WO2022001575A1 - 一种有机硅乳液及制备方法 - Google Patents

一种有机硅乳液及制备方法 Download PDF

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WO2022001575A1
WO2022001575A1 PCT/CN2021/098240 CN2021098240W WO2022001575A1 WO 2022001575 A1 WO2022001575 A1 WO 2022001575A1 CN 2021098240 W CN2021098240 W CN 2021098240W WO 2022001575 A1 WO2022001575 A1 WO 2022001575A1
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emulsion
fatty acid
catalyst
preparation
glycerol
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French (fr)
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黄伟
苏芳
曹添
胡佳新
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江苏四新科技应用研究所股份有限公司
扬州四新新材料科技有限公司
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

  • the invention relates to an organic silicon emulsion and a preparation method, belonging to the technical field of fine chemical preparations.
  • Silicone emulsion is one of the important silicone products. Because of its unique temperature resistance, high hydrophobicity and physiological inertness, it has been widely used in industry and is widely used in papermaking, textiles, sizing, coatings, construction, etc. , leather, medicine, cosmetics and other industrial fields.
  • the silicone emulsion used in the industrial process is mainly oil-in-water type.
  • the preparation methods include conventional emulsion polymer method, phase inversion emulsion polymerization method, and ultrasonic emulsification method. To evaluate a silicone emulsion, its function and stability are usually closely related.
  • the emulsifier the key component of the silicone emulsion
  • silicone emulsions are mainly used to disperse active substances; a large number of experimental experiences have shown that too much emulsifier will affect the main function of the silicone emulsion; too little emulsifier, the resulting Silicone emulsions are very unstable and may cause losses; on the other hand, silicone emulsions contain a large amount of water.
  • silicone emulsions are prevented from deteriorating by adding preservatives to ensure the stability of emulsion performance.
  • preservatives for silicone emulsions are getting higher and higher, which will eventually limit the application of silicone emulsions.
  • the purpose of the present invention is to provide a kind of silicone emulsion and preparation method.
  • active material preferably polyether modified polysiloxane and glycerin fatty acid Ester compound emulsifying active substance, glycerol fatty acid ester not only has emulsifying performance, but also has certain antiseptic performance, the final prepared silicone emulsion is stable and has excellent performance.
  • the active material of the present invention is the reaction product of hydrogen-containing polyorganosiloxane and hydrophobic particles under the action of a catalyst.
  • Me is methyl, subscript c is 0, 1 or 2
  • a is an integer from 2 to 100
  • b is an integer from 20 to 300
  • each molecule has at least 2 silicon-bonded hydrogen atoms
  • the dosage is the total amount of active material. 90 to 95% of the mass.
  • hydrophobic particles are hydrophobic silica, the specific surface area is 150-250 m 2 /g, and the dosage accounts for 4-8% of the total mass of the active material.
  • the catalyst is selected from LiOH, CsOH, NaOH, KOH, Me 4 NOH, preferably NaOH in the present invention, and the amount of the catalyst is 1-3% of the total mass of the active material.
  • the preparation process of the active substance is as follows: firstly, the polyorganosiloxane and the hydrophobic particles are mixed uniformly at room temperature to maintain full contact. Then the temperature is raised to 80-250° C., a catalyst is added to react for 2-8 hours, and after the reaction is completed, the temperature is lowered to room temperature to obtain an active substance, and the amount of the active substance accounts for 10-30% of the total mass of the silicone emulsion.
  • the glycerol fatty acid ester of the present invention is obtained by esterifying glycerol and fatty acid as raw materials under alkaline catalyst conditions; the fatty acid is selected from one or more of propionic acid, caprylic acid, capric acid and lauric acid;
  • the catalyst is selected from sodium bicarbonate, potassium hydroxide, sodium hydroxide and potassium bicarbonate; the mass ratio of glycerol, fatty acid and basic catalyst is glycerol: fatty acid: basic catalyst is 20-100:25-300:0.3-3.0;
  • the preparation method of the glycerol fatty acid ester is that glycerol and fatty acid are used as raw materials to be esterified at 200-250 DEG C for 40-90min in the presence of an alkaline catalyst; 8%.
  • R 2 is methyl, ethyl, propyl, butyl or phenyl
  • R 3 is hydrogen atom, methyl, ethyl, propyl or butyl
  • subscript r, s is the polymerization of silicon chain degree, s is an integer from 1 to 50, and r is an integer from 1 to 200
  • the subscripts e and f are the polymerization degrees of ethylene oxide (EO) and propylene oxide (PO), respectively, and e and f are both 1 ⁇ 200.
  • the thickener is selected from polyacrylamide, carbomer, xanthan gum, polyacrylate, and cellulose ether, and the amount of the thickener accounts for 0.5-3% of the total mass of the silicone emulsion.
  • the dosage of water accounts for 50-80% of the total mass of the silicone emulsion.
  • the active substance, glycerol fatty acid ester, and silicon polyether are fully mixed for 10 to 50 minutes under stirring to form a mixture M; the thickener and water are mixed and fully stirred to obtain a mixture N; then the temperature of the mixture M is raised to Keep the system temperature at 55°C to 85°C, slowly add mixture N, increase the stirring speed to change from water-in-oil emulsion to oil-in-water emulsion, and further emulsify the coarse emulsion by colloid mill to obtain the silicone emulsion.
  • Active substances A, B, C, D and E were prepared according to the preparation method of active substances mentioned above using the reaction raw materials and conditions in the following table.
  • Silicon polyether E-1 E-2 E-3 E-4 E-5 R 2 —CH 3 —C 2 H 5 —C 4 H 9 —C 3 H 7 -C 6 H 5 R 3 —H —CH 3 —C 2 H 5 —CH 3 —C 4 H 9 r 1 152 84 200 100 s 1 50 26 38 15 e 50 twenty two 1 15 40 f 30 twenty four 50 1 40 t 3 4 1 6 5
  • the performance of the high-viscosity organosilicon composition emulsion prepared by the method of the present invention is mainly evaluated from the following aspects:

