CN107551609B - Organic silicon-containing modified castor oil defoaming agent for PVA production and preparation method thereof - Google Patents
Organic silicon-containing modified castor oil defoaming agent for PVA production and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic silicon-containing modified castor oil defoaming agent for PVA production and a preparation method thereof, belonging to the organic silicon modified defoaming agentThe field of the technology. Firstly at N2In the protected catalyst system, hydrogen-containing silicone oil and castor oil are subjected to addition reaction to prepare an organic silicon modified castor oil defoamer active substance; and then preparing the defoaming agent containing the organic silicon modified castor oil by using the modified defoaming agent active matter, microcrystalline wax, monoglyceride, isooctyl stearate, an emulsifier, a thickening agent and a carrier. The defoaming agent containing the organic silicon modified castor oil, which is produced according to the invention, is applied to eliminating foam generated in PVA production, has little negative influence on slurry adhesiveness and slurry film mechanical property, and has the characteristics of small dosage, high defoaming speed, strong foam inhibition capability, no toxicity, no harm, simple process and the like.
Description
Technical Field
The invention relates to the technical research and development field of fine chemicals, in particular to a preparation method of an organic silicon-containing modified castor oil defoaming agent for PVA production.
Background
The defoaming agent is used for inhibiting and eliminating various harmful foams, is a relatively effective chemical method for controlling foams, and is widely applied to the fields of chemical industry, medicine, textile, printing and dyeing, mineral separation, coating, sewage treatment and the like. In general, in industrial production, foam brings adverse factors such as reduced productivity, pigment waste, product quality reduction and the like. Conventional defoamers have a certain specificity because the foaming mechanism is different for each foaming system, resulting in different defoamers being required for different foaming systems. In the production of PVA, due to the existence of acetyl in the molecular chain of PVA, certain surface activity is shown, slurry is easy to foam, and the production and use effects of PVA are seriously restricted. CN106267909A in chinese patent database discloses a polyether modified silicone defoamer and a preparation method thereof, CN 35 104086775B discloses a preparation and compounding method of a long-chain alkyl ester modified silicone defoamer, CN102343165A discloses a silicone defoamer mainly comprising a silicone grease mixture added with polyether silicone oil, a thickener, a preservative and other active substances, CN104069654A discloses a preparation method of a high-viscosity silicone defoamer and the like. These patents all relate to polyether modified silicone type defoamers and the compounding of silicone type defoamers with certain polyethers. The preparation method is complex in process, the preparation operation of polyether is difficult, the polyether chain is easy to oxidize and break in the air, and the adhesive property of slurry and the mechanical property of a slurry film are negatively affected, so that the defoaming performance of the defoaming agent is affected.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the silicone-containing modified castor oil defoamer for PVA production, which is simple, short in reaction period and convenient to operate and contains silicone-modified castor oil, and the preparation method thereof. And the prepared defoaming agent is applied to PVA production, so that the defoaming efficiency is improved, and the production cost is reduced.
The invention is realized by the following technical scheme.
A preparation method of an organic silicon-containing modified castor oil defoaming agent for PVA production comprises the following steps:
1) firstly, the molar ratio is 1: 0.5 to 2.5 portions of hydrogen-containing silicone oil and castor oil are put into a reaction kettle, stirred under set pressure and temperature to remove water and low boiling point impurities, and then added with chloroplatinic acid catalyst with the total mass of 0.01 to 1 percent and added with N2Heating to react under the environment to prepare an organic silicon modified castor oil defoamer active matter;
2) according to the mass ratio of (15-30): (2-5): (3-12): (5-15): (2-8) respectively putting the organosilicon modified castor oil defoamer active matter, the microcrystalline wax, the monoglyceride, the isooctyl stearate and the emulsifier into a reaction kettle according to the proportion, stirring, heating and preserving heat;
3) the mass ratio of the raw materials in the step 2) is (60-40): (40-60), slowly adding the thickener-carrier solution into the reaction system, continuously stirring, and cooling to obtain the defoaming agent containing the organic silicon modified castor oil.
Further, the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2%.
