first aspect, the present invention provides an organosilicon copolymer, the structural formula of which is shown below:

[0012]

[0013] Among them, the structural formula of R1 is m is 2 to 10, p is 1 to 4, q is 1 to 8, m+p+q is 4 to 20; the structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O) x CH3, x is 1~7.

[0014] In a second aspect, the present invention provides a method for preparing an organosilicon copolymer as described in the aforementioned embodiment, comprising: subjecting hydrogen-containing polysiloxane, allylmethyl-terminated polytetramethylene furan polyether and naphthyl acrylate to an addition reaction to obtain an organosilicon copolymer.

[0015] In an optional embodiment, the molar ratio of the hydrogen-containing polysiloxane, the allyl methyl terminated polytetramethylene furan polyether and the naphthyl acrylate is 1.0:(0.6-1.1):(0.3-0.8);

[0016] Preferably, the reaction temperature of the addition reaction is 110-150° C., and the reaction time is 3-8 hours.

[0017] In an optional embodiment, the preparation method of the allyl methyl terminated polytetrahydrofuran polyether comprises: using allyl alcohol as an initiator and tetrahydrofuran and methyl chloride to obtain the polyether through ring-opening addition polymerization;

[0018] Preferably, the molar ratio of the allyl alcohol, the tetrahydrofuran and the methyl chloride is 1.0:(1.0-5.0):(1.3-1.6);

[0019] Preferably, the molecular weight of the allyl methyl terminated polytetramethylene furan polyether is 100-400.

[0020] In an optional embodiment, a polymerization inhibitor is further added to the addition reaction, and the amount of the polymerization inhibitor added is 50 to 500 ppm;

[0021] Preferably, the polymerization inhibitor is at least one of p-phenylenediamine, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, 2,4-dimethyl-6-tert-butylphenol and tetramethylpiperidinium nitrophosphite triester.

[0022] In an optional embodiment, a catalyst is further added to the addition reaction, and the amount of the catalyst added is 5 to 15 ppm;

[0023] Preferably, the catalyst is chloroplatinic acid or platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex.

[0024] In a third aspect, the present invention provides the use of the organosilicon copolymer as described in the above embodiment or the organosilicon copolymer prepared by the preparation method of the organosilicon copolymer as described in any one of the above embodiments in the preparation of a foam stabilizer;

[0025] Preferably, the foam stabilizer is a polyurethane microcellular elastomer foam stabilizer.

[0026] In a fourth aspect, the present invention provides a polyurethane microporous elastomer foam stabilizer, which comprises a solvent and an organosilicon copolymer as described in the aforementioned embodiment or an organosilicon copolymer prepared by the method for preparing an organosilicon copolymer as described in any one of the aforementioned embodiments.

[0027] In an optional embodiment, the mass ratio of the organosilicon copolymer to the solvent is 1.0:(1.0-20.0);

[0028] Preferably, the solvent is at least one of phthalates, fatty acid esters, polyoxypropylene ethers, epoxy esters, phosphates and chlorinated alkanes.

[0029] In a fifth aspect, the present invention provides a polyurethane microcellular elastomer, which is prepared by the organosilicon copolymer described in the aforementioned embodiment or the polyurethane microcellular elastomer foam stabilizer described in the aforementioned embodiment.

[0030] The present invention has the following beneficial effects:

[0031] The organosilicon copolymer provided by the present invention introduces R1 group and R2 group, wherein the R1 group contains a naphthalene group, which is beneficial to increase the weather resistance and mechanical properties of the organosilicon copolymer, and helps to improve the wear resistance and folding resistance of the subsequent polyurethane microporous elastomer. R2 contains polytetrahydrofuran polyether, which can increase the flexibility of the organosilicon copolymer, which is beneficial to reduce the density and hardness of the subsequent polyurethane microporous elastomer, improve the tensile strength and tear strength, and make the polyurethane microporous elastomer have better dimensional stability and better mechanical properties. The organosilicon copolymer provided by the present invention can be widely used in the preparation of various foam stabilizers, and the polyurethane microporous elastomer prepared by the foam stabilizer has excellent performance. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0033] The present invention provides an organosilicon copolymer, the structural formula of which is shown below:

[0034]

[0035] Among them, the structural formula of R1 is; m is 2 to 10, p is 1 to 4, q is 1 to 8, m+p+q is 4 to 20; the structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O) x CH3, x is 1~7.

