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CN101307181B - Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications - Google Patents

Anion polyurethane and amino silicon oil composite water dispersion, preparation and applications Download PDF

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CN101307181B
CN101307181B CN 200810053726 CN200810053726A CN101307181B CN 101307181 B CN101307181 B CN 101307181B CN 200810053726 CN200810053726 CN 200810053726 CN 200810053726 A CN200810053726 A CN 200810053726A CN 101307181 B CN101307181 B CN 101307181B
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oil
polyurethane
amino
dispersion
silicone
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CN 200810053726
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CN101307181A (en )
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孙多先
郭睿威
鲍容容
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天津大学
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Abstract

The invention discloses an anionic polyurethane and amino silicone oil composite aqueous dispersion and a preparation method and an application thereof. High molecular weight polyether glycol and anionic diol chain extender react with diisocyanate to form anionic polyurethane after end capping. The anionic polyurethane and low molecular weight amino terminated silicone oil are blended and added with a salt forming agent for tertiary amine and biacrylic ester to conduct self-emulsification at the room temperature to form amino silicone oil/polyurethane blended anionic aqueous dispersion microemulsion. The anionic aqueous dispersion microemulsion is heated to complete a chain extension of amino silicone oil on opposite terminals of the biacrylic ester, and thus the preparation of high molecular weight amino silicone oil/polyurethane composite aqueous dispersion is realized. The high molecular weight amino silicone oil/polyurethane composite aqueous dispersion has characteristics of smallgrain size and good stability, and can be coated on the surfaces of fabrics to improve the hand feeling of the fabrics and the hydrophilcity and hydrophobicity of the surfaces of the fabrics.

Description

阴离子聚氨酯与氨基硅油复合的水分散液及其制备和应用 Amino silicone compound and anionic polyurethane aqueous dispersion and its preparation and application

技术领域 FIELD

[0001] 本发明属于高分子复合水分散液及其制备,特别是一种离子型聚氨酯/氨基硅油 [0001] The present invention pertains to a polymer composite aqueous dispersion and its preparation, especially an ionic urethane / amino silicone oil

复合水分散液及其制备,此类复合水分散液可用于织物柔软整理。 Composite aqueous dispersion and its preparation, such composites can be used in aqueous dispersion of fabric softening finishing. 背景技术 Background technique

[0002] 水分散聚氨酯和水分散有机硅油是重要的织物后整理助剂,可以赋予织物良好的柔软性和一定的抗皱性能,以及改变织物表面的亲水、亲油、透水性能。 [0002] The aqueous dispersion of water-dispersible polyurethane and the silicone oil is an important finishing auxiliaries, can impart good flexibility and a certain fabric wrinkle resistance, and varying the hydrophilic surface of the fabric, oleophilic, water permeability. 聚氨酯(PU)是由多异氰酸酯(主要是二异氰酸酯)和多元醇聚合而成的链段型嵌段高聚物(segmented blockpolymer)。 Polyurethane (PU) is a polyisocyanate (mainly diisocyanate), and polymerization of a polyol segment type block polymer (segmented blockpolymer). 由于综合了氨基甲酸酯硬段的强极性和聚醚或聚酯软段的柔顺性,聚氨酯材料具有高强度、耐溶剂、良好的附着性和高弹性、耐磨、抗撕裂、抗屈挠性等良好的物理机械性能,以及反应性。 Since the combination of flexibility, strongly polar urethane hard segment and soft segment of polyether or polyester, polyurethane material having a high strength, solvent resistance, good adhesion and high flexibility, abrasion resistance, tear resistance, anti- flex, such as good physical and mechanical properties, and reactivities. 利用荷电聚氨酯的自乳化能力,可以方便地制备纳米级的水分散液。 Ability to use self-emulsifying the polyurethane charged, can be conveniently prepared aqueous dispersion of nanoscale. 水基聚氨酯分散液已被用于织物的免烫整理剂、织物涂层整理剂和羊毛织物防毡縮剂等织物后整理工艺中。 Press finishing agents, textile finishing agents and coating-proofing wool water based polyurethane dispersions have been used in textile finishing process or the like after the fabric shrinkage.

