CN101952350A - 带有氨基甲酸酯官能团的聚二有机硅氧烷、它们的制备和它们作为纺织工业中的软化剂的用途 - Google Patents
带有氨基甲酸酯官能团的聚二有机硅氧烷、它们的制备和它们作为纺织工业中的软化剂的用途 Download PDFInfo
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- CN101952350A CN101952350A CN2009801061601A CN200980106160A CN101952350A CN 101952350 A CN101952350 A CN 101952350A CN 2009801061601 A CN2009801061601 A CN 2009801061601A CN 200980106160 A CN200980106160 A CN 200980106160A CN 101952350 A CN101952350 A CN 101952350A
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- C08G77/04—Polysiloxanes
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- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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Abstract
本发明涉及具有支化氨基甲酸酯官能团的聚二有机硅氧烷油、它们的制备和它们作为纺织工业中的软化剂的用途。
Description
本发明涉及具有支化氨基甲酸酯官能团的聚二有机硅氧烷、它们的制备和它们作为软化剂在纺织工业中的用途。关于氨基或酰氨基官能的有机硅化合物,有大量的文献资料。这些化合物例如用作纺织工业中的增塑剂,用作表面处理剂、用作增稠剂或用于化妆品工业。尽管如此,在纺织工业中需要使产品具有优异手感的且在使用中没有不稳定乳液的缺点的软化物质。
US 4,104,296描述了具有经由一个含至少三个碳原子的二价烃基残基连接到有机硅链上的羟烷基酰氨基官能团的有机官能有机硅组分。通过氨基烷基硅烷或氨基烷基硅氧烷与衍生自链长为C3至C9的α,β-羟基羧酸的内酯的反应制备该有机硅组分。这些组分被认为会改进各种树脂与无机基底的粘合性。
WO 2008/008077描述了通过封端的氨基官能的聚有机硅氧烷与异氰酸酯或环状碳酸酯的反应制得的氨基甲酸酯官能的聚有机硅氧烷。这些化合物进一步经由它们的游离OH基团与内酯反应以形成聚硅氧烷-聚内酯聚合物。由此获得的官能化聚硅氧烷可用于各种环境,如海洋环境中的防污材料。
现在也已经发现,具有侧链氮原子的某些硅油容易与环状碳酸酯反应以产生相应的氨基甲酸酯官能化硅油,这些化合物可以加工成在用作纺织工业中的软化剂时具有惊人地好的性质的稳定的水性分散体并产生具有舒适的柔软手感的产品。
本发明的目的是提供尤其用作整理剂的具有支化氨基甲酸酯官能团的聚二有机硅氧烷,其除改进的柔软感性质外还表现出高的抗黄化性并可毫无困难地用于高剪切施涂系统。
在第一个具体实施方案中,本发明涉及通式(I)的具有支化氨基甲酸酯官能团的聚二有机硅氧烷
其中
R1代表相同或不同的一价C1至C18烃残基,
m具有1至50的平均值;且
n具有10至1500的平均值。
C1-C18烃残基R1的例子包括烷基残基,如甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔丁基,正戊基,新戊基,叔戊基残基,己基残基,庚基残基,如正庚基残基,辛基残基和异辛基残基,如2,2,4-三甲基戊基残基,壬基残基,如正壬基残基,癸基残基,如正癸基残基,十二烷基残基,如正十二烷基残基,环烷基残基,如环戊基,环己基,环庚基残基和甲基环己基残基,芳基残基,如苯基和萘基残基,烷芳基残基,如邻-、间-、对-甲苯基残基,二甲苯基残基和乙基苯基残基,芳烷基残基,如苄基残基,α-和β-苯乙基残基。