[0036] In the present invention, by introducing R1 group and R2 group, wherein the R1 group contains a naphthalene group, it is beneficial to increase the rigidity and heat resistance of the organosilicon copolymer; it is beneficial to increase the wear resistance and folding resistance of the polyurethane microporous elastomer. R2 contains polytetrahydrofuran polyether, which is beneficial to improve the flexibility of the organosilicon copolymer, and can make the polyurethane microporous elastomer have a lower density, better dimensional stability, and better mechanical properties.

[0037] The present invention provides a method for preparing the above-mentioned organosilicon copolymer, which comprises the following steps:

[0038] (1) Hydrogen-containing polysiloxane, allylmethyl-terminated polytetrahydrofuran polyether and naphthyl acrylate are subjected to addition reaction to obtain an organosilicon copolymer, wherein the molar ratio of hydrogen-containing polysiloxane, allylmethyl-terminated polytetrahydrofuran polyether and naphthyl acrylate is 1.0:(0.6-1.1):(0.3-0.8); the reaction temperature of the addition reaction is 110-150° C., and the reaction time is 3-8 hours.

[0039] In the present invention, the structural formula of hydrogen-containing polysiloxane is:

[0040] Among them, m is 2 to 10, p is 1 to 4, q is 1 to 8, and m+p+q is 4 to 20.

[0041] In the present invention, the preparation method of allyl methyl terminated polytetrahydrofuran polyether comprises: using allyl alcohol as an initiator and tetrahydrofuran and methyl chloride to obtain the obtained product through ring-opening addition polymerization; in the present invention, polytetrahydrofuran polyether is formed and terminated with allyl and methyl groups, wherein the polytetrahydrofuran polyether can make the polyurethane microporous elastomer have lower density, better dimensional stability and better mechanical properties. Wherein, the molar ratio of allyl alcohol, tetrahydrofuran and methyl chloride is 1.0: (1.0-5.0): (1.3-1.6); the molecular weight of the allyl methyl terminated polytetrahydrofuran polyether is 100-400. It should be understood that the ring-opening addition polymerization needs to be carried out under the action of a certain catalyst, and the catalyst is selected as a conventional catalyst, including but not limited to at least one of sodium hydroxide, potassium hydroxide or sodium methoxide, and the reaction conditions are, for example, stirring and reacting for 4-6 hours at 50-95°C and a pressure of 0.3-0.4MPa.

[0042] In the present invention, the structural formula of naphthyl acrylate is The double bond at the end can be used to introduce a naphthalene group into the hydrogen-containing polysiloxane, thereby increasing the rigidity and heat resistance of the silicone copolymer, and further increasing the wear resistance and folding resistance of the polyurethane microporous elastomer.

[0043] Furthermore, a polymerization inhibitor and / or a catalyst are added to the addition reaction, and the amount of the polymerization inhibitor added is 50 to 500 ppm; the amount of the catalyst added is 5 to 15 ppm.

[0044] The polymerization inhibitor is used to prevent the polymerization. Specifically, the polymerization reaction of allyl methyl terminated polytetramethylene furan polyether and naphthyl acrylate can be prevented by adding the polymerization inhibitor, which is beneficial to promote the independent grafting of allyl methyl terminated polytetramethylene furan polyether and naphthyl acrylate onto the hydrogen-containing polysiloxane.

[0045] Preferably, the inhibitor includes but is not limited to at least one of p-phenylenediamine, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, 2,4-dimethyl-6-tert-butylphenol and tetramethylpiperidinium nitrogen oxide phosphite; the catalyst includes but is not limited to chloroplatinic acid or platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex.

[0046] (2) Mixing the organosilicon copolymer and the solvent.

[0047] The mass ratio of the organosilicon copolymer to the solvent is 1.0:(1.0-20.0); the mixing includes mixing and stirring at 40-70°C for 1-3 hours, and the organosilicon copolymer can be fully dispersed and diluted in the solvent through mixing and stirring. The present invention has found that if the organosilicon copolymer is directly used as a foaming stabilizer, its effect is poor, and it needs to be mixed with a solvent first for dispersion, which is more conducive to improving mechanical properties.

[0048] Preferably, the solvent includes, but is not limited to, at least one of phthalates, fatty acid esters, polyoxypropylene ethers, epoxy esters, phosphates and chlorinated alkanes.