Further, in the step 1), stirring for 20-30min at the pressure of less than or equal to-0.09 MPa and the temperature of 80-95 ℃ to remove water and low-boiling-point impurities; put out N2Then heating to 80-95 ℃ and preserving the heat for 0.5-5 h.
Further, in the step 2), the temperature is increased to 55-70 ℃ at the stirring speed of 1200r/min, and the heat preservation and the stirring are carried out for 5-10 min.
Further, in the step 3), the prepared thickener aqueous solution with the temperature of 55-70 ℃ is slowly added into the reaction system, and the mixture is continuously stirred for 5-10min and cooled to 25 ℃.
Further, the emulsifier includes but is not limited to one or more compound emulsifiers selected from span 20, tween 20, span 60, tween 60, span 80, tween 80, Op-10 or polyoxyethylene 40 stearate.
Further, the thickener-carrier fluid is prepared by mixing the thickener and the carrier according to the mass ratio of (0.5-2): (40-60) in the presence of water or an organic solvent as a carrier.
Further, the organic solvent is ethanol, ethyl acetate, diethylene glycol ethyl ether or ethylene glycol propyl ether.
Further, the thickener is carboxymethyl cellulose or hydroxyethyl cellulose.
The invention correspondingly provides the organosilicone-containing modified castor oil defoaming agent for PVA production, which is prepared by the method and comprises the following raw materials in percentage by mass:
the modified organic silicon defoamer prepared by the invention is only modified by using castor oil which is a more common vegetable oil as a modified product, and is obtained by reacting active hydrogen in hydrogen-containing silicone oil with castor oil and compounding. The defoamer is applied to PVA production, has little negative influence on slurry adhesiveness and slurry film mechanical property, and has the characteristics of small dosage, high defoaming speed, strong foam inhibition capability, no toxicity, no harm, simple process and the like. At present, the research and development of the field of polyether modified organic silicon in the domestic market tend to be mature, and the production of castor oil modified organic silicon defoaming agent is less. Therefore, the research and development of the products in the field have great potential value and better competitiveness.
The innovation points and advantages of the invention are as follows:
1. organic silicon and castor oil are subjected to grafting reaction to synthesize a novel compound, and the novel compound is applied to the preparation of the defoaming agent, so that the defoaming agent applied to PVA production is prepared.
2. Compared with the polyether modified organic silicon defoamer, the modified organic silicon defoamer has the advantages that the conventional vegetable oil-castor oil is used as an organic silicon modifier, the proportion of oleophylic and hydrophilic chain segments of the modified organic silicon defoamer is adjusted through graft modification of the organic silicon, the surface tension of the castor oil is further reduced, the defoaming capability of the castor oil is improved, and the modified organic silicon defoamer is more suitable for eliminating foam in PVA production. Solves the problem of poor demulsification, defoaming and foam inhibition capabilities of the traditional defoaming agent.
3. The defoaming agent prepared by the method has low surface tension, good chemical stability, heat resistance, acid, alkali salt resistance and high temperature resistance.
4. When the method is applied to PVA production, the negative influence on the slurry adhesiveness and the slurry film mechanical property is small, and the method has the characteristics of small using amount, high defoaming speed, strong foam inhibition capability, no toxicity, no harm, simple process and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
The invention discloses a preparation method of an organic silicon-containing modified castor oil defoaming agent for PVA production, which comprises the following steps:
1) firstly, the molar ratio is 1: 0.5-2.5 of hydrogen-containing silicone oil and castor oil are put into a reaction kettle and stirred for 20-30min under the pressure of less than or equal to-0.09 MPa and the temperature of 80-95 DEG CRemoving water and low-boiling-point impurities, adding chloroplatinic acid catalyst with the total mass of 0.01-1%, and adding N2Heating to 80-95 deg.C in atmosphere, and keeping the temperature for 0.5-5 h; reacting to obtain an organic silicon modified castor oil defoamer active matter;
wherein, the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2%.
2) According to the mass ratio of (15-30): (2-5): (3-12): (5-15): (2-8) putting the organosilicon modified castor oil defoamer active matter, the microcrystalline wax, the monoglyceride, the isooctyl stearate and the emulsifier into a reaction kettle in proportion, heating to 55-70 ℃ at the stirring speed of 1200r/min, and stirring for 5-10min under heat preservation;
3) according to the mass ratio of (0.5-2): (40-60), preparing a thickener-carrier liquid, and mixing the prepared thickener-carrier liquid with the temperature of 55-70 ℃ according to the mass ratio of (40-60): (60-40), continuously stirring for 5-10min, cooling to 25 ℃, and obtaining the defoaming agent containing the organic silicon modified castor oil.