上述烃残基任选含有脂族双键。其例子是烯基残基,如乙烯基、烯丙基、5-己烯-1-基、E-4-己烯-1-基、Z-4-己烯-1-基、2-(3-环己烯基)乙基和环十二碳-4,8-二烯基残基。具有脂族双键的优选残基是乙烯基、烯丙基和5-己烯-1-基残基。但是,优选最多1%的烃残基R1含有双键。
在上述通式(I)中,优选和独立地:
R1代表甲基和/或苯基;
m具有1至10的值;且
n具有40至600的值。
式I的化合物可以通过首先合成式(II)的氨基烷基支化聚二有机硅氧烷来制造。这些氨基取代的聚二有机硅氧烷的合成是本领域技术人员已知的,如在US 3355424、US 2947771、US 3890269中所公开,并且是导致带有烷基氨基的二烷氧基烷基硅烷单元插入硅氧烷链中的缩聚反应。该反应通常在酸性或碱性催化剂存在下进行。该反应也可以作为使用二烷氧基烷基硅烷和环状硅氧烷的聚合反应进行。
随后,添加环状碳酸酯,如碳酸甘油酯(式A的化合物)以形成式(I)的氨基甲酸羟烷酯支化的聚硅氧烷聚合物。
因此,本发明的另一个具体实施方案在于通过使式(II)的氨基官能的聚二有机硅氧烷与下列化合物(A)反应来制备上述式I的聚二有机硅氧烷
其中R1如式(I)中所定义;R5是-H或-CH2-CH2-NH2,
m具有1至50的平均值;
n具有10至1500的平均值;
在上式(II)中,优选地且独立地:
R1代表甲基和/或苯基;
m具有1至10的值;
n具有40至600的值;
优选的通式(II)的支化氨基官能的聚二有机硅氧烷是线型α,ω二甲基聚二甲基硅氧烷。
式II的化合物中可滴定氮的含量优选为An=0.01毫摩尔/克至2.0毫摩尔/克,尤其是0.1毫摩尔/克至1.0毫摩尔/克。An代表胺值。通式(II)的支化氨基聚二有机硅氧烷优选具有在25℃下50至100,000厘泊,尤其是100至15,000厘泊的平均粘度。
该反应可任选在合适的溶剂存在下进行。优选的是极性溶剂,如醇或酮,其例子是甲醇、乙醇、丙醇、异丙醇、丙酮或乙基甲基酮。
该反应优选根据所用溶剂在40至150℃的范围内进行。
该反应更优选在无溶剂的情况下在80至120℃的范围内进行。
所得式I的化合物中可滴定氮的含量优选小于An=0.1毫摩尔/克。An代表胺值。
通式(I)的聚二有机硅氧烷优选以水性制剂形式使用。优选的制剂是乳液。
基于总组合物,这类制剂含有2至80重量%的一种或多种式(I)的聚二有机硅氧烷。聚二有机硅氧烷乳液的合适制备方法例如从US5,302,657中获知。
在本发明中,优选在两个步骤中用可溶解在式I的聚二有机硅氧烷中的乳化剂制备该乳液,其中第一步骤产生浓缩物,其在第二步骤中用水稀释。这样的乳液含有以总组合物计2至40重量%的一种或多种乳化剂。
特别合适的阴离子型乳化剂包括:
1.烷基硫酸盐,尤其是具有8至18个碳原子链长的那些,和在疏水残基中具有8至18个碳原子和具有1至40个氧化乙烯(EO)或氧化丙烯(PO)单元的烷基醚硫酸盐。
2.磺酸盐,尤其是具有8至18个碳原子的烷基磺酸盐,牛磺酸盐、磺酸与具有4至15个碳原子的一元醇或烷基酚的酯和半酯;任选地,这些醇或烷基酚也可用1至40个EO单元乙氧基化。
3.具有8至20个碳原子以及烷基、芳基、烷基芳基或芳烷基残基的羧酸的碱金属和铵盐。
4.磷酸偏酯和它们的碱金属盐和铵盐,尤其是在有机残基中具有8至20个碳原子的烷基磷酸盐和烷基芳基磷酸盐,在烷基或烷基芳基残基中具有8至20个碳原子和具有1至40个EO单元的烷基醚磷酸盐或烷芳基醚磷酸盐。
特别合适的非离子型乳化剂包括:
1.烷基聚乙二醇醚,优选为具有4至40个EO单元和含8至20个碳原子的烷基残基的那些。
2.烷基芳基聚乙二醇醚,优选为具有4至40个EO单元和在烷基中含8至20个碳原子的烷基残基和芳基残基的那些。
3.氧化乙烯/氧化丙烯(EO/PO)嵌段聚合物,优选为具有4至40个EO或PO单元的那些。
4.含6至24个碳原子的脂肪酸。
5.天然物质和它们的衍生物,如卵磷脂、羊毛脂、皂草苷、纤维素;纤维素烷基醚和羧烷基纤维素,它们的烷基分别含有最多4个碳原子。
6.含有极性基团的线型聚二有机硅氧烷,尤其是含有聚醚基团的线型聚二有机硅氧烷。
7.具有8至24个碳原子的饱和和不饱和烷氧基化脂肪胺。
特别合适的阳离子型乳化剂包括:
8.具有8至24个碳原子的伯、仲和叔脂肪胺与乙酸、盐酸和磷酸的盐。
