氨基硅油的合成及其微乳化研究
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摘要
本文简介了有机硅织物柔软剂发展简史、分类概况以及氨基硅油柔软剂的一般性能。研究了氨基硅油的合成方法及其微乳化工艺，讨论了影响聚合反应及微乳化的各种因素。研究结果表明：
1．以八甲基环四硅氧烷(D4)和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅氧烷(N602)为原料，氢氧化钾(KOH)为催化剂，通过本体聚合可合成得到不同氨值、不同粘度的氨基硅油。
2．最佳工艺条件为：反应温度135～145℃，反应时间4～5小时，催化剂用量0.06～0.08％。
3．用脂肪醇聚氧乙烯醚(NE0-9)和壬基酚聚氧乙烯醚(TX—4)复配的复合乳化剂可将氨基硅油乳化制成透明清晰的微乳液，其粒径小于0.15μm(150nm)。
4．复合乳化剂的配比为脂肪醇聚氧乙烯醚60％，烷基酚聚氧乙烯醚40％。其用量为氨基硅油质量的43％。
5．将氨基硅油制成微乳液的乳化工艺为：将氨基硅油和复合乳化剂在常规设备内搅拌混合，搅拌器转速在80～100r／min，不需高速高剪切设备或均化器，也不需升温，常温下搅拌混合30分钟即可得到稳定性良好的氨基硅油微乳液。
6．微乳液中加入少量有机酸酯(NZ)和亚硫酸氢钠(NS)，可有效降低泛黄性，且不增加成本、不降低柔软性。
7．氨基硅油微乳液用于织物的柔软整理，具有良好的使用效果。
In this thesis, the development history, classification of
textile softener of silicones and the common property of amino-
silicone oil are briefly introduced. Moreover, synthetic methods
and the techniques of micro-emulsifying of amino-silicone oil are
especially explained and the factors affecting the polymerization
and micro-emulsification are discussed. The results show that:
1.A series of amino-silicone oil with different-value and viscosity
were prepared with octamethylcyclotetrasilane and N-beta-
aminoethyl-gamma-aminopropylmethydimethoxysilane at potassium
hydroxide catalyst by bulk polymerization.
2. The optimized synthesis conditions is the reaction time 4~~5h; the reaction temperature 135-145@ and the dosage of catalyst =0.06?.08% of the reactant mass.
3. The compound emulsifier made through blending fatty alcohol polyoxyethylene ether and alkyphenol polyoxyethylene ether can emulsify and prepare ami no-si 1icone oi] into a transparent and clear micro-emulsions, with the diameter of its granule less than 0. 15um(150nm)
4. The ratio of compound emulsifier is fatty alcohol polyoxyethylene ether taking up 60% and alkyphenol polyoxyethylene ether taking
up 40%. The volume of usage is 43% of gravity of amino-silicone oil amino-silicone oil.
5. The micro-emulsifying technique of amino-silicone oil is to stir the amino-si1icone oil in routine facilities together with the compound emulsifier with the speed of the agitator at 80 ~ 100r/min, no need of facilities with high speed and high shearing force and no need of raising temperature as well. On the condition of common temperature with 30 minutes stirring, the micro-emulsion of amino-si 1 icone fluid with good stability could be obtained.
6. Adding a little of NZ and NS in mi croemulsion, the nature of its yellowing is considerably reduced with no concerns of increasing cost and decreasing softness .