[0049] The above preparation method can introduce allyl methyl terminated polytetrahydrofuran polyether and naphthalene groups into hydrogenated polysiloxane, so that the polyurethane microporous elastomer has lower density, better dimensional stability, and better mechanical properties; the wear resistance and folding resistance of the polyurethane microporous elastomer are increased. The prepared organosilicon copolymer can be widely used in the preparation of foam stabilizers; preferably, the foam stabilizer is a polyurethane microporous elastomer foam stabilizer.

[0050] Correspondingly, the present invention also provides a polyurethane microporous elastomer foam stabilizer, which includes the above-mentioned organosilicon copolymer or the organosilicon copolymer prepared by the preparation method of the above-mentioned organosilicon copolymer.

[0051] Further, the present invention also provides a polyurethane microporous elastomer, which is prepared by the above-mentioned organosilicon copolymer or the above-mentioned polyurethane microporous elastomer foam stabilizer. It should be understood that the polyurethane microporous elastomer may also include other conventional ingredients, including but not limited to polyester polyol (2 functionalities, molecular weight 2000), polyether polyol (3 functionalities, molecular weight 5000), ethylene glycol, water, triethylene diamine, stannous octoate, polyether polyol (2 functionalities, molecular weight 4000), diphenylmethane diisocyanate (MDI) and other components.

[0052] Specifically, the components of the polyurethane microporous elastomer include component A and component B, the mass ratio of component A to component B is 100:(60-100), and the specific material selection is as follows:

[0053] Table 1. Component selection of polyurethane microcellular elastomer

[0054]

[0055]

[0056] The preparation method of the polyurethane microporous elastomer comprises:

[0057] Preparation of component A: put the measured polyether polyol and polyester polyol into the device and stir, then add the measured cross-linking agent, catalyst, stabilizer and foaming agent and stir evenly;

[0058] Preparation of component B: Add the polyether polyol based on the formula into the reactor, stir and then heat it to 90-110°C, vacuum dehydrate for a certain period of time and then cool it to 20-40°C, add isocyanate, heat it to 80-90°C, react for a certain period of time and then cool it down;

[0059] The polyurethane microporous elastomer can be prepared by mixing the A and B component materials according to the mass ratio of A:B=100:(60-100).

[0060] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0061] Example 1

[0062] This embodiment provides an organosilicon copolymer, which includes the following steps:

[0063] S1: 71.2g is structured as Hydrogenated polysiloxane (abbreviated as MD5D'3M, the same below), 80.9g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 289, 31.7g of naphthyl acrylate and 100ppm of hydroquinone were put into a four-necked flask, stirred evenly, and then 10ppm of chloroplatinic acid catalyst was added, the temperature was raised to 130-140℃, and then the temperature was kept for reaction for 5h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0064]

[0065] Among them, the structural formula of R1 is

[0066] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)3CH3.

[0067] S2: Weigh 40.0 g of the organosilicon copolymer prepared in step S1 and 160.0 g of dioctyl phthalate and stir at 50° C. for 2 h.

[0068] The preparation method of allyl methyl terminated polytetrahydrofuran polyether is as follows: adding measured allyl alcohol and potassium hydroxide into a stainless steel autoclave, drawing the vacuum degree to -0.09 to -0.1 MPa, heating to 100°C, gradually introducing measured tetrahydrofuran, controlling the reaction temperature not to exceed 130°C, drawing the vacuum after the reaction is completed to remove small molecular residues, and refining the allyl polytetrahydrofuran polyether with a specific structure by neutralization treatment with phosphoric acid; and then adding measured allyl alcohol and potassium hydroxide into the stainless steel autoclave according to the measured amount. The prepared specific structure allyl polytetrahydrofuran polyether and sodium methoxide are added, evacuated to -0.09-0.1 MPa, heated to 100-110°C, maintained for 1-3 hours, then cooled to 80-90°C, gradually introduced measured methyl chloride, maintained at a pressure of 0.3-0.5 MPa, reacted for a certain time, added measured distilled water, allowed to stand for stratification, removed the aqueous phase, vacuum dehydrated, filtered to remove solid impurities to obtain a specific structure methyl-terminated allyl polytetrahydrofuran polyether (the same below).