9.季烷基苯铵盐,尤其是其烷基具有6至24个碳原子的那些,尤其是卤化物、硫酸盐、磷酸盐和乙酸盐。
10.烷基吡啶鎓、烷基咪唑鎓和烷基噁唑啉鎓盐,尤其是其烷基链具有最多18个碳原子的那些,尤其是卤化物、硫酸盐、磷酸盐和乙酸盐。
适用于制备该乳液的乳化剂进一步包括脂肪酸聚乙二醇酯、聚乙氧基化脂肪酸甘油酯和失水山梨糖醇酯、烷基聚糖苷、脂肪酸烷醇酰胺、烷基醚羧酸、烷芳基醚羧酸、乙氧基化季铵盐、胺氧化物、甜菜碱、磺基甜菜碱和磺基丁二酸酯。
任选地,在式I的化合物的水性制剂中可以以总组合物计0至20重量%的量使用有机水溶助长剂。“水溶助长剂”是指改进难溶物质的水溶性并由此充当增溶剂的物质。同时,水溶助长剂降低要加工的物质的粘度。
该水溶助长剂可以选自多官能醇。因此,可以使用每分子含2至10个,优选2至6个,尤其是2至4个碳原子的二醇。同样非常合适的是它们的单醚和二醚以及这些二醇的单酯和二酯。要使用的它们的例子更优选包括1,2-丙二醇、二丙二醇和丁基二甘醇。
式(I)的聚二有机硅氧烷的制剂可任选含有0至96重量%的水。
任选以总组合物计0至5重量%的量使用无机和有机酸和/或它们的酸酐调节该制剂的pH值。因此,例如,使用盐酸、硫酸或磷酸作为无机酸。或者,可以使用有机酸,如甲酸、乙酸、乙醇酸、醛糖酸如葡糖酸、抗坏血酸、或糖醛酸如葡糖醛酸,和作为多元酸,例如草酸、柠檬酸或醛糖二酸,如葡糖二酸或半乳糖二酸。作为有机酸酐的例子,可以提到乙酸酐。
可以在10至90℃的范围内在均匀混合下用0.5至10小时形成该制剂,特别是乳液。优选的是在20至70℃范围内的温度。
根据本发明形成该制剂,尤其是乳液用的反应时间取决于所用温度。因此,在非常低的温度下,该反应时间优选为5至10小时,而在升高的温度下,较短反应时间,尤其是0.5至5小时是足够的。
本发明进一步涉及在水浴和施涂液中使用式(I)的聚二有机硅氧烷整理有机纤维和织物,任选与传统的氨基官能的改性聚二有机硅氧烷一起,以实现产品的特别柔软和精致的手感。
特别可提到在浸轧机上使用时通过浸轧加压施涂,其中可以使用干碰湿和湿碰湿法。浸涂(Exhausting)、喷涂或泡沫施涂法也非常适用于施涂该乳液。
用本发明的式I的聚二有机硅氧烷制剂整理的白色织物材料与相当的传统氨基官能的聚二有机硅氧烷乳液相比表现出显著降低的由在热应力过程中施加的高温引起的黄化。
除了这些有利性质外,本发明的乳液甚至在强碱性或强酸性pH值下也具有在施涂过程中的高稳定性,以便即使在极不利的条件累加时,例如在如快速运行的织物整理机上常见的同时存在高pH值和/或高液体温度和/或非常高的剪切应力时,防止聚结造成的有机硅沉淀和因此在织物产品上的污点。
与在剪切稳定性、黄化和pH稳定性方面具有类似性质的阳离子官能化聚二有机硅氧烷乳液相比的优点是本发明的制剂,尤其是乳液的明显更好的阴离子稳定性。阳离子官能化的聚二有机硅氧烷乳液常常倾向于在例如夹带的阴离子染料残留物或阴离子织物助剂存在下造成有机硅沉淀和转移到织物产品上,这在使用本发明的电中性氨基甲酸酯官能氨基聚二有机硅氧烷乳液时不发生。
本发明的氨基甲酸酯官能的聚二有机硅氧烷乳液可以在任何时刻与织物整理中常见的其它化学品,如纤维素交联剂、交联催化剂、基于脂肪酸酯和/或脂肪酸胺缩合产物的织物软化剂、各种组成的感官改性聚合物分散体和荧光增白剂组合。
下列实施例例证本发明,但不是限制性的。
实施例
实施例中所用的材料:氨基丙基二甲氧基甲基硅烷(APMDS)、氨基乙基氨基丙基二甲氧基甲基硅烷(DYNAS)(两者都来自Dynasilan系列)、八甲基环四硅氧烷(D4)、α,ω-二羟基-聚二甲基硅氧烷(Dow200fluid系列)和α,ω-二甲基-聚二甲基硅氧烷(AK系列)、以GC为名来自Huntsman Chemicals的碳酸甘油酯。来自Aldrich Chemicals的苄基三甲基氢氧化铵(在甲醇中的40%溶液)。所有材料不不进一步提纯的情况下按来样使用。
式II的化合物的制造方法