[0003] 氨基改性有机硅是在聚硅氧烷大分子链上引入端烃氨基或侧烃氨基。 [0003] The amino-modified silicone is an amino group or a hydrocarbon side terminal amino group introduced into the hydrocarbon on the polysiloxane macromer chain. 将其用于织物整理剂,因氨基与织物纤维的定向结合作用,赋予织物优良的成膜性、耐久防皱性、回弹性、柔软性、疏水性、手感滑爽舒适性,成为织物柔软整理的主要品种。 Which was used in textile finishing agents, due to the orientation of the amino group binding to the textile fibers, giving good film forming fabric, durable wrinkle resistance, resilience, flexibility, hydrophobicity, smooth feel comfort, fabric softening finishing become the main varieties. 常用的氨基硅油乳液可以通过乳液聚合或机械乳化法制取。 Commonly used amino-silicone oil emulsion can be taken by emulsion polymerization or mechanical emulsification. 乳化剂通常可选择阳离子型非离子型。 Alternatively cationic emulsifiers are generally nonionic. 大量乳化剂的存在会影响氨基硅油对织物的附着,降低柔软效果。 Emulsifiers can affect a large number of amino-silicone oil is attached on the fabric, to reduce the softening effect. 另一方面,采用机械乳化法虽可以方便将氨基硅油乳化成微乳液,制得粒径小于150nm的分散液,但氨基硅油的分子量不能太高,否则因粘度高而不易乳化。 On the other hand, although the use of mechanical emulsification dispersion method can be easily emulsified into the amino silicone microemulsion having a particle diameter of less than 150nm, but the molecular weight of the amino silicone is not too high, otherwise difficult to emulsify due to high viscosity. 采用乳液聚合法可以制得高分子量的氨基硅油,但由于环氧硅烷开环聚合的平衡性,体系内仍存有较大含量的低分子量级分,对氨基硅油水分散液的使用造成一定的不利。 It may be prepared by emulsion polymerization of a high molecular weight amino silicone oil, but since the ring-opening polymerization of the epoxy silane balance, the system still has a large content of low molecular weight fraction using an aqueous dispersion of amino silicone cause some unfavorable. 因此有必要制备不含低分子乳化剂的高分子量氨基硅油纳米水分散液。 Therefore necessary to prepare a low-molecular emulsifier-free high molecular weight aqueous dispersion of nano-amino silicone.

[0004] 综合聚氨酯和氨基硅油两者的性能,制备聚氨酯/有机硅复合水分散液可望获得特殊的性能。 [0004] The performance of the two amino silicone and polyurethane synthesis, the preparation of polyurethane / silicone composite aqueous dispersion is expected to achieve a particular performance. 尤其是利用荷电聚氨酯的自乳化和高反应活性等特性,可以去除低分子乳化剂、降低分散粒子尺寸、提高分散体的稳定性,以及与其他助剂的相容性,实现织物整理剂的多功能化。 In particular, the use of self-emulsifying polyurethane charge and other characteristics of high reactivity, low-molecular emulsifiers may be removed, reducing the particle size dispersion, improved dispersion stability, and compatibility with other additives, to achieve a fabric finishing agent multifunctional. 因此聚氨酯/有机硅复合水分散液具有很大的应用潜力。 Thus polyurethane / silicone composite aqueous dispersion having a great potential.

[0005] 实现聚氨酯与有机硅复合的方法可分为共聚法和共混法两大类。 [0005] The method to achieve a composite of polyurethane and silicone copolymerization process can be divided into two categories, and blending. 虽然共聚法得到的有机硅改性聚氨酯PSU水分散液稳定,化学连接较易克服两者的不相容性,已获得较为广泛的研究和应用。 Although the silicone-modified polyurethane obtained by copolymerization PSU aqueous dispersion stable, chemically linked easier to overcome the incompatibility of both, it has been widely studied and applied. 但共聚法会降低有机硅分子链的柔软性,损害有机硅的实用性能,或者引入的有机硅成分太少,不能充分的发挥两种聚合物的优点。 However copolymerization reduces the flexibility of the molecular chain of the silicone, silicone practical performance damage, or the introduction of the silicone component is too small, not sufficiently play the advantages of both polymers. 因此,共混法实现有机硅对水性聚氨酯的改性有着重要的意义。 Therefore, blending to achieve a silicone-modified great significance to the aqueous polyurethane. 但目前有关聚氨酯/有机硅复合体系共混的研究都集中于将两种聚合物分别制成分散体系,再进行乳液共混。 For the present study, but a blend of a polyurethane / silicone composite systems have focused on two polymers prepared dispersions were then blended emulsion. 这种方法避免了聚氨酯和有机硅的极性差别大而引起的共混性差的问题。 This method avoids the problem of poor blending of polarities polyurethanes and silicones caused large. 但乳液共混法难以达到两相间的均匀复合,同时由于有大量的乳化剂存在于体系中,降低了有机硅对纤维和聚氨酯间的结合力,使复合体系的使用性能受到了影响,难以制得有满意的应用性能的聚氨酯/有机硅复合体系。 However, the emulsion is difficult to achieve uniform blending of the two phases complex, and because a large amount of emulsifier present in the system, reducing the binding force between the silicone and polyurethane fiber pairs, so that performance of the composite system affected, difficult to produce application must have satisfactory performance polyurethane / silicone composite system. [0006] 另一类使有机硅与聚氨酯复合的方法是在同一分散粒子内实现有机硅与聚氨酯的混合,制备聚氨酯/有机硅核壳型水分散液。 [0006] Another type of organosilicon compound with the polyurethane dispersion at the same method the silicone particles are mixed with the polyurethane to achieve, the preparation of polyurethane / silicone core-shell type aqueous dispersion. 利用荷电聚氨酯的自乳化能力,实现纳米级复合水分散,有效地增加聚氨酯与有机硅的混合均匀性。 Using a self emulsifying capacity charged polyurethane, the aqueous dispersion achieve nanocomposite, effectively increasing the uniformity of mixing of the silicone and polyurethane.