[0069] Example 2

[0070] This embodiment provides an organosilicon copolymer, which includes the following steps:

[0071] S1: Convert 87.6g into MD3D' 2.5 M hydrogen-containing polysiloxane, 126.8g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 369, 53.6g of naphthyl acrylate and 200ppm of 2,4-dimethyl-6-tert-butylphenol were put into a four-necked flask, stirred evenly, and then 12ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 7h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0072]

[0073] Among them, the structural formula of R1 is

[0074] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)4CH3.

[0075] S2: Weigh 80.0 g of the organosilicon copolymer prepared in step S1 and 120.0 g of butyl polyoxypropylene ether and stir at 65° C. for 1 hour.

[0076] Example 3

[0077] This embodiment provides an organosilicon copolymer, which includes the following steps:

[0078] S1: 68.5 g of MD4D'4M hydrogen-containing polysiloxane, 65.3 g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 221, 58.2 g of naphthyl acrylate and 150 ppm of p-hydroxyanisole were put into a four-necked flask, stirred evenly, and then 11 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 6 hours, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0079]

[0080] Among them, the structural formula of R1 is

[0081] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)2CH3.

[0082] S2: Weigh 100.0 g of the organosilicon copolymer prepared in step S1 and 100.0 g of sorbitan trioleate and stir at 65° C. for 1 hour.

[0083] Example 4

[0084] This embodiment provides an organosilicon copolymer, which includes the following steps:

[0085] S1: 76.6g structure as MD 3.5 D' 3.5 M hydrogen-containing polysiloxane, 105.3g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 289, 63.8g of naphthyl acrylate and 300ppm of 2,6-di-tert-butyl-p-cresol were put into a four-necked flask, stirred evenly, and then 9ppm of chloroplatinic acid catalyst was added, the temperature was raised to 130-140°C, and then the temperature was kept for reaction for 6h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0086]

[0087] Among them, the structural formula of R1 is

[0088] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)3CH3.

[0089] S2: Weigh 10.0 g of the organosilicon copolymer prepared in step S1 and 190.0 g of epoxy octyl oleate and stir at 45° C. for 2.5 h.

[0090] Example 5

[0091] This embodiment provides an organosilicon copolymer, which includes the following steps:

[0092] S1: 91.4 g of MD6D'5M hydrogen-containing polysiloxane, 80.0 g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 184, 66.2 g of naphthyl acrylate and 80 ppm of tetramethylpiperidinium nitrogen oxide phosphite triester were added into a four-necked flask, stirred evenly, and then 8 ppm of chloroplatinic acid catalyst was added, the temperature was raised to 140-150° C., and then the temperature was kept for reaction for 4 hours, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0093]

[0094] Among them, the structural formula of R1 is

[0095] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O) 1.5 CH3.

[0096] S2: Weigh 20.0 g of the organosilicon copolymer prepared in step S1 and 180.0 g of tri(2-ethylhexyl) phosphate and stir at 55° C. for 2 h.

[0097] Example 6

[0098] This embodiment provides an organosilicon copolymer, which includes the following steps:

[0099] S1: 85.8g structure as MD 4.5 D'4M hydrogen-containing polysiloxane, 116.1g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 221, 40.9g of naphthyl acrylate and 400ppm of 2-tert-butylhydroquinone were put into a four-necked flask, stirred evenly, and then 8ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 5h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0100]

[0101] Among them, the structural formula of R1 is

[0102] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)2CH3.

[0103] S2: Weigh 60.0 g of the organosilicon copolymer prepared in step S1 and 140.0 g of chlorinated paraffin and stir at 50° C. for 2 h.

[0104] Comparative Example 1

[0105] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0106] S1: 71.2 g of MD5D'3M hydrogen-containing polysiloxane and 121.4 g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 289 were placed in a four-necked flask, stirred evenly, and then 10 ppm of chloroplatinic acid catalyst was added, the temperature was raised to 130-140°C, and then the temperature was kept for reaction for 5 hours, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0107]

[0108] Among them, the structural formula of R is -CH2CH2CH2O(CH2CH2CH2CH2O)3CH3.

[0109] S2: Weigh 40.0 g of the organosilicon copolymer prepared in step S1 and 160.0 g of dioctyl phthalate and stir at 50° C. for 2 h.

[0110] Comparative Example 2

[0111] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0112] S1: Convert 87.6g into MD3D' 2.5 M hydrogen-containing polysiloxane and 196.7g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 369 were put into a four-necked flask, stirred evenly, and then 12ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 7h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0113]

[0114] Among them, the structural formula of R is -CH2CH2CH2O(CH2CH2CH2CH2O)4CH3.