对于含有氨基乙基氨基丙基的α,ω-烷基封端聚二烷基硅氧烷,主要通过使100至800份α,ω-二甲基-聚二甲基硅氧烷与100至1000份α,ω-二羟基-聚二甲基硅氧烷或八甲基环四硅氧烷和10至150份氨基丙基二甲氧基甲基硅烷(APMDS)或氨基乙基氨基丙基二甲氧基甲基硅烷(DYNAS)在催化量的苄基三甲基氢氧化铵存在下反应来进行相应的合成。通过改变α,ω-二甲基-聚二甲基硅氧烷与相关胺的比率来调节低聚物的分子量。该反应在80℃下进行10小时。在反应完成后,将温度升至170℃并在此温度下保持1小时以分解该催化剂。这产生下式的化合物,其中m+n为30至600的数。
式I的化合物的制造方法
实施例1
将4.69克(0.04摩尔)碳酸甘油酯在室温下添加到50克可滴定氮含量An=0.53毫摩尔/克的含有氨基乙基氨基丙基的α,ω-甲基封端聚二甲基硅氧烷中。将该混合物在120℃下搅拌8小时。所得白色油表现出An=0.015毫摩尔/克的可滴定氮最终含量。转化率:97%。该方法产生下式的产物,其中m+n为70至100的数。
实施例2
将6.4克(0.051摩尔)碳酸甘油酯添加到50克可滴定氮含量An=0.98毫摩尔/克的含有氨基乙基氨基丙基的α,ω-甲基封端聚二甲基硅氧烷中。将该混合物在60℃下搅拌90分钟。将所得油冷却至室温,其氮含量测得为An=0.06毫摩尔/克。粘度:3620Cps。转化率:94%。
实施例3至6
表1显示式II的各种氨基乙基氨基丙基-聚二甲基硅氧烷与碳酸甘油酯反应的反应产物的性质的进一步例子。通过遵循如实施例1和2中的反应参数,进行该反应。Ani:原材料的初始胺含量。Anf:所得聚合物的最终胺含量。二甲基硅氧烷单元和甲基氨基硅氧烷的总和作为m+n显示在下表中。
实施例7:
乳液法
将25克根据实施例2获得的化合物在室温下添加到11克含7个氧化乙烯单元的异十三烷基乙氧基化物、5克己二醇和64克水中。将该混合物在室温下搅拌90分钟。用乙酸将所得微乳液调节至pH 5。
对比例1
将36克含有氨基乙基氨基丙基、粘度为3300mpa·s且An为0.1毫摩尔/克的可滴定氮含量的聚二有机硅氧烷添加到6克含5个氧化乙烯单元的异十三烷基乙氧基化物、20克含7个氧化乙烯单元的异十三烷基乙氧基化物和70克水中。将该混浊乳液用另外68克水稀释并用乙酸调节至pH 6以获得清澈的微乳液。
性质评测
测试根据实施例7和对比例1的方法制成的在实施例1至6中获得的化合物的乳液的下列性质:
a)通过制备400毫升浓度为20克/升的溶液、加热至40℃并用乙酸调节至pH 5,检测该聚二有机硅氧烷乳液在酸性介质中的剪切稳定性。然后,用高速搅拌器(24,000rpm,Janke & Kunkel供应的UltraTurrax)搅拌该液体1分钟。在浊度和沉积方面评测该液体在24小时后的外观。
b)通过制备400毫升浓度为20克/升的溶液、加热至40℃并用10%氨水溶液调节至pH 7.5,检测该聚二有机硅氧烷乳液在弱碱性介质中的剪切稳定性。然后,用高速搅拌器(24,000rpm,Janke & Kunkel供应的Ultra Turrax)搅拌该液体1分钟。在浊度和沉积方面评测该液体在24小时后的外观。
c)阴离子稳定性:将200毫升水与6克聚二有机硅氧烷乳液和20克染料溶液(0.48克/升Solar Discharge Orange 3LG和0.24克/升Indosol Rubinol SF-RGN,两者都是Clariant Produkte(Schweiz)GmbH的产品)混合,随后用60%乙酸调节至pH 5。该液体用桨叶搅拌器在2000rpm下搅拌10分钟并在24小时后评测。
d)手感性质的评测:为了评测手感性质,汇集有经验的团队,其用手感试验以0至10的相对标度评测用实施例1至6的化合物的乳液整理和根据对比例1处理的织物的匿名手感样品,值10代表最佳柔软感性质。作为对比样品,包括该测试系列的未处理织物。
也可以使用handle-O-meter(例如21 1-5Twing Albert)测试柔软度。在评估之前先对该整理过的样品进行调节(24小时,20℃,65%相对湿度)。
e)黄化趋势的评测。在用实施例1至6的化合物的乳液的所述整理和根据对比例1的处理后,将上文提到的荧光增白的棉织物(100克/平方米)在180℃下另外干燥1分钟。评测在120℃下干燥后和在180℃下处理后的黄化趋势。作为对比样品,包括该试验系列的未处理织物。
用颜色测量装置(Minolta Chromameter CR 331C)确立黄化程度并标作b+值。降低的黄化趋势意味着较小的b+值。