Wherein the emulsifier is one or more of span 20, Tween 20, span 60, Tween 60, span 80, Tween 80, Op-10 or polyoxyethylene 40 stearate; the carrier is water or organic solvent (ethanol, ethyl acetate, diethylene glycol ethyl ether or ethylene glycol propyl ether); the thickener is carboxymethyl cellulose or hydroxyethyl cellulose.
The principle of the invention is as follows:
the reaction formula of the hydrogen-containing silicone oil and ricinoleic acid in castor oil is as follows:
wherein:
Si-H groups in the hydrogen-containing silicone oil and C ═ C double bonds in the castor oil are subjected to a hydrosilylation reaction to form Si-C groups. Ricinoleic acid has both hydrophilic group and hydrophobic group, can be used as defoaming agent, but has not very strong defoaming capability, and lipophilic and hydrophilic chains of ricinoleic acid are adjusted through grafting modification of organic siliconThe proportion of section has further reduced the surface tension of castor oil, has improved the defoaming ability of castor oil, makes it more be fit for being applied to the elimination of foam in PVA production.
The silicone defoaming agent has specific defoaming performance, while the castor oil also has certain defoaming effect in some fields, and when the silicone defoaming agent and the castor oil are combined, the advantages of the silicone defoaming agent and the castor oil are combined.
Specific examples are given below to further illustrate the preparation of the present invention.
Example 1
Mixing a mixture of 1: 0.5 hydrogen-containing silicone oil and castor oil are placed in a reaction kettle to be mixed and stirred, then the system is dewatered and low boiling point impurity removal treatment is carried out under the conditions that the pressure is less than or equal to-0.09 MPa and the temperature is 95 ℃ and the stirring is carried out for 20min, then chloroplatinic acid catalyst with the total mass of 0.1 percent is added, and the reaction kettle is stirred under the condition of N2Heating to react in the environment to obtain the active matter of the defoaming agent, cooling and discharging. Wherein the hydrogen content in the hydrogen-containing silicone oil is 0.1 percent, and the proportion of the hydrogen-containing silicone oil to the castor oil is 1: 0.5, complete N addition2Then heating up to 80 ℃ and preserving the heat for 1.5 h; and finally, detecting the hydrogen content in the reaction system by using an active hydrogen chemical titration method until the reaction conversion rate reaches more than 95 percent, thus obtaining the active substance of the organic silicon modified castor oil defoaming agent.
2) 20g of organic silicon modified castor oil defoamer active substance, 5g of microcrystalline wax, 10g of monoglyceride, 7g of isooctyl stearate, 20g of emulsifier span and 20g of tween 20 are placed in a 1200r/min stirring reaction kettle, the temperature is raised to 55 ℃, and the stirring is carried out for 10min under the condition of heat preservation. Then slowly adding thickener aqueous solution with the same temperature, wherein the thickener is carboxymethyl cellulose 1g, and the water is 49 g. And continuously stirring for 10min, and cooling the reaction system to 25 ℃ to obtain the defoaming agent containing the organic silicon modified castor oil.
Placing the defoamed substance into a 2000ml measuring cylinder, adding 600ml of sodium dodecyl benzene sulfonate aqueous solution with the mass concentration of 0.5%, then respectively adding 0.05% of emulsion type castor oil modified organic silicon defoaming agent based on the total mass of the system, and measuring the defoaming and foam inhibiting capacity by a bubbling method.