[0007] 但由于聚氨酯与有机硅的相容性差,溶解度差异很大,在共混体系中处于严重的相分离状态,很难制得纳米级的复合分散液,尤其对于高分子量的氨基硅油。 [0007] However, because of compatibility with silicone polyurethanes difference, very different solubility, in a serious state of phase separation in blends, it is difficult to obtain composite nano dispersion, especially for high molecular weight amino silicone oil. 而采用低分子量的氨基硅油将降低硅油的附着性和耐久性。 The use of low molecular weight aminosilicone will reduce the adhesion and durability of the silicone oil.

发明内容 SUMMARY

[0008] 本发明旨在提供一种阴离子聚氨酯与氨基硅油复合的水分散液及其制备和应用。 [0008] The present invention is directed to an anionic polyurethane complexed with an amino silicone oil aqueous dispersion and its preparation and use. 采用低分子量的端氨基硅油与聚氨酯在特定溶剂中混合完成复合乳化后,再与双丙烯酸酯通过Micheal加成反应实现氨基硅油的扩链反应,从而制备了聚氨酯/高分子量氨基硅油的复合纳米水分散液,该复合分散液具有良好的贮存稳定性。 With low molecular weight silicone oil and amino-terminated polyurethane hybrid emulsion complex completed in a particular solvent, and then diacrylate achieve chain extension reaction and thus the amino-silicone composite polyurethane / nano molecular weight aminosilicone water prepared by Micheal addition reaction, dispersion, the composite dispersion having good storage stability. 该复合聚氨酯/高分子量氨基硅油复合纳米水分散液可用于织物的后整理,提供柔软、抗皱等多功能。 The composite polyurethane / silicone composite nano molecular weight amino aqueous dispersion can be used after finishing the fabric, providing a soft, anti-wrinkle and other functions. [0009] 本发明提供的一种阴离子聚氨酯与氨基硅油复合的水分散液包括阴离子型聚氨酯与氨基硅油复合构成,该分散液的分散粒子的粒径在150nm以下,氨基硅油在分散粒子中的质量组成是10〜50%。 [0009] The aqueous polyurethane and an anionic amino silicone of the present invention provides a composite comprising a dispersion of an anionic polyurethane with a composite composed of amino silicone oil, the particle size of the dispersed particles in the dispersion liquid 150nm or less, in the amino silicone oil dispersed particles of mass the composition is 10~50%.

[0010] 所述的氨基硅油的分子量是20, 000以上,它是由分子量2, 000〜10, 000的端氨基硅油经双丙烯酸酯的Micheal加成反应扩链而制得。 [0010] The molecular weight of the amino silicone is 20, 000 or more, a molecular weight which is 2, 000~10, Micheal addition reaction of the terminal amino group of the chain 000 through the silicone diacrylate prepared.

[0011] 所述的阴离子聚氨酯由聚醚多元醇、阴离子二醇扩链剂、异佛尔酮二异氰酸酯反应制得。 [0011] The anionic polyurethanes from polyether polyol, glycol chain extender anionic, isophorone diisocyanate reaction.

[0012] 本发明提供的阴离子聚氨酯与氨基硅油复合的水分散液的制备方法,其特征在于包含如下步骤: [0012] Preparation of amino silicone anionic polyurethane of the present invention provides a composite aqueous dispersion, characterized by comprising the steps of:

[0013] 1)将聚醚多元醇、阴离子二醇扩链剂和二异氰酸酯在60〜9(TC间反应4〜10小时,经封端后制得阴离子聚氨酯。具体是: [0013] 1) polyether polyols, anionic glycol chain extender and a diisocyanate reacted in 60~9 (between TC 4~10 hours, after terminated anionic polyurethane prepared in particular:

[0014] (a)通常将聚醚多元醇在100〜12(TC、真空下通氮脱水处理2小时。冷到60〜 90。C后,加入二异氰酸酯,保持60〜90。C反应4〜6小时; [0014] (a) polyether polyols typically 100~12 (TC, vacuum dehydration under nitrogen for 2 hours. After cooling to 60~ 90.C, the diisocyanate was added, maintaining the reaction 60~90.C 4 ~ 6 hours;

[00巧](b)加入用N-吡咯烷(NMK)溶解的阴离子型二醇扩链剂,在60〜9(TC反应2〜 [Qiao 00] (B) adding anionic diol chain extender pyrrolidine with N- (the NMK) dissolved, (TC in the reaction 2 ~ 60~9

3小时,再加入封端剂,于60〜9(TC下反应2〜3小时,制得阴离子型聚氨酯。 3 hours, capping agent was added, the reaction (TC ~ 3 hours under 60~9 prepare an anionic polyurethane.