[0115] S2: Weigh 80.0 g of the organosilicon copolymer prepared in step S1 and 120.0 g of butyl polyoxypropylene ether and stir at 65° C. for 1 hour.

[0116] Comparative Example 3

[0117] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0118] S1: 68.5 g of MD4D'4M hydrogen-containing polysiloxane and 105.3 g of allyl methyl terminated polyoxypropylene polyether with a molecular weight of 189 were placed in a four-necked flask, stirred evenly, and then 11 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 6 hours, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0119]

[0120] Among them, the structural formula of R is -CH2CH2CH2O(CH2CH(CH3)O)2CH3.

[0121] S2: Weigh 100.0 g of the organosilicon copolymer prepared in step S1 and 100.0 g of sorbitan trioleate and stir at 65° C. for 1 hour.

[0122] The preparation method of allyl methyl terminated polyoxypropylene polyether comprises: adding measured allyl alcohol and potassium hydroxide into a stainless steel autoclave, evacuating to -0.09-0.1 MPa, heating to 100°C, gradually introducing measured propylene oxide, controlling the reaction temperature not to exceed 130°C, evacuating to remove small molecular residues after the reaction is completed, and refining by neutralization treatment with phosphoric acid to obtain allyl polyoxypropylene polyether with a specific structure; then adding the obtained allyl polyoxypropylene polyether with a specific structure and sodium methoxide into the stainless steel autoclave according to the measurement, evacuating to -0.09-0.1 MPa, heating to 100-110°C, maintaining for 1-3 hours, then cooling to 80-90°C, gradually introducing measured methyl chloride, maintaining the pressure at 0.3-0.5 MPa, reacting for a certain time, adding measured distilled water, standing to separate, removing the water phase, vacuum dehydrating, filtering to remove solid impurities, and obtaining methyl terminated allyl polyoxypropylene polyether with a specific structure (the same below).

[0123] Comparative Example 4

[0124] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0125] S1: 76.6g structure as MD 3.5 D' 3.5 M hydrogen-containing polysiloxane and 146.8 g of allyl methyl terminated polyoxypropylene polyether with a molecular weight of 247 were put into a four-necked flask, stirred evenly, and then 9 ppm of chloroplatinic acid catalyst was added, the temperature was raised to 130-140°C, and then the temperature was kept for reaction for 6 hours, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0126]

[0127] Among them, the structural formula of R is -CH2CH2CH2O(CH2CH(CH3)O)3CH3.

[0128] S2: Weigh 10.0 g of the organosilicon copolymer prepared in step S1 and 190.0 g of epoxy octyl oleate and stir at 45° C. for 2.5 h.

[0129] Comparative Example 5

[0130] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0131] S1: 91.4 g of MD6D'5M hydrogen-containing polysiloxane, 72.6 g of allyl methyl-terminated polyoxypropylene polyether with a molecular weight of 160, 66.2 g of naphthyl acrylate and 80 ppm of tetramethylpiperidinium nitrogen-oxygen phosphite triester were added into a four-necked flask, stirred evenly, and then 8 ppm of chloroplatinic acid catalyst was added, the temperature was raised to 140-150° C., and then the temperature was kept for reaction for 4 hours, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0132]

[0133] Among them, the structural formula of R1 is

[0134] The structural formula of R2 is -CH2CH2CH2O(CH2CH(CH3)O) 1.5 CH3.

[0135] S2: Weigh 20.0 g of the organosilicon copolymer prepared in step S1 and 180.0 g of tri(2-ethylhexyl) phosphate and stir at 55° C. for 2 h.

[0136] Comparative Example 6

[0137] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0138] S1: 85.8g structure as MD 4.5 D'4M hydrogen-containing polysiloxane, 94.7g of allylmethyl-terminated polyoxypropylene polyether with a molecular weight of 189, 40.9g of naphthyl acrylate and 400ppm of 2-tert-butylhydroquinone were put into a four-necked flask, stirred evenly, and then 8ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 5h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0139]

[0140] Among them, the structural formula of R1 is

[0141] The structural formula of R2 is -CH2CH2CH2O(CH2CH(CH3)O)2CH3.

[0142] S2: Weigh 60.0 g of the organosilicon copolymer prepared in step S1 and 140.0 g of chlorinated paraffin and stir at 50° C. for 2 h.