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

本发明的目的是提供一种有机硅乳液及制备方法，首先将含氢聚有机硅氧烷与疏水粒子在催化剂作用下反应制得活性物质，优选聚醚改性聚硅氧烷与甘油脂肪酸酯复配乳化活性物质，甘油脂肪酸酯不仅具有乳化性能，同时具有一定的防腐性能，最终制备的有机硅乳液稳定，性能优异。

Description

一种有机硅乳液及制备方法 技术领域
本发明涉及一种有机硅乳液及制备方法，隶属于精细化工制剂技术领域。
背景技术
有机硅乳液是重要的有机硅产品之一，由于它的独特的耐温性、高度疏水性已经生理惰性，在工业上得到广泛的应用，被广泛用于造纸、纺织、浆料、涂料、建筑、皮革、医药、化妆品等工业领域。工业过程中使用的有机硅乳液主要是水包油型的，制备方法包括常规乳液聚合物法、转相乳液聚合法、超声波乳化法；评价一种有机硅乳液，通常将其功能与稳定性紧密联系在一起，有机硅乳液的关键组分乳化剂主要是用来分散活性物质的；大量的实验经验表明，乳化剂过多，会影响到有机硅乳液的主要功能；乳化剂过少，得到的有机硅乳液则很不稳定，可能会造成损失；另一方面有机硅乳液中含有大量的水，一般的有机硅乳液都是通过添加防腐剂防止乳液变质，保证乳液性能的稳定性，但是随着化学品安全法规的不断完善以及有机硅乳液的应用范围越来越广泛，有机硅乳液对防腐剂的限制要求越来越高，最终会限制有机硅乳液的应用。
发明内容
本发明的目的是提供一种有机硅乳液及制备方法，首先将含氢聚 有机硅氧烷与疏水粒子在催化剂作用下反应制得活性物质，优选聚醚改性聚硅氧烷与甘油脂肪酸酯复配乳化活性物质，甘油脂肪酸酯不仅具有乳化性能，同时具有一定的防腐性能，最终制备的有机硅乳液稳定，性能优异。
本发明所述的有机硅乳液，其特征在于由以下组分组成：
A、活性物质：
本发明所述的活性物质为含氢聚有机硅氧烷、疏水粒子在催化剂作用下的反应产物。
(1)所述的含氢聚有机硅氧烷的结构通式如下：
H c Me 3-cSiO( MeHSiO) a( Me 2SiO) bSi Me 3-cH c
Me为甲基，下标c是0、1或2，a是2～100的整数，b是20～300的整数，每个分子具有至少2个硅键合的氢原子，用量为活性物质总质量的90～95％。
(2)所述的疏水粒子为疏水二氧化硅，比表面积150～250m 2/g，用量占活性物质总质量的4～8％。
(3)所述的催化剂选自LiOH、CsOH、NaOH、KOH、Me 4NOH，本发明优选为NaOH，催化剂的用量为活性物质总质量1～3％。
所述的活性物质的制备工艺如下：先将聚有机硅氧烷和疏水粒子室温下混合均匀，以保持充分接触。然后升温至80～250℃，加入催化剂反应2～8h，反应完毕降温至室温即得活性物质，活性物的用量占有机硅乳液总质量的10-30％。
B、甘油脂肪酸酯
本发明所述的甘油脂肪酸酯是以甘油与脂肪酸为原料在碱性催化剂条件下酯化得到；所述的脂肪酸选自丙酸、辛酸、癸酸、月桂酸中的一种或多种；催化剂选自碳酸氢钠、氢氧化钾、氢氧化钠、碳酸氢钾；甘油、脂肪酸、碱性催化剂的质量比为甘油：脂肪酸：碱性催化剂为20-100:25-300:0.3-3.0；
所述甘油脂肪酸酯的制备方法为以甘油与脂肪酸为原料在碱性催化剂存在下200-250℃保温40-90min酯化制得；甘油脂肪酸酯的用量占有机硅乳液总质量的2-8％。
C、聚醚改性聚硅氧烷
所述的聚醚改性聚硅氧烷的结构式如下：
Figure PCTCN2021098240-appb-000001
其中，字母R 2为甲基、乙基、丙基、丁基或苯基；R 3为氢原子、甲基、乙基、丙基或丁基；下标r，s是硅链节的聚合度，s为1～50的整数，r为1～200的整数；下标e和f分别为环氧乙烷(EO)和环氧丙烷(PO)的聚合度，e和f均为1～50的整数；下标t为—CH 2的聚合度，为1～6的整数，聚醚改性聚硅氧烷的用量占有机硅乳液总质量的5-15％。
D、增稠剂
增稠剂选自聚丙烯酰胺、卡波姆、汉生胶、聚丙烯酸酯、纤维素 醚类，增稠剂的用量占有机硅乳液总质量的0.5-3％。
E、水
水的用量占有机硅乳液总质量的50-80％。
所述的有机硅乳液的制备方法如下：
室温下，将活性物质、甘油脂肪酸酯、硅聚醚在搅拌下充分混合10～50min，形成混合物M；将增稠剂和水混合充分搅拌得到混合物N；然后将混合物M的温度升高至55℃～85℃保持体系温度，缓慢地加入混合物N，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