[0016] 2)将此阴离子聚氨酯与低分子量的端氨基硅油在溶剂作用下共混,在室温下加入 [0016] 2) of this low molecular weight anionic polyurethane with terminal amino silicone oil blend, added at room temperature under the action of the solvent

叔胺类成盐剂中和,以及加入扩链剂双丙烯酸酯后,加水自乳化形成水分散微乳液; After the tertiary amine and a salt-forming agent, and adding a chain extender diacrylate, add water, self-emulsifying microemulsion form an aqueous dispersion;

[0017] 3)升高温度至60〜8(TC间,反应1〜6小时,完成双丙烯酸酯对端氨基硅油的扩 [0017] 3) 60~8 to elevated temperatures (between TC, the reaction 1~6 hours to complete diacrylate terminal amino silicone oil to spread

链反应,制得产物。 Chain reaction, to obtain the product.

[0018] 4)在40〜60°C、0. 01〜0. 05MPa或真空下脱除有机溶剂。 [0018] 4) at 40~60 ° C, 0. 01~0. 05MPa or organic solvent removed under vacuum.

[0019] 所述的阴离子扩链剂与聚醚多元醇的摩尔比在1〜3 : 1, NCO/OH的摩尔比在1. 1〜1.5 : l,NCO表示异氰酸酯基,OH表示羟基。 [0019] The molar ratio of said anionic chain extender and a polyether polyol in ~ 3: 1 molar ratio of NCO / OH in 1. 1~1.5: l, NCO represents the isocyanate group, OH represents a hydroxyl group.

[0020] 所述的聚醚多元醇为聚环氧丙烷醚或部分环氧乙烷(EO)改性的聚环氧丙烷醚(EO含量小于50% ),分子量在1, 000〜6, 000。 [0020] The polyether polyol is polypropylene oxide ether or a part of ethylene oxide (EO) ether-modified polypropylene oxide (EO content of less than 50%), molecular weight of 1, 000~6, 000 .

[0021] 采用聚醚型聚氨酯可以提供良好的耐水解性。 [0021] The polyether polyurethane may provide good hydrolysis resistance. 引入部分氧化乙烯(EO)链节可以改善聚氨酯的亲水性,有利于乳化成更小的粒子。 Introduction portion of ethylene oxide (EO) chain link can be improved hydrophilic polyurethane conducive emulsified into smaller particles. 所述聚醚可以采用常规的以KOH为催化剂的聚合方法合成,也可以采用双金属催化剂来制备较高分子量的低不饱和度聚醚。 The polyether may be employed conventional KOH as a polymerization catalyst synthesis, it can also be prepared low unsaturation polyether of higher molecular weight bimetallic catalyst. 较高分子量的聚醚有利于改善与氨基硅油的相容性,也有利于提供更为柔软和良好弹性的聚氨酯。 Higher molecular weight polyether will help to improve compatibility with the amino silicone oil is also beneficial to provide more flexibility and good resilience polyurethane.

[0022] 所述的双丙烯酸酯具有如下结构: [0023] Diacrylate [0022] has the structure: [0023]

<formula>formula see original document page 5</formula> <Formula> formula see original document page 5 </ formula>

:少时易于发 : Hair came easy

CH2=CH—C—O—R~0—C—CH=CH2 [0024] 其中R基团为碳数不大于6的烷基或含氧醚烷基; CH2 = CH-C-O-R ~ 0-C-CH = CH2 [0024] wherein the R group is an alkyl group having a carbon number of not greater than 6, or an oxygen-containing ether group;

[0025] 双丙烯酸酯:氨基硅油=1.1〜l. 5 : i,摩尔比。 [0025] bisacrylate: amino silicone = 1.1~l 5:. I, molar ratio. 双丙烯酸酯的用: 生交联。 Diacrylate used: raw crosslinking.

[0026] 端氨基硅油是含伯胺或仲胺基的改性聚二甲基硅氧烷,其分子量在2,000 10, 000间,具有如下的分子结构: [0026] The terminal amino-modified silicone oil is a primary or secondary amine-containing polydimethyl siloxane having a molecular weight of 2,000 at 10, between 000 having the following molecular structure:

-CH。 -CH. , GH, , GH,

[0027] [0027]

CjH: CjH:

.CH_d~Si—Oh$i"~0.CH。 .CH_d ~ Si-Oh $ i "~ 0.CH.

—S卜 -S Bu

I I

nCH. nCH.

CH2_-RHN R为烷基或H CH2_-RHN R is H or an alkyl group

[0028] [0029] [0028] [0029]

[0030] [0030]

(m < 4的整数) (M <integer 4)

R = H时,所述的端氨基硅油具有如下结构-GH, , GH,NH。 When R = H, the amino-terminated silicone oil has a structure -GH,, GH, NH.