[0143] Comparative Example 7

[0144] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0145] S1: 85.8g structure as MD 4.5 D'4M hydrogen-containing polysiloxane, 120.2g naphthyl acrylate and 400ppm 2-tert-butylhydroquinone were put into a four-necked flask, stirred evenly, and then 8ppm platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 5h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0146]

[0147] Among them, the structural formula of R is

[0148] S2: Weigh 60.0 g of the organosilicon copolymer prepared in step S1 and 140.0 g of chlorinated paraffin and stir at 50° C. for 2 h.

[0149] Comparative Example 8

[0150] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0151] S1: 85.8g structure as MD 4.5 D'4M hydrogen-containing polysiloxane, 116.1g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 221, 40.9g of naphthyl acrylate and 400ppm of 2-tert-butylhydroquinone were put into a four-necked flask, stirred evenly, and then 8ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 5h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0152]

[0153] Among them, the structural formula of R1 is

[0154] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)2CH3.

[0155] Comparative Example 9

[0156] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0157] S1: 85.8g structure as MD 4.5 D'4M hydrogen-containing polysiloxane, 114.5g allyl polytetrahydrofuran polyether 、 40.9 g of naphthyl acrylate and 400 ppm of 2-tert-butylhydroquinone were put into a four-necked flask, stirred evenly, and then 8 ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130° C., and then the temperature was kept for reaction for 5 hours, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0158]

[0159] Among them, the structural formula of R1 is

[0160] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)2H.

[0161] S2: Weigh 60.0 g of the organosilicon copolymer prepared in step S1 and 140.0 g of chlorinated paraffin and stir at 50° C. for 2 h.

[0162] Comparative Example 10

[0163] This comparative example provides an organosilicon copolymer, which comprises the following steps:

[0164] S1: 85.8g structure as MD 4.5 D'4M hydrogen-containing polysiloxane, 340.4g of allyl methyl terminated polytetrahydrofuran polyether with a molecular weight of 648, 40.9g of naphthyl acrylate and 400ppm of 2-tert-butylhydroquinone were put into a four-necked flask, stirred evenly, and then 8ppm of platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex catalyst was added, the temperature was raised to 120-130°C, and then the temperature was kept for reaction for 5h, and the temperature was lowered to obtain an organosilicon copolymer with the structure:

[0165]

[0166] Among them, the structural formula of R1 is

[0167] The structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O)8CH3.

[0168] S2: Weigh 60.0 g of the organosilicon copolymer prepared in step S1 and 140.0 g of chlorinated paraffin and stir at 50° C. for 2 h.

[0169] Experimental example

[0170] The organosilicon copolymers of Examples 1 to 6 and Comparative Examples 1 to 10 are respectively used as polyurethane foam stabilizers to prepare polyurethane microporous elastomers by prepolymerization. The operation and process conditions for preparing the polyurethane microporous elastomers are the same except for the polyurethane foam stabilizers, and are all existing methods for preparing polyurethane microporous elastomers. The specific method for preparing polyurethane microporous elastomers of the present invention is as follows:

[0171] Table 2. Component selection of polyurethane microcellular elastomer

[0172]

[0173] The method for preparing the polyurethane microcellular elastomer composite material of the present invention comprises:

[0174] Preparation of component A: put the measured polyether polyol and polyester polyol into the device and stir, then add the measured cross-linking agent, catalyst, stabilizer and foaming agent and stir evenly;

[0175] Preparation of component B: Add the polyether polyol based on the formula into the reactor, stir and then heat it to 90-110°C, vacuum dehydrate for a certain period of time and then cool it to 20-40°C, add isocyanate, heat it to 80-90°C, react for a certain period of time and then cool it down;

[0176] The polyurethane microporous elastomer can be prepared by mixing the A and B components in a mass ratio of A:B=100:80.

[0177] The performance of the polyurethane microcellular elastomer prepared by using the above different polyurethane foam stabilizers according to the above formula was tested, and the test results are shown in Table 3 below, wherein the density test method is in accordance with the national standard "GB / T 6343-2009 Determination of apparent density of foam plastics and rubber", the hardness test method is in accordance with the national standard "GB / T2411-1980 Plastic Shore hardness test method", the tensile strength test method is in accordance with the national standard "GB / T 528-1992 Determination of tensile properties of vulcanized rubber and thermoplastic rubber", the tear strength test method is in accordance with the national standard "GB / T 529-2008 Determination of tear strength of vulcanized rubber and thermoplastic rubber", the abrasion resistance test method is in accordance with the national standard "GB / T 9867-2008 Determination of abrasion resistance of vulcanized rubber or thermoplastic rubber", and the folding resistance test method is in accordance with the national standard "GB / T3903.1-1994 General test method for footwear - folding resistance test method".