具体实施方式
活性物质的制备：
采用下表中的反应原料及条件，按照前面提到的活性物质的制备方法，制得活性物质A、B、C、D和E。
Figure PCTCN2021098240-appb-000002
甘油脂肪酸酯的制备
采用下表中的反应原料及条件，按照前面提到的甘油脂肪酸酯的制备方法，制得甘油脂肪酸酯A、B、C、D和E。
Figure PCTCN2021098240-appb-000003
硅聚醚的实施例取值
硅聚醚 E-1 E-2 E-3 E-4 E-5
R 2 —CH 3 —C 2H 5 —C 4H 9 —C 3H 7 -C 6H 5
R 3 —H —CH 3 —C 2H 5 —CH 3 —C 4H 9
r 1 152 84 200 100
s 1 50 26 38 15
e 50 22 1 15 40
f 30 24 50 1 40
t 3 4 1 6 5
有机硅乳液的制备：
实施例1：
室温下，将10g活性物质A-1、8g甘油脂肪酸酯B-1、15g硅聚醚E-1在搅拌下充分混合10min，形成混合物M1；将3g增稠剂聚丙 烯酰胺和64g水混合充分搅拌得到混合物N1；然后将混合物M1的温度升高至55℃保持体系温度，缓慢地加入混合物N1，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
实施例2：
室温下，将30g活性物质A-2、2g甘油脂肪酸酯B-2、5g硅聚醚E-2在搅拌下充分混合20min，形成混合物M2；将0.5g增稠剂卡波姆和62.5g水混合充分搅拌得到混合物N2；然后将混合物M2的温度升高至85℃保持体系温度，缓慢地加入混合物N2，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
实施例3：
室温下，将30g活性物质A-3、6g甘油脂肪酸酯B-3、12g硅聚醚E-3在搅拌下充分混合30min，形成混合物M3；将2g增稠剂汉生胶和50g水混合充分搅拌得到混合物N3；然后将混合物M3的温度升高至60℃保持体系温度，缓慢地加入混合物N3，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
实施例4：
室温下，将12.5g活性物质A-4、2g甘油脂肪酸酯B-4、5g硅聚醚E-4在搅拌下充分混合45min，形成混合物M4；将0.5g增稠剂聚丙烯酸酯和80g水混合充分搅拌得到混合物N4；然后将混合物M4的 温度升高至70℃保持体系温度，缓慢地加入混合物N4，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
实施例5
室温下，将20g活性物质A-5、4g甘油脂肪酸酯B-5、8g硅聚醚E-5在搅拌下充分混合50min，形成混合物M5；将1g增稠剂羧甲基纤维素和67g水混合充分搅拌得到混合物N5；然后将混合物M5的温度升高至75℃保持体系温度，缓慢地加入混合物N5，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
对比例1：-去掉防腐乳化剂
室温下，将10g活性物质A-1、23g硅聚醚E-1在搅拌下充分混合10min，形成混合物M6；将3g增稠剂聚丙烯酰胺和64g水混合充分搅拌得到混合物N1；然后将混合物M6的温度升高至55℃保持体系温度，缓慢地加入混合物N1，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
对比例2：替换成普通的非离子乳化剂
室温下，将30g活性物质A-2、2g油酸聚氧乙烯醚、5g硅聚醚E-2在搅拌下充分混合20min，形成混合物M7；将0.5g增稠剂卡波姆和62.5g水混合充分搅拌得到混合物N2；然后将混合物M7的温度升高至85℃保持体系温度，缓慢地加入混合物N2，提高搅拌速度使 其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
测试方法：
本发明方法制备的高粘度有机硅组合物乳液的性能主要从以下几个方面进行评估：
(1)乳液的漂油温度：
按照1％的有机硅乳液加入到99％的水中，升温后观察水稀释液的液面状况，漂油温度越高，则乳液越稳定。
(2)乳液的防腐性能：
参考GB4799.2-2016(食品微生物菌落总数的测定)测试有机硅乳液的菌落总数。
测试结果：
Figure PCTCN2021098240-appb-000004
由以上数据可以看出，引入甘油脂肪酸酯可以提高乳液的稳定性和防腐性能。