7. Micro-emulsion should have an excellent effect while applied to soft treatment of textile.
1．以八甲基环四硅氧烷(D4)和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅氧烷(N602)为原料，氢氧化钾(KOH)为催化剂，通过本体聚合可合成得到不同氨值、不同粘度的氨基硅油。
2．最佳工艺条件为：反应温度135～145℃，反应时间4～5小时，催化剂用量0.06～0.08％。
3．用脂肪醇聚氧乙烯醚(NE0-9)和壬基酚聚氧乙烯醚(TX—4)复配的复合乳化剂可将氨基硅油乳化制成透明清晰的微乳液，其粒径小于0.15μm(150nm)。
4．复合乳化剂的配比为脂肪醇聚氧乙烯醚60％，烷基酚聚氧乙烯醚40％。其用量为氨基硅油质量的43％。
5．将氨基硅油制成微乳液的乳化工艺为：将氨基硅油和复合乳化剂在常规设备内搅拌混合，搅拌器转速在80～100r／min，不需高速高剪切设备或均化器，也不需升温，常温下搅拌混合30分钟即可得到稳定性良好的氨基硅油微乳液。
6．微乳液中加入少量有机酸酯(NZ)和亚硫酸氢钠(NS)，可有效降低泛黄性，且不增加成本、不降低柔软性。
7．氨基硅油微乳液用于织物的柔软整理，具有良好的使用效果。
In this thesis, the development history, classification of
textile softener of silicones and the common property of amino-
silicone oil are briefly introduced. Moreover, synthetic methods
and the techniques of micro-emulsifying of amino-silicone oil are
especially explained and the factors affecting the polymerization
and micro-emulsification are discussed. The results show that:
1.A series of amino-silicone oil with different-value and viscosity
were prepared with octamethylcyclotetrasilane and N-beta-
aminoethyl-gamma-aminopropylmethydimethoxysilane at potassium
hydroxide catalyst by bulk polymerization.
2. The optimized synthesis conditions is the reaction time 4~~5h; the reaction temperature 135-145@ and the dosage of catalyst =0.06?.08% of the reactant mass.
3. The compound emulsifier made through blending fatty alcohol polyoxyethylene ether and alkyphenol polyoxyethylene ether can emulsify and prepare ami no-si 1icone oi] into a transparent and clear micro-emulsions, with the diameter of its granule less than 0. 15um(150nm)
4. The ratio of compound emulsifier is fatty alcohol polyoxyethylene ether taking up 60% and alkyphenol polyoxyethylene ether taking
up 40%. The volume of usage is 43% of gravity of amino-silicone oil amino-silicone oil.
5. The micro-emulsifying technique of amino-silicone oil is to stir the amino-si1icone oil in routine facilities together with the compound emulsifier with the speed of the agitator at 80 ~ 100r/min, no need of facilities with high speed and high shearing force and no need of raising temperature as well. On the condition of common temperature with 30 minutes stirring, the micro-emulsion of amino-si 1 icone fluid with good stability could be obtained.
6. Adding a little of NZ and NS in mi croemulsion, the nature of its yellowing is considerably reduced with no concerns of increasing cost and decreasing softness .
7. Micro-emulsion should have an excellent effect while applied to soft treatment of textile.
引文
1 有机硅生产及应用技术。化学工业部科学技术情报研究所，1985。
2 李光亮，有机硅高分子化学，科学出版社，1998。
3 张济邦。有机硅柔软剂的现状和发展方向。印染，1996，22(6)：34-36．
4 朱清峰等。改性有机硅柔软剂的研制。印染，1997，23(7)：27-29。
5 李干佐等。硅氧烷表面活性剂。日用化学工业，1998，(1)；25-27。
6 穆森晶。八甲基环四硅氧烷(D4)阴离子乳液聚合反应的研究(J)。高分子通讯，1983，(3)：213-218。
7 上海二印纺织学会论文。含氢有机硅乳液研制和工艺探讨，1987。
8 王绪荣等。特种有机硅丝绸整理剂NTF-3应用研究。印染助剂，1995，12(5)：15。
9 Ciba Geigy Wool Rec.,1985(Dec. 37),144.
10 Walter Noll. Chem and Technol. Of Silic. Academic Press, 1968.
11 陈临吉。聚硅氧烷改性及其在纺织印染上的应用。浙江省印染助剂五届年会，1995。
12 Floyd DT, Jenni KR. Polymeric Materials Encyclopedia[M].Boca Raton New York London Tokyo :CRC Press, 1996, (10):7677.
13 Auxiliariers & Synthetic Organic Textile Chemicals. V.A Shenor & Natesh M Saraf, 1990.414
14 Harvey HH. Railrd. Lightweight concrete Using Polymer Filled Aggregate for Ocean Applications [P] [美国专利] US 4, 330.632
15 陈熔圻，氨基聚硅酮柔软剂，印染助剂，1999，16(1)：1
16 幸松民、王一路，有机硅合成工艺及产品应用，北京化学工业出版社，2000、32。
17 Sabia AJ. Use of Silicones to Enhance the Aesthetic and Functional Properties of Microfibers [J].Textile Chemist and Colorist, 1994,26(8):13-16.