[0178] Table 3. Performance test statistics of polyurethane microcellular elastomers of different examples

[0179]

[0180] It can be seen from the above table that the density and hardness of the polyurethane microporous elastomers obtained in Examples 1-6 of the present invention are significantly lower than those of the comparative example, while the tensile strength and tear strength are significantly higher than those of the comparative example, and the abrasion index and folding resistance are also significantly higher than those of the comparative example. This fully proves that in the present invention, the organosilicon copolymer synthesized by allyl methyl-terminated polytetramethylene furan polyether and naphthyl acrylate is used as a polyurethane foam stabilizer to form a polyurethane microporous elastomer, which not only has a lower density and better mechanical properties, but also, in particular, has better wear resistance and folding resistance.

[0181] Comparative Examples 1-2 both use hydrogen-containing polysiloxane and a single allyl methyl-terminated polytetrahydrofuran polyether for reaction. At this time, although the density and hardness of the polyurethane microporous elastomer are higher than those of Example 1 and Example 2, they are significantly lower than the polyoxypropylene polyether used in Comparative Examples 3-4. Although the tensile strength and tear strength are lower than those of Example 1 and Example 2, they are significantly higher than the polyoxypropylene polyether used in Comparative Examples 3-4. This fully proves that the effect of introducing allyl methyl-terminated polytetrahydrofuran polyether is better than other polyethers; further, due to the lack of introduction of naphthalene groups, its abrasion index and folding resistance are significantly lower than those of Example 1 and Example 2.

[0182] Comparative Examples 3-4 all use hydrogen-containing polysiloxane and a single polyoxypropylene polyether for reaction. Since the polyoxypropylene polyether is harder than the allyl methyl-terminated polytetrahydrofuran polyether, its density and hardness are significantly higher than those of the embodiments and other comparative examples, and its tensile strength and tear strength are significantly lower than those of the embodiments and other comparative examples. Furthermore, since no naphthalene group is introduced, its abrasion index and folding resistance are significantly lower than those of Examples 3 and 4.

[0183] Comparative Examples 5-6 all use hydrogen-containing polysiloxane, polyoxypropylene polyether and naphthyl acrylate for reaction. At this time, due to the introduction of naphthalene groups, their abrasion index and folding resistance are better than those of Comparative Examples 1-4, but still lower than those of the embodiment. At the same time, the introduction of naphthalene groups also helps to reduce density and improve strength.

[0184] In Comparative Example 7, hydrogen-containing polysiloxane and naphthyl acrylate alone were reacted. At this time, naphthyl acrylate was introduced only on the side chain of hydrogen-containing polysiloxane. It can be seen that its density, hardness, tensile strength, tear strength, abrasion index and folding resistance all showed significant increases, proving that the introduction of naphthyl acrylate can improve the above properties. However, the introduction of only naphthyl acrylate will cause its density and hardness to increase significantly, resulting in poor elasticity and significantly increased processing difficulty, making it unsuitable as a sole material.

[0185] In Comparative Example 8, the organosilicon copolymer prepared in step S1 is directly used as the product, and is not dispersed or diluted with a solvent. At this time, due to the lack of dispersion and dilution, its foaming effect is poor, the density and hardness are increased, and the tensile strength, tear strength, abrasion index and folding resistance are significantly reduced, which fully proves that dispersing the organosilicon copolymer with a solvent can improve its performance.

[0186] The different end-capping groups of the polytetramethylene oxide in Comparative Example 9 also lead to an increase in density and hardness, while the tensile strength, tear strength, abrasion index and folding resistance are significantly reduced, proving that the end-capping groups of the polytetramethylene oxide can improve the performance of the silicone copolymer by dispersing it.

[0187] The molecular weight of the allyl methyl-terminated polytetrahydrofuran polyether introduced in Comparative Example 10 is relatively large, resulting in the value range of R2 exceeding the scope of the present application, resulting in a significant increase in the density and hardness of the polyurethane microporous elastomer, but due to the increase in the amount of polyether, the tensile strength, tear strength, abrasion index and folding resistance are significantly reduced.