Example 2
Mixing a mixture of 1: 2.5 mixing hydrogen-containing silicone oil and castor oil in a reaction kettle, stirring, and mixingThe method comprises the steps of dewatering and removing low boiling point impurities under the conditions that the pressure is less than or equal to-0.09 MPa and the temperature is 85 ℃ and stirring is carried out for 30min, then chloroplatinic acid catalyst with the total mass of 0.01 percent is added, and N is added2Heating to react in the environment to obtain the active matter of the defoaming agent, cooling and discharging. Wherein the hydrogen content in the hydrogen-containing silicone oil is 0.05 percent, and the proportion of the hydrogen-containing silicone oil to the castor oil is 1: 2.5, after N is put in2Then heating up to 85 ℃, and preserving heat for 0.5 h; and finally, detecting the hydrogen content in the reaction system by using an active hydrogen chemical titration method until the reaction conversion rate reaches more than 95 percent, thus obtaining the active substance of the organic silicon modified castor oil defoaming agent.
2) Putting 25g of active substance of the organic silicon modified castor oil defoaming agent, 2g of microcrystalline wax, 12g of monoglyceride, 5g of isooctyl stearate, span 60 and tween 60 which are 3g respectively into a stirring reaction kettle at 1200r/min, heating to 70 ℃, preserving heat and stirring for 5 min. Then slowly adding thickener water solution with the same temperature, wherein the thickener is 0.5g of hydroxyethyl cellulose and 49.5g of ethanol. And continuously stirring for 10min, and cooling the reaction system to 25 ℃ to obtain the defoaming agent containing the organic silicon modified castor oil.
Placing the defoamed substance into a 2000ml measuring cylinder, adding 600ml of sodium dodecyl benzene sulfonate aqueous solution with the mass concentration of 0.5%, then respectively adding 0.05% of emulsion type castor oil modified organic silicon defoaming agent based on the total mass of the system, and measuring the defoaming and foam inhibiting capacity by a bubbling method.
Example 3
Mixing a mixture of 1: 1.5 placing hydrogen-containing silicone oil and castor oil into a reaction kettle for mixing and stirring, then dewatering and removing low-boiling point impurities of the system under the conditions that the pressure is less than or equal to-0.09 MPa and the temperature is 95 ℃ and stirring is carried out for 25min, then adding chloroplatinic acid catalyst with the total mass of 1 percent, and adding into N2Heating to react in the environment to obtain the active matter of the defoaming agent, cooling and discharging. Wherein the hydrogen content in the hydrogen-containing silicone oil is 0.2 percent, and the proportion of the hydrogen-containing silicone oil to the castor oil is 1: 2.5, after N is put in2Then heating to 90 ℃ and preserving the heat for 5 hours; and finally, detecting the hydrogen content in the reaction system by using an active hydrogen chemical titration method until the reaction conversion rate reaches more than 95 percent, thus obtaining the active substance of the organic silicon modified castor oil defoaming agent.
2) Placing 30g of active substance of the organic silicon modified castor oil defoaming agent, 5g of microcrystalline wax, 3g of monoglyceride, 15g of isooctyl stearate, 803 g of span and 804 g of tween in a stirring reaction kettle at 1200r/min, heating to 60 ℃, preserving heat and stirring for 5 min. Then slowly adding the thickening agent water solution with the same temperature, wherein the thickening agent is hydroxyethyl cellulose 2g, and the ethyl acetate is 38 g. And continuously stirring for 10min, and cooling the reaction system to 25 ℃ to obtain the defoaming agent containing the organic silicon modified castor oil.
Placing the defoamed substance into a 2000ml measuring cylinder, adding 600ml of sodium dodecyl benzene sulfonate aqueous solution with the mass concentration of 0.5%, then respectively adding 0.05% of emulsion type castor oil modified organic silicon defoaming agent based on the total mass of the system, and measuring the defoaming and foam inhibiting capacity by a bubbling method.
Example 4
Mixing a mixture of 1: 1.0 hydrogen-containing silicone oil and castor oil are placed in a reaction kettle for mixing and stirring, then the system is dehydrated and low boiling point impurity removal treatment is carried out under the conditions that the pressure is less than or equal to-0.09 MPa and the temperature is 90 ℃ and the stirring is carried out for 20min, then chloroplatinic acid catalyst with the total mass of 0.08 percent is added, and the reaction kettle is stirred under the condition of N2Heating to react in the environment to obtain the active matter of the defoaming agent, cooling and discharging. Wherein the hydrogen content in the hydrogen-containing silicone oil is 0.15 percent, and the proportion of the hydrogen-containing silicone oil to the castor oil is 1: 0.7, complete N placement2Then heating up to 95 ℃ and preserving heat for 3 h; and finally, detecting the hydrogen content in the reaction system by using an active hydrogen chemical titration method until the reaction conversion rate reaches more than 95 percent, thus obtaining the active substance of the organic silicon modified castor oil defoaming agent.