18 Lautenschlager HJ, Bind J, Huhn KG. Structure Activity Relationships of Aminofunctional Siloxanes as Components in softening Finishes[J]. Textile Chemist and Colorist[J]. 1995, 27(3) :27-29.
19 Sabia AJ. Modificalion of the tactile and Physical Proper ties of Microfiber Fabric blends With Silicone Polymers[J]. Textile Chemist and Colorist, 1995,27(9):79-81.
20 黄文润。氨基硅油与织物柔软剂[J]。有机硅材料及应用，1998，(5)：16-18。
21 符书臻。氨基硅油的合成工艺[A]。江苏省印染助剂情报站第十六届年会资料汇编[C]。2000，9，57-64。
22 Maryline A, Van Der Spuy Andre. Use of Polysiloxanes Comprising Polyether and/or Amine Units as Antimisting Agents[P].PCT [国际专利: WO 9 927 031, 1999-06-03。
23 Edward CS, Daniel Rfa. Method of Treating Fibrous Materials for Improved Softness and Good Whiteness Retention[P]欧洲专利:EP 399 706,1990-11-28.
24 Lautenschlager HJ. Hubn, Textile chemist and Colorist, 1994.26(8):13-16;1995.27(3):27-29;1995.27(9):79-81
25 安秋凤，氨基硅整理剂的研究进展[J]，西北轻工学院学报，2000(3)，：86-94。
26 Waker, Textiles and Silicones-Amino Silicone Fluids. 1992,5;1994,2
27 崔正刚，微乳化技术及应用[M]，北京：中国轻工业出版社。
28 吕世静、高会宁，氨基改性有机硅氨基硅油微乳液技术的探讨[J]，北京服装学院学报，1998(4)：34-38
29 Adamson AW, Physical Chemistry of Surface (4thed). New York: Wilry, 1982.
30 Gerbacia W ,Rosano HL.J. Colloid Interface Sci, 1973, (44):242.
31 Ostrovsky MV, Good RJ.J. Colloid Interferce Sci, 1984, (102) :206.
32 赵国玺。表面活性剂物理化学。北京：北京大学出版社，1984。
33 Rosen MJ. Surfactants and Interfacial Phenomena (Chapter 8). New York: John-Wiley & Sons, 1978.
34 日本，特公平4-66 896．1992
35 日本，特开昭63-286 434．1998
36 日本，特公平6-220 777．1994
37 扬萌堂，我国纺织印染助剂的发展和展望[J]，印染助剂，1997，14(4)：39-42
38 Molly M, Joyner, Development of Silicone Micro-emulsion Based Softeners [J]. American Dye Stuff Repoter, 1998(8):36-38