[0188] In summary, the organosilicon copolymer provided by the present invention, by introducing R1 group and R2 group, wherein the R1 group contains a naphthalene group, which is beneficial to increase the weather resistance and mechanical properties of the organosilicon copolymer, and helps to improve the wear resistance and folding resistance of the subsequent polyurethane microporous elastomer. R2 contains polytetrahydrofuran polyether, which can increase the flexibility of the organosilicon copolymer, which is beneficial to reduce the density and hardness of the subsequent polyurethane microporous elastomer, improve the tensile strength and tear strength, and make the polyurethane microporous elastomer have better dimensional stability and better mechanical properties. The organosilicon copolymer provided by the present invention can be widely used in the preparation of various foam stabilizers, and the polyurethane microporous elastomer prepared by the foam stabilizer has excellent performance.

[0189] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An organosilicon copolymer, characterized in that: Its structural formula is as follows: Among them, the structural formula of R1 is m is 2 to 10, p is 1 to 4, q is 1 to 8, m+p+q is 4 to 20; the structural formula of R2 is -CH2CH2CH2O(CH2CH2CH2CH2O) x CH3, x is 1~7.

2. A method for preparing an organosilicon copolymer as claimed in claim 1, characterized in that: It includes: The organic silicon copolymer is obtained by adding hydrogen-containing polysiloxane, allylmethyl-terminated polytetrahydrofuran polyether and naphthyl acrylate.

3. The method for preparing the organosilicon copolymer according to claim 2, characterized in that: The molar ratio of the hydrogen-containing polysiloxane, the allyl methyl terminated polytetramethylene furan polyether and the naphthyl acrylate is 1.0:(0.6-1.1):(0.3-0.8); Preferably, the reaction temperature of the addition reaction is 110-150° C., and the reaction time is 3-8 hours.

4. The method for preparing the organosilicon copolymer according to claim 2, characterized in that: The preparation method of the allyl methyl terminated polytetrahydrofuran polyether comprises: using allyl alcohol as an initiator and tetrahydrofuran and methyl chloride to obtain the polyether through ring-opening addition polymerization; Preferably, the molar ratio of the allyl alcohol, the tetrahydrofuran and the methyl chloride is 1.0:(1.0-5.0):(1.3-1.6); Preferably, the molecular weight of the allyl methyl terminated polytetramethylene furan polyether is 100-400.

5. The method for preparing an organosilicon copolymer according to claim 2, characterized in that: A polymerization inhibitor is also added in the addition reaction, and the amount of the polymerization inhibitor added is 50 to 500 ppm; Preferably, the polymerization inhibitor is at least one of p-phenylenediamine, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, 2,4-dimethyl-6-tert-butylphenol and tetramethylpiperidinium nitrophosphite triester.

6. The method for preparing an organosilicon copolymer according to claim 2, characterized in that: A catalyst is also added in the addition reaction, and the amount of the catalyst added is 5 to 15 ppm; Preferably, the catalyst is chloroplatinic acid or platinum-1,3-divinyl-1,1,3,3-tetramethylsiloxane complex.

7. Use of the organosilicon copolymer according to claim 1 or the organosilicon copolymer prepared by the method for preparing the organosilicon copolymer according to any one of claims 2 to 6 in the preparation of a foam stabilizer; Preferably, the foam stabilizer is a polyurethane microcellular elastomer foam stabilizer.

8. A polyurethane microcellular elastomer foam stabilizer, characterized in that: The invention comprises a solvent and the organic silicon copolymer according to claim 1 or an organic silicon copolymer prepared by the method for preparing the organic silicon copolymer according to any one of claims 2 to 7.

9. The polyurethane microcellular elastomer foam stabilizer according to claim 8, characterized in that: The mass ratio of the organosilicon copolymer to the solvent is 1.0:(1.0-20.0); Preferably, the solvent is at least one of phthalates, fatty acid esters, polyoxypropylene ethers, epoxy esters, phosphates and chlorinated alkanes.

10. A polyurethane microcellular elastomer, characterized in that: The foam stabilizer is prepared by using the organic silicon copolymer described in claim 1 or the polyurethane microcellular elastomer foam stabilizer described in any one of claims 8 to 9.

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