2) Taking 15g of organic silicon modified castor oil defoamer active substance, 5g of microcrystalline wax, 10g of monoglyceride, 8g of isooctyl stearate, Op-10 and 1g of polyoxyethylene 40 stearate respectively, placing in a stirring reaction kettle at 1200r/min, heating to 70 ℃, and preserving heat and stirring for 10 min. Then slowly adding the thickening agent water solution with the same temperature, wherein the thickening agent carboxymethyl cellulose is 2g, and the diethylene glycol ethyl ether is 58 g. And continuously stirring for 10min, and cooling the reaction system to 25 ℃ to obtain the defoaming agent containing the organic silicon modified castor oil.
Placing the defoamed substance into a 2000ml measuring cylinder, adding 600ml of sodium dodecyl benzene sulfonate aqueous solution with the mass concentration of 0.5%, then respectively adding 0.05% of emulsion type castor oil modified organic silicon defoaming agent based on the total mass of the system, and measuring the defoaming and foam inhibiting capacity by a bubbling method.
Example 5
Mixing a mixture of 1: 1.0 hydrogen-containing silicone oil and castor oil are placed in a reaction kettle for mixing and stirring, then the system is dehydrated and low boiling point impurity removal treatment is carried out under the conditions that the pressure is less than or equal to-0.09 MPa and the temperature is 90 ℃ and the stirring is carried out for 20min, then chloroplatinic acid catalyst with the total mass of 0.08 percent is added, and the reaction kettle is stirred under the condition of N2Heating to react in the environment to obtain the active matter of the defoaming agent, cooling and discharging. Wherein the hydrogen content in the hydrogen-containing silicone oil is 0.15 percent, and the proportion of the hydrogen-containing silicone oil to the castor oil is 1: 0.7, complete N placement2Then heating up to 95 ℃ and preserving heat for 3 h; and finally, detecting the hydrogen content in the reaction system by using an active hydrogen chemical titration method until the reaction conversion rate reaches more than 95 percent, thus obtaining the active substance of the organic silicon modified castor oil defoaming agent.
2) 20g of active substance of the organic silicon modified castor oil defoaming agent, 5g of microcrystalline wax, 5g of monoglyceride, 4g of isooctyl stearate, Op-10 and 3g of polyoxyethylene 40 stearate are respectively put into a stirring reaction kettle at 1200r/min, the temperature is raised to 70 ℃, and the stirring is carried out for 10min under the condition of heat preservation. Then slowly adding thickener aqueous solution with the same temperature, wherein the thickener is carboxymethyl cellulose 1g, and ethylene glycol propyl ether 59 g. And continuously stirring for 10min, and cooling the reaction system to 25 ℃ to obtain the defoaming agent containing the organic silicon modified castor oil.
Placing the defoamed substance into a 2000ml measuring cylinder, adding 600ml of sodium dodecyl benzene sulfonate aqueous solution with the mass concentration of 0.5%, then respectively adding 0.05% of emulsion type castor oil modified organic silicon defoaming agent based on the total mass of the system, and measuring the defoaming and foam inhibiting capacity by a bubbling method.
The defoaming time and foam suppressing effect of examples 1 to 5 of the present invention are shown in Table 1.