39 Okinoshima, Hirshige, Kashiwagi, Tdutmu. Finishing Farics for Removal of Glitters Without Discoloration [P] 日本专利。
40 王树根．氨基改性硅油的研制[J]．印染助剂，1998，15(6)：5-8
41 史保川。氨烷基硅硅烷偶联剂的合成及其应用油[A]．江苏省印染助剂情报站第14届年会资料汇编[C]．1998，10。
42 曾庆福等。蓖麻织物的超级柔软整理方法探讨。印染，1998：24(2)：33-36。
43 王运来。蓖麻织物的超级柔软整理。纺织学报，1997：23(4)：35-37。
2 李光亮，有机硅高分子化学，科学出版社，1998。
3 张济邦。有机硅柔软剂的现状和发展方向。印染，1996，22(6)：34-36．
4 朱清峰等。改性有机硅柔软剂的研制。印染，1997，23(7)：27-29。
5 李干佐等。硅氧烷表面活性剂。日用化学工业，1998，(1)；25-27。
6 穆森晶。八甲基环四硅氧烷(D4)阴离子乳液聚合反应的研究(J)。高分子通讯，1983，(3)：213-218。
7 上海二印纺织学会论文。含氢有机硅乳液研制和工艺探讨，1987。
8 王绪荣等。特种有机硅丝绸整理剂NTF-3应用研究。印染助剂，1995，12(5)：15。
9 Ciba Geigy Wool Rec.,1985(Dec. 37),144.
10 Walter Noll. Chem and Technol. Of Silic. Academic Press, 1968.
11 陈临吉。聚硅氧烷改性及其在纺织印染上的应用。浙江省印染助剂五届年会，1995。
12 Floyd DT, Jenni KR. Polymeric Materials Encyclopedia[M].Boca Raton New York London Tokyo :CRC Press, 1996, (10):7677.
13 Auxiliariers & Synthetic Organic Textile Chemicals. V.A Shenor & Natesh M Saraf, 1990.414
14 Harvey HH. Railrd. Lightweight concrete Using Polymer Filled Aggregate for Ocean Applications [P] [美国专利] US 4, 330.632
15 陈熔圻，氨基聚硅酮柔软剂，印染助剂，1999，16(1)：1
16 幸松民、王一路，有机硅合成工艺及产品应用，北京化学工业出版社，2000、32。
17 Sabia AJ. Use of Silicones to Enhance the Aesthetic and Functional Properties of Microfibers [J].Textile Chemist and Colorist, 1994,26(8):13-16.
18 Lautenschlager HJ, Bind J, Huhn KG. Structure Activity Relationships of Aminofunctional Siloxanes as Components in softening Finishes[J]. Textile Chemist and Colorist[J]. 1995, 27(3) :27-29.
19 Sabia AJ. Modificalion of the tactile and Physical Proper ties of Microfiber Fabric blends With Silicone Polymers[J]. Textile Chemist and Colorist, 1995,27(9):79-81.
20 黄文润。氨基硅油与织物柔软剂[J]。有机硅材料及应用，1998，(5)：16-18。
21 符书臻。氨基硅油的合成工艺[A]。江苏省印染助剂情报站第十六届年会资料汇编[C]。2000，9，57-64。
22 Maryline A, Van Der Spuy Andre. Use of Polysiloxanes Comprising Polyether and/or Amine Units as Antimisting Agents[P].PCT [国际专利: WO 9 927 031, 1999-06-03。
23 Edward CS, Daniel Rfa. Method of Treating Fibrous Materials for Improved Softness and Good Whiteness Retention[P]欧洲专利:EP 399 706,1990-11-28.
24 Lautenschlager HJ. Hubn, Textile chemist and Colorist, 1994.26(8):13-16;1995.27(3):27-29;1995.27(9):79-81
25 安秋凤，氨基硅整理剂的研究进展[J]，西北轻工学院学报，2000(3)，：86-94。
26 Waker, Textiles and Silicones-Amino Silicone Fluids. 1992,5;1994,2
27 崔正刚，微乳化技术及应用[M]，北京：中国轻工业出版社。
28 吕世静、高会宁，氨基改性有机硅氨基硅油微乳液技术的探讨[J]，北京服装学院学报，1998(4)：34-38
29 Adamson AW, Physical Chemistry of Surface (4thed). New York: Wilry, 1982.
30 Gerbacia W ,Rosano HL.J. Colloid Interface Sci, 1973, (44):242.
31 Ostrovsky MV, Good RJ.J. Colloid Interferce Sci, 1984, (102) :206.
32 赵国玺。表面活性剂物理化学。北京：北京大学出版社，1984。
33 Rosen MJ. Surfactants and Interfacial Phenomena (Chapter 8). New York: John-Wiley & Sons, 1978.
34 日本，特公平4-66 896．1992
35 日本，特开昭63-286 434．1998
36 日本，特公平6-220 777．1994
37 扬萌堂，我国纺织印染助剂的发展和展望[J]，印染助剂，1997，14(4)：39-42
38 Molly M, Joyner, Development of Silicone Micro-emulsion Based Softeners [J]. American Dye Stuff Repoter, 1998(8):36-38
39 Okinoshima, Hirshige, Kashiwagi, Tdutmu. Finishing Farics for Removal of Glitters Without Discoloration [P] 日本专利。
40 王树根．氨基改性硅油的研制[J]．印染助剂，1998，15(6)：5-8
41 史保川。氨烷基硅硅烷偶联剂的合成及其应用油[A]．江苏省印染助剂情报站第14届年会资料汇编[C]．1998，10。
42 曾庆福等。蓖麻织物的超级柔软整理方法探讨。印染，1998：24(2)：33-36。
43 王运来。蓖麻织物的超级柔软整理。纺织学报，1997：23(4)：35-37。