Claims (2)

  1. 一种有机硅乳液及制备方法，其特征在于所述有机硅乳液由以下组分组成：
    A、活性物质：
    本发明所述的活性物质为含氢聚有机硅氧烷、疏水粒子在催化剂作用下的反应产物；
    (1)所述的含氢聚有机硅氧烷的结构通式如下：
    H c Me 3-cSiO( MeHSiO) a( Me 2SiO) bSi Me 3-cH c
    Me为甲基，下标c是0、1或2，a是2～100的整数，b是20～300的整数，每个分子具有至少2个硅键合的氢原子，用量为活性物质总质量的90～95％；
    (2)所述的疏水粒子为疏水二氧化硅，比表面积150～250m 2/g，用量占活性物质总质量的4～8％；
    (3)所述的催化剂选自LiOH、CsOH、NaOH、KOH、Me 4NOH，催化剂的用量为活性物质总质量1～3％；
    所述的活性物质的制备工艺如下：先将聚有机硅氧烷和疏水粒子室温下混合均匀，以保持充分接触。然后升温至80～250℃，加入催化剂反应2～8h，反应完毕降温至室温即得活性物质，活性物的用量占有机硅乳液总质量的10-30％；
    B、甘油脂肪酸酯
    本发明所述的甘油脂肪酸酯是以甘油与脂肪酸为原料在碱性催化剂条件下酯化得到；所述的脂肪酸选自丙酸、辛酸、癸酸、月桂酸 中的一种或多种；催化剂选自碳酸氢钠、氢氧化钾、氢氧化钠、碳酸氢钾；甘油、脂肪酸、碱性催化剂的质量比为甘油：脂肪酸：碱性催化剂为20-100:25-300:0.3-3.0；
    所述甘油脂肪酸酯的制备方法为以甘油与脂肪酸为原料在碱性催化剂存在下200-250℃保温40-90min酯化制得；甘油脂肪酸酯的用量占有机硅乳液总质量的2-8％；
    C、聚醚改性聚硅氧烷
    所述的聚醚改性聚硅氧烷的结构式如下：
    Figure PCTCN2021098240-appb-100001
    其中，字母R 2为甲基、乙基、丙基、丁基或苯基；R 3为氢原子、甲基、乙基、丙基或丁基；下标r，s是硅链节的聚合度，s为1～50的整数，r为1～200的整数；下标e和f分别为环氧乙烷(EO)和环氧丙烷(PO)的聚合度，e和f均为1～50的整数；下标t为—CH 2的聚合度，为1～6的整数，聚醚改性聚硅氧烷的用量占有机硅乳液总质量的5-15％；
    D、增稠剂
    增稠剂选自聚丙烯酰胺、卡波姆、汉生胶、聚丙烯酸酯、纤维素醚类，增稠剂的用量占有机硅乳液总质量的0.5-3％；
    E、水
    水的用量占有机硅乳液总质量的50-80％；
    所述的有机硅乳液的制备方法如下：
    室温下，将活性物质、甘油脂肪酸酯、硅聚醚在搅拌下充分混合10～50min，形成混合物M；将增稠剂和水混合充分搅拌得到混合物N；然后将混合物M的温度升高至55℃～85℃保持体系温度，缓慢地加入混合物N，提高搅拌速度使其由油包水型乳液变为水包油型乳液，粗乳液通过胶体磨进一步乳化，得到所述的有机硅乳液。
  2. 根据权利要求1所述的一种有机硅乳液及制备方法，其特征在于所述的活性物质制备方法中催化剂优选氢氧化钠。
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