应用例
进行下列整理操作:
浸涂法:
在实验室喷射机中,将基底(经编织物,染色,经或不经定形,100%棉或聚酯(50%)/棉(50%))添加到水成液中,该水成液含有以该基底计0.5%至4.0%的根据实施例1至6的最终产物,在大约40℃下,且液比为6∶1至20∶1。在该基底在pH 5.0至6.0(40℃)下连续搅拌20分钟后,将基底从该液体中取出,离心分离并在140℃下无张力干燥70-90秒。
浸轧法:
将基底(经编织物,染色,经或不经定形,100%棉或聚酯(50%)/棉(50%)或聚酯(100%)或聚丙烯腈(100%)或尼龙6(100%))在室温下用含有15至60克/升根据实施例1至7的最终产物的水成液浸轧至100%干重量增加。随后,将该浸轧的材料在140℃下干燥70-90秒。
结论
应用例造成整理过的织物基底的非常柔软、舒适、丝滑和精致的手感。此外,所得织物具有高弹性和改进的抗皱性。该成品还表现出比用对比例1整理的织物更好的亲水性。此外,该成品没有表现出老化后的黄化。根据实施例7制成的乳液表现出良好的总体稳定性(pH稳定性和剪切力)和优异的与树脂的相容性。
Claims (6)
2.根据权利要求1的聚二有机硅氧烷,其中
R1是相同或不同的甲基和/或苯基,
m具有1至10的值;且
n具有40至600的值。
4.根据权利要求3的方法,其中
R1是相同或不同的甲基和/或苯基,
m具有1至10的值;且
n具有40至600的值。
5.根据权利要求1或2的氨基甲酸酯官能的聚二有机硅氧烷的用途,用于在水浴和施涂液中整理有机纤维和织物。
6.根据权利要求5的用途,其特征在于该聚二有机硅氧烷以水性制剂形式,优选以乳液形式使用。
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CN103946445A (zh) * | 2011-11-29 | 2014-07-23 | 道康宁公司 | 氨基官能化有机硅氧烷 |
CN104530433A (zh) * | 2014-12-18 | 2015-04-22 | 南雄鼎成化工有限公司 | 抗黄变亲水氨基硅油的制备方法 |
CN108779415A (zh) * | 2016-04-26 | 2018-11-09 | 瓦克化学股份公司 | 含有氨基甲酸酯官能化的有机聚硅氧烷和阳离子型表面活性剂的组合物 |
CN109152723A (zh) * | 2016-04-26 | 2019-01-04 | 瓦克化学股份公司 | 氨基甲酸酯官能化的有机聚硅氧烷的含水乳液 |
CN111201268A (zh) * | 2018-08-10 | 2020-05-26 | 瓦克化学股份公司 | 草酰胺基酯官能化的有机聚硅氧烷的水性乳液 |
CN114854024A (zh) * | 2022-05-26 | 2022-08-05 | 东华大学 | 一种改性氨基甲酸酯硅油乳液及其制备方法和制备聚丙烯腈碳纤维的方法 |
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EP1972330B1 (en) * | 2008-06-13 | 2012-09-12 | Clariant Finance (BVI) Limited | Cosmetic or pharmaceutical compositions comprising modified polysiloxanes with at least one carbamate group |
JP5795231B2 (ja) | 2011-10-11 | 2015-10-14 | 信越化学工業株式会社 | グリセロール基含有オルガノポリシロキサン、化粧料及びグリセロール基含有オルガノポリシロキサンの製造方法 |
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CN111201268B (zh) * | 2018-08-10 | 2022-04-19 | 瓦克化学股份公司 | 草酰胺基酯官能化的有机聚硅氧烷的水性乳液 |
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