CjH: CjH:

-Si—O"f"Si一O'CH。 -Si-O "f" Si a O'CH.

,3 3

nCH, nCH,

,(m < 4的整数) , (Integer m <4) of

[0031] 所述的溶剂为二氯甲烷或四氢呋喃,优选二氯甲烷。 [0031] The solvent is methylene chloride or tetrahydrofuran, preferably dichloromethane. 溶剂的用量为30〜50%。 The amount of solvent is 30 ~ 50%. [0032] 所述的阴离子聚氨酯与氨基硅油复合的水分散液作为织物整理剂。 [0032] The aqueous anionic polyurethane dispersion of amino silicone compound as textile finishing agent. [0033] 所用的二异氰酸酯可以为芳香族异氰酸酯或脂肪族异氰酸酯,最好采用脂肪族氰酸酯,具有较好的耐黄变性,如异佛尔酮二异氰酸酯IPDI,六次甲基二异氰酸酯HDI。 [0033] The diisocyanates used may be aromatic isocyanates or aliphatic isocyanates, preferably using an aliphatic diisocyanate, having good yellowing resistance, such as isophorone diisocyanate of IPDI, hexamethylene diisocyanate HDI . [0034] 所述的阴离子扩链剂可以为二羟甲基丙酸或二羟甲基丁酸。 [0034] The anion may be a chain extender of dimethylolpropionic acid or dimethylolbutanoic acid.

[0035] 所用的封端剂可以是能形成稳定氨基甲酸酯的化合物,如异丙醇,也可以是能与 [0035] The blocking agent used may be capable of forming a stable carbamate compounds, such as isopropanol, it may be able to

NCO基团形成封闭型异氰酸酯的化合物,如二异丙胺、酮肟、咪唑等。 Compounds formed NCO groups of the blocked isocyanate, such as diisopropylamine, oxime, imidazole and the like. 采用封闭型异氰酸酯的 Using blocked isocyanate

分散液在使用过程中,可在适宜的加工温度(140〜180°C)下解封生成异氰酸酯基,进而与 Dispersion during use, deblocking can generate an isocyanate group at a suitable processing temperature (140~180 ° C), and further

被处理物中的活性基团,如羟基、胺基、羧基等反应,提高结合力和耐久性。 Be treated active groups, such as hydroxyl, amine, carboxyl and other reactions, to improve adhesion and durability.

[0036] 制备中NCO/OH的摩尔比控制在1. 1〜1. 5 : 1 (NCO表示异氰酸酯基,OH表示羟 [0036] prepared in a molar ratio of NCO / OH in control 1. 1~1 5:. 1 (NCO represents the isocyanate group, OH represents a hydroxyl

基)。 base). 较高的NCO/OH比值可以获得更高分子量的聚氨酯。 Higher NCO / OH ratio of higher molecular weight polyurethane can be obtained. 当需要制备链端封闭型PU时,可 When the closed end of the chain is desired to prepare PU, can

以采用较高的NCO/OH比值。 To use a higher NCO / OH ratio. 在含羟基的聚醚与扩链剂部分,扩链剂/聚醚多元醇的摩尔比 In the polyether portion of the hydroxyl-containing chain extender, the molar ratio of chain extender / polyether polyol

控制在1〜5 : 1。 Control 1 ~ 5: 1. 较高扩链剂用量可以降低分散粒子的粒径,提高分散液在处理过程中的 The amount of chain extender may be higher to reduce the diameter of dispersed particles to improve the dispersion in the process of

渗透性。 Permeability.

[0037] 在聚氨酯与氨基硅油的混合物中,氨基硅油是含伯胺或仲胺的端胺基硅油,其分子量在2, 000〜10, 000,即氨值在0. 20〜1. Ommol/g。 [0037] In a mixture of polyurethane and the amino silicone oil, amino silicone is a silicone oil containing terminal primary amine or secondary amine with a molecular weight of 2, 000~10, 000, i.e., the ammonia value 0. 20~1. Ommol / g. 更低分子量的氨基硅油不易控制扩链程度,当希望获得高的分子量时,易发生支化或交联。 Amino lower molecular weight silicone oil is difficult to control the degree of chain extension, when it is desired to obtain a high molecular weight, branched or prone to crosslinking. 更高分子量的氨基硅油不易与聚氨酯形成均匀的混合体。 Higher molecular weight aminosilicone easily formed uniformly mixed with the polyurethane. 氨基硅油的加入量占体系固形量的10〜50%。 Solid amount of 10~50% amino silicone oil added in an amount of the system. 由于氨基硅油与聚 Since the amino-silicone oil with polyethylene

5氨酯的极性相差很大,加入适当的溶剂对形成均相溶液,以及后继的共乳化至关重要。 5 very different polar urethane, homogeneous solution is added a suitable solvent, and subsequent co-formed emulsion is essential. [0038] 本发明制备的阴离子型聚氨酯/氨基硅油复合水分散液可用于织物的抗皱与柔软整理。 [0038] Preparation of an anionic polyurethane of the present invention / aminosilicone compound can be used in aqueous dispersion with a soft finishing fabric wrinkle. 经过扩链后的高分子量硅油对织物具有更好的附着力和耐久性,增加了耐洗性及整理效果。 After the high molecular weight silicone oil after the chain extender has better adhesion and durability of the fabric, increasing the washability and finishing results. 同时,扩链过程中产生的一定交联度可以增加织物的弹性(丰满度)。 At the same time, a certain degree of cross-linking chain may be produced during the increase of elastic fabric (fullness).