TABLE 1 Compound emulsifier of examples 1-4
As can be seen from the table 1, the defoaming time of the silicone modified castor oil-containing defoamer for PVA production prepared by the invention is less than 5s, and the foam inhibition height is less than 1.5cm when the system foam reaches 8cm in defoaming performance. And the defoaming time of the common PVA defoaming agent is more than 8s when the foam height reaches 8cm, and the foam inhibition height is also more than 2 cm. Therefore, the silicone-containing modified castor oil defoaming agent is a good defoaming agent with the characteristics of high defoaming speed, strong foam inhibition capability, no toxicity, no harm, simple process and the like.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (7)
1. A preparation method of an organic silicon-containing modified castor oil defoaming agent for PVA production is characterized by comprising the following steps:
1) firstly, the molar ratio is 1: 0.5-2.5 of hydrogen-containing silicone oil and castor oil are placed in a reaction kettle, stirred under set pressure and temperature to remove water and low-boiling-point impurities, then a chloroplatinic acid catalyst with the total mass of 0.01-1% is added, and N is added2Heating to react under the environment to prepare an organic silicon modified castor oil defoamer active matter;
in the step 1), stirring for 20-30min at the pressure of less than or equal to-0.09 MPa and the temperature of 80-95 ℃ to remove water and low-boiling-point impurities; after being filled with N2Then heating up to 80-95 ℃ and preserving heat for 0.5-5 h;
2) according to the mass ratio of (15-30): (2-5): (3-12): (5-15): (2-8) respectively putting the organosilicon modified castor oil defoamer active matter, the microcrystalline wax, the monoglyceride, the isooctyl stearate and the emulsifier into a reaction kettle according to the proportion, stirring, heating and preserving heat;
in the step 2), heating to 55-70 ℃ at a stirring speed of 1200r/min, and stirring for 5-10min under heat preservation;
3) the mass ratio of the raw materials in the step 2) is (60-40): (40-60), slowly adding the thickener-carrier solution into the reaction system, continuously stirring, and cooling to obtain the defoaming agent containing the organic silicon modified castor oil;
the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2%;
when the foam of the system reaches 8cm, the defoaming time of the organosilicon modified castor oil is less than 5s, and the foam inhibition height is less than 1.5 cm.
2. The preparation method of the silicone-containing modified castor oil defoamer for PVA production according to claim 1, wherein in step 3), the prepared thickener aqueous solution with the temperature of 55-70 ℃ is slowly added into the reaction system, and the mixture is continuously stirred for 5-10min and cooled to 25 ℃.
3. The method for preparing the defoaming agent of castor oil containing silicone modification used in PVA production according to claim 1, wherein the emulsifier includes but is not limited to one or more of span 20, Tween 20, span 60, Tween 60, span 80, Tween 80, Op-10 or polyoxyethylene 40 stearate.
4. The preparation method of the silicone-containing modified castor oil defoamer for PVA production according to claim 1, wherein the thickener-carrier solution is prepared by mixing a thickener and a carrier according to a mass ratio of (0.5-2): (40-60) in the presence of water or an organic solvent as a carrier.
5. The method for preparing the silicone-containing modified castor oil antifoaming agent for use in PVA production according to claim 4, wherein the organic solvent is ethanol, ethyl acetate, diethylene glycol ethyl ether, or ethylene glycol propyl ether.
6. The method of claim 1, wherein the thickener is carboxymethyl cellulose or hydroxyethyl cellulose.
7. An organosilicon-containing modified castor oil defoamer for PVA production prepared by the method of any one of claims 1 to 6, comprising the following raw materials in mass ratio:
15-30 parts of organic silicon modified castor oil defoaming agent active matter;
2-5 parts of microcrystalline wax;
3-12 parts of monoglyceride;
5-15 parts of isooctyl stearate;
2-8 parts of emulsifier;
0.5-2 parts of thickening agent;
40-60 of carrier.
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| CN109173351A (en) * | 2018-10-23 | 2019-01-11 | 西安三业新材料股份有限公司 | A kind of organic-silicon-modified castor oil polyether antifoam agent of emulsion-type and preparation method |
| CN112057906A (en) * | 2020-08-27 | 2020-12-11 | 江苏赛欧信越消泡剂有限公司 | Low COD defoaming agent for water body without toxicity to microorganisms and preparation method thereof |
| CN113730964B (en) * | 2021-09-14 | 2023-01-10 | 浙江传化华洋化工有限公司 | Defoaming agent and preparation method and application thereof |
| CN114344955A (en) * | 2021-12-01 | 2022-04-15 | 大连大平油脂化学有限公司 | Defoaming agent containing rare earth oxide and preparation method thereof |
| CN114057973B (en) * | 2021-12-07 | 2023-04-28 | 广州予能新材料科技有限公司 | Organosilicon modified polyurethane material and preparation method thereof |
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