具体实施方式 detailed description

[0039] 下面给出本发明的具体实施例,以便更为详细地体现本发明的内容和具体操作过程。 Given the present invention [0039] The following specific examples, in order to embody the present invention and the specific operation in more detail. 实施例中所用的原料均是工业化原料,所用代号仅表明其主要结构特征,而不反映其具体的商业代号或商标。 Example The raw materials are used in industrial materials, which show only the main structural features with the code, rather than reflecting the specific code or commercial trademarks. 主要使用的原料及代号如下: [0040] IPDI :异佛尔酮二异氰酸酯[0041] DMPA:二羟甲基丙酸 The main raw material used and the following code: [0040] IPDI: isophorone diisocyanate [0041] DMPA: dimethylolpropionic acid

[0042] SDA-1 :氨值为1. 04mmol/g的端氨基聚二甲基硅氧烷[0043] SDA-2 :氨值为0. 22mmol/g的端氨基聚二甲基硅氧烷[0044] DAR:扩链剂乙二醇双丙烯酸酯(170) [0045] N-210 :羟值为112mgK0H/g的聚环氧丙烷醚二醇[0046] N-220 :羟值为55mgK0H/g的聚环氧丙烷醚二醇[0047] N-240 :羟值为27mgK0H/g的聚环氧丙烷醚二醇[0048] N-260 :羟值为18mgK0H/g的聚环氧丙烷醚二醇[0049] NMK :N-妣咯烷[0050] DCM:二氯甲烷[0051] THF:四氢呋喃 [0042] SDA-1: Ammonia is 1. 04mmol / g of terminal amino polydimethylsiloxane [0043] SDA-2: Ammonia is 0. 22mmol / g of terminal amino polydimethylsiloxane [0044] DAR: chain extender glycol diacrylate (170) [0045] N-210: hydroxyl value 112mgK0H / g of polypropylene oxide ether glycol [0046] N-220: hydroxyl value 55mgK0H / g of polypropylene oxide ether glycol [0047] N-240: hydroxyl value 27mgK0H / g of polypropylene oxide ether glycol [0048] N-260: hydroxyl value 18mgK0H / g of polypropylene oxide ether two alcohol [0049] NMK: N- deceased mother pyrrolidine [0050] DCM: dichloromethane [0051] THF: tetrahydrofuran

[0052] 使用的原料依聚氨酯合成要求,必要时需进行脱水处理。 [0052] The starting material used in the synthesis of polyurethanes according to requirements, be dehydrated if necessary. 所述原料份数无特别说 The raw material is not particularly said parts

明时均指质量份数。 Refer to the quality of copies Ming. [0053] 实施例1 [0053] Example 1

[0054] 在装有冷凝管和搅拌装置的四口瓶中,加入20g(20mmo1)已脱水的聚醚N-210和8. 0g(36mmol)IPDI,在60。 [0054] In the 4-neck flask equipped with a condenser and a stirring device, was added 20g (20mmo1) of dehydrated N-210 polyether and 8. 0g (36mmol) IPDI, 60. C水浴下反应4. 5h。 C water bath under the reaction 4. 5h. 加入用4g NMK溶解的1. 34g(lOmmol)DMPA, 继续在8(TC下反应2h,加入1. Og异丙醇封端,反应2h。降温到4(TC,加入20. 0g 二氯甲烷溶剂和6. 0g(3mmo1)端氨基硅油SDA-1和0. 6g(3. 6mmo1)乙二醇双丙烯酸酯扩链剂,混合均匀。加入1.2g(12mmo1)三乙胺中和15min。搅拌下滴加150g水完成乳化,将乳液放热到6(TC扩链2h。真空下脱出溶剂,得产物阴离子型聚氨酯/氨基硅油复合水分散液,分散粒径为110nm,固含量为20%。 [0055] 实施例2 4g NMK dissolved was added with 1. 34g (lOmmol) DMPA, the reaction was continued (at TC 8 2h, isopropanol was added 1. Og terminated, the reaction 2h. Lowered to 4 (TC, the solvent methylene chloride was added 20. 0g and stirred 6. 0g (3mmo1) terminal amino silicone SDA-1 and 0. 6g (3. 6mmo1) ethylene glycol diacrylate chain extender, mixed added 1.2g (12mmo1) and triethylamine 15min. 150g of water was added dropwise to complete the emulsion, the emulsion exothermed to 6 (TC 2H chain. prolapse solvent under vacuum to give the product an anionic urethane / amino silicone composite aqueous dispersion, the dispersion particle diameter of 110 nm, a solids content of 20%. [ 0055] Example 2

[0056] 在装有冷凝管和搅拌装置的四口瓶中,加入20g(20mmo1)已脱水的聚醚N-210和8. 0g(36mmol)IPDI,在90。 [0056] In the 4-neck flask equipped with a condenser and a stirring device, was added 20g (20mmo1) of dehydrated N-210 polyether and 8. 0g (36mmol) IPDI, 90. C水浴下反应4. 5h。 C water bath under the reaction 4. 5h. 加入用4g NMK溶解的1. 34g(lOmmol)DMPA, 继续在8(TC下反应2h,加入1. Og异丙醇封端,反应2h。降温到4(TC,加入30. 0g 二氯甲烷溶剂和20. 0g(2. Ommol)端氨基硅油SDA-2和0. 4g(2. 4mmo1)乙二醇双丙烯酸酯扩链剂,混合均匀。加入1. 2g(12mmo1)三乙胺中和15min。搅拌下滴加200g水完成乳化,将乳液放热到8(TC扩链6h。真空下脱出溶剂,得产物阴离子型聚氨酯/氨基硅油复合水分散液,分散粒径为150nm,固含量为25%。[0057] 其他相类似的配方列于表1 (实施例3-8)。反应步骤与条件同实例二。 4g NMK dissolved was added with 1. 34g (lOmmol) DMPA, the reaction was continued (at TC 8 2h, isopropanol was added 1. Og terminated, the reaction 2h. Lowered to 4 (TC, the solvent methylene chloride was added 30. 0g and 20. 0g (2. Ommol) terminal amino silicone SDA-2 and 0. 4g (2. 4mmo1) ethylene glycol diacrylate chain extender, mixed added 1. 2g (12mmo1) and triethylamine 15min . 200g of water was added dropwise with stirring to complete the emulsion, the emulsion exothermed to 8 (TC 6H chain. prolapse solvent in vacuo to give the product an anionic urethane / amino silicone composite aqueous dispersion, the dispersion particle diameter of 150nm, a solids content of 25 %. [0057] other similar formulations are listed in table 1 (examples 3-8). the reaction steps and conditions as in Example II.

[0058] 表1聚氨酯/高分子氨基硅油复合水分散液制备 Preparation of liquid [0058] Table 1 Polyurethane / water-dispersible polymer compound aminosilicone

[0059] [0059]

<table>table see original document page 7</column></row> <table> <Table> table see original document page 7 </ column> </ row> <table>

[0060] 实施例9 [0060] Example 9

[0061] 在装有冷凝管和搅拌装置的四口瓶中,加入20g(5mmo1)已脱水的聚醚N-240和5.8g(26mmol)IPDI,在8(TC水浴下反应6h。加入用5g NMK溶解的2. Og(15mmol)匿PA,继续在8(TC下反应2h,加入1. Og异丙醇封端,反应3h。降温到40°C ,加入30. Og 二氯甲烷溶剂和10. Og(l. Ommol)端氨基硅油SDA-2和0. 2g(l. 2mmo1)乙二醇双丙烯酸酯扩链剂,混合均匀。加入1.2g(12mmo1)三乙胺中和15min。搅拌下滴加150g水完成乳化,将乳液放热到8(TC扩链4h。真空下脱出溶剂,得产物阴离子型聚氨酯/氨基硅油复合水分散液,分散粒径为120nm,固含量为20%。 [0061] In the 4-neck flask equipped with a condenser and a stirring device, was added 20g (5mmo1) polyether dehydrated N-240 and 5.8g (26mmol) IPDI, the reaction 6h (TC water bath at 8 was added with 5g NMK dissolved 2. Og (15mmol) hide PA, the reaction was continued (at TC 8 2h, isopropanol was added 1. Og terminated, the reaction 3h. cooled to 40 ° C, and the solvent methylene chloride was added 30. Og 10 . Og (l. Ommol) terminal amino silicone SDA-2 and 0. 2g (l. 2mmo1) ethylene glycol diacrylate chain extender, mixed added 1.2g (12mmo1) and triethylamine 15min. stirring 150g of water was added dropwise to complete the emulsification, the emulsion was heat to 8 (TC 4H chain. prolapse solvent under vacuum to give the product an anionic urethane / amino silicone composite aqueous dispersion, the dispersion particle diameter of 120 nm, a solids content of 20%.

Claims (8)

  1. 一种阴离子聚氨酯与氨基硅油复合的水分散液,包括阴离子型聚氨酯与氨基硅油复合构成,该分散液的分散粒子的粒径在150nm以下,氨基硅油在分散粒子中的质量组成是10~50%,其特征在于所述的氨基硅油的分子量是20,000以上,它是由分子量2,000~10,000的端氨基硅油经双丙烯酸酯的Micheal加成反应扩链而制得。 An anionic polyurethane complexed with an amino silicone oil aqueous dispersion comprising a polyurethane and an anionic compound composed of amino silicone oil, the particle size of the dispersed particles in the dispersion liquid 150nm or less, amino silicone particles dispersed in the mass of the composition is 10 to 50% wherein the molecular weight of the amino silicone is 20,000 or more, it is the terminal amino silicone oil having a molecular weight of 2,000 to 10,000 through diacrylate Micheal addition reaction of the chain extender prepared.
  2. 2. 根据权利要求1所述的阴离子聚氨酯与氨基硅油复合的水分散液,其特征在于所述的阴离子聚氨酯由聚醚多元醇、阴离子二醇扩链剂、异佛尔酮二异氰酸酯反应制得。 The anionic polyurethane and the amino silicone is a water dispersion of a composite as claimed in claim, wherein said anionic polyurethane is a polyether polyol, glycol chain extender anionic, isophorone diisocyanate prepared by reacting .
  3. 3. 权利要求1所述的阴离子聚氨酯与氨基硅油复合的水分散液的制备方法,其特征在于包含如下步骤:1) 将聚醚多元醇、阴离子二醇扩链剂和二异氰酸酯在60〜9(TC间反应4〜10小时, 经封端后制得阴离子聚氨酯;2) 将此阴离子聚氨酯与低分子量的端氨基硅油在溶剂作用下共混,在室温下加入叔胺类成盐剂中和,以及加入双丙烯酸酯后,加水自乳化形成水分散微乳液;3) 升高温度至60〜80°C间,反应1〜6小时,完成双丙烯酸酯对端氨基硅油的扩链反应,制得产物;4) 在40〜60°C、0. 01〜0. 05MPa或真空下脱除有机溶剂。 The method of preparing an aqueous dispersion of anionic polyurethane and the amino silicone compound according to claim 1, characterized by comprising the steps of: a) polyether polyol, glycol chain extender, and an anionic diisocyanate in 60~9 (TC reaction between 4~10 hours, after terminated anionic polyurethane prepared; 2) this low molecular weight anionic polyurethane with terminal amino silicone oil blend, a tertiary amine is added at room temperature under the action of a solvent and a salt forming agent , and after adding diacrylate, add water, self-emulsifying microemulsion form an aqueous dispersion; 3) Room temperature was raised to 60~80 ° C, the reaction 1~6 hours to complete chain extension diacrylate terminal amino silicone oil to prepare product was obtained;. 4) at 40~60 ° C, 0 01~0 05MPa or organic solvent removed under vacuum.
  4. 4. 根据权利要求3所述的制备方法,其特征在于所述的阴离子扩链剂与聚醚多元醇的摩尔比在i〜3 : i,异氰酸酯基:羟基的摩尔比为i. i〜i.5 : i。 4. The method of preparation according to claim 3, wherein the molar ratio of chain extender to polyether polyol is in the anionic i~3: i, an isocyanate group: hydroxyl molar ratio of i i~i .5: i.
  5. 5. 根据权利要求3所述的制备方法,其特征在于所述的聚醚多元醇为聚环氧丙烷醚或部分环氧乙烷改性的聚环氧丙烷醚,EO的质量含量小于50%,分子量在1, 000〜6, 000。 The production method according to claim 3, wherein said polyether polyol is polypropylene oxide ether or a part of ethylene oxide-modified polypropylene oxide ether, EO content by mass is less than 50% , a molecular weight, 000~6, 000.
  6. 6. 根据权利要求3所述的制备方法,其特征在于所述的双丙烯酸酯具有如下结构:<formula>formula see original document page 2</formula>其中R基团为碳数不大于6的烷基或含氧醚烷基;双丙烯酸酯:氨基硅油=1.1〜i. 5 : i,摩尔比。 6. The method of preparation according to claim 3, wherein said diacrylate, has the following structure: <formula> formula see original document page 2 </ formula> wherein the R group is alkyl having a carbon number of not greater than 6, or an ether oxygen-containing alkyl group; diacrylate: amino silicone = 1.1~i 5: i, a molar ratio.
  7. 7. 根据权利要求3所述的制备方法,其特征在于所述的端氨基硅油具有如下结构: CjH3 ,3<formula>formula see original document page 2</formula>•NH2 (m < 4的整数)其分子量在2, 000〜10, 000间。 7. The method of preparation according to claim 3, wherein said amino terminated silicone oil has the structure: CjH3, 3 <formula> formula see original document </ formula> (integer m <4 a) • NH2 page 2 2 in which the molecular weight, 000~10, 000 between.
  8. 8.根据权利要求1所述的阴离子聚氨酯与氨基硅油复合的水分散液的应用,其特征在于它作为织物整理剂。 Application of an aqueous dispersion of an anionic polyurethane according to claim 1, wherein said amino silicone compound, characterized in that as textile finishing agents.
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