CN100408585C - 制造硅烷醇封端的低聚材料的方法 - Google Patents
制造硅烷醇封端的低聚材料的方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title description 7
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 7
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
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- 239000002253 acid Substances 0.000 claims description 19
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 5
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
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- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
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- Silicon Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
一种生产线型硅烷醇封端硅氧烷类化合物的方法,包含:a)具有下列通式的六有机环三硅氧烷在包含水与挥发性极性非质子传递有机溶剂的混合物的溶剂中在催化数量强碱存在下进行开环聚合:D3=(R1R2SiO)3其中R1和R2独立地选自1~40个碳原子的一价基团;b)用多元酸的部分中和盐中和该催化数量的强碱,其中pH范围介于约6~约8;以及c)用水洗。
Description
与相关申请的交叉引用
本申请要求美国申请序列号60/263,911的优先权,后者于2001年1月24日提交,其在此全文收入本文作为参考。
技术领域
本发明涉及一种通过六有机环三硅氧烷类化合物与水在催化数量的强碱的存在下起反应生产低分子量硅烷醇封端的材料的方法。反应优选在水/丙酮体系中进行。
相关的现有技术简述
目前,硅烷醇封端的低聚硅氧烷材料采用两种方法制造。第一种方法涉及二氯二甲基硅烷在水/极性溶剂混合物中在中和剂如碳酸氢钠或氨存在下的受控水解。该方法产生相当数量废物和约30%环状低聚物,不得不通过真空汽提从最终产物中除去。
第二种方法涉及六甲基环三硅氧烷在水/有机溶剂混合物中在酸-活化的粘土(例如FILTROL-20)存在下,正如美国专利3,853,932中公开的,或者在酸性或碱性离子交换树脂存在下,例如在美国专利3,309,390中描述的存在下进行开环聚合。该方法要求过滤出催化剂和高真空蒸馏以除掉开环聚合期间生成的环状低聚物。
发明概述
广义地说,本发明提供一种生产线型硅烷醇封端硅氧烷类化合物的方法,该方法包含:
具有下列通式的六有机环三硅氧烷在包含水与挥发性极性非质子传递有机溶剂的混合物的溶剂中,在催化数量的强碱的存在下进行开环聚合:
D3=(R1R2SiO)3
其中R1和R2独立地选自1~40个碳原子的一价基团;
用多元酸的部分中和盐中和该催化数量的强碱,其中pH范围介于约6~约8;并且任选地
用水洗涤以除去盐,或者可替代地,从批料中汽提出水和丙酮并过滤出中性盐。
发明详述
本发明通过参照下面本发明的优选实施方案和其中包括的实施例的详细描述将会更容易理解。
在公开和描述本发明物质组合物和方法之前,要知道,本发明不限于特定的合成方法或特定的配方,因为,这些显然还可变化。还应道了解,这里使用的术语仅用于描述特定实施方案的目的,因此不拟具有限制性。
在下面的说明中,将提到许多术语,它们应定义为具有下面的含义:
单数形式“a”、“an”和“the”包括多数所指对象,除非上下文明确要求其他含义。
“任选的”或“任选地”是指后面所描述的事件或环境可能发生或可能不发生,而且描述的内容包括发生该事件的情况和不发生该事件的情况。
现已发现,六甲基环三硅氧烷D3在水/挥发性极性非质子传递有机溶剂混合物中在催化数量强碱如LiOH、NaOH、KOH或其混合物存在下的开环聚合以高速进行并以高收率,通常高于约90%,生成线型低聚硅烷醇封端的硅氧烷类化合物。用来与水形成该方法溶剂的挥发性极性有机溶剂必须与水混溶。此种挥发性极性非质子传递有机溶剂的非限制性例子是低分子量酮,例如丙酮。环状低聚副产物如八甲基环四硅氧烷D4的数量非常低。本文所使用的术语D3,亦称六有机环三硅氧烷,被定义如下:
D3=(R1R2SiO)3
其中R1和R2独立地选自1~40个碳原子的一价基团,其中此种基团可以或不可以被其他取代基如卤素原子取代。除了短语“1~40个碳原子的一价基团”所涵盖的烷基、芳烷基和芳基基团之外,该定义具体地包括但不限于,氟取代的基团如3,3,3-三氟丙基以及全卤代烷基基团和全卤代-芳基基团。
强碱用弱酸如二氧化碳或酸性盐中和并随后以水洗涤之后,系统是稳定的。通过简单蒸馏除掉挥发性极性非质子传递有机溶剂例如丙酮后,以高收率获得所要求的硅烷醇封端的有机硅氧烷类化合物。曾出乎意料地发现,该方法不要求过滤(因为水洗后不再有固体存在),和高真空蒸馏(因为仅生成少量非官能环状硅氧烷类化合物如八甲基环四硅氧烷)。
至于中和,催化剂必须加以中和以防止溶剂除去期间硅烷醇类的缩合。优选在碱性催化剂中和之后pH值近似7,优选在中和后pH范围介于约6.7~约7.3,更优选约6.5~约7.5,最优选约6.0~约8.0。这可通过测定反应的碱含量并精确地测定任何酸,包括盐酸、硫酸、乙酸等来实现。然而,此种做法要求严格控制酸的浓度,因为倘若此种酸与精确化学计量略有过量或不足,势必导致pH过高或过低并从而导致汽提期间硅烷醇的损失。有用的减活化剂包括二氧化碳和多元酸的酸性盐。在某些条件下,即使二氧化碳也可能生成pH过高的钝化盐。这里所使用的多元酸是每分子包含一个以上可中和的酸官能团的酸,当被部分地中和后,能起到控制pH的缓冲剂的作用。因此,最优选的是这样的盐,其水溶液近似pH7并且将与碱性催化剂起反应生成同样也处于pH6~pH8范围的钝化盐。优选的是二或三元酸(多元酸的一个子类)的一价盐。此种盐将包括此种多元酸的部分中和的碱金属盐,例如硫酸氢钠或钾、草酸一钠或钾以及其它二元有机酸的,例如磷酸二氢一钠或钾。最优选的是磷酸二氢一钠或钾。这里所使用的术语碱金属包括锂、钠、钾、铷和铯。通过改变此种盐对催化剂的摩尔比,钝化的催化剂的pH值很容易维持在近似pH7。即便磷酸二氢钠的用量过量或不足,pH也将维持在近似pH7。最优选的比例是2摩尔磷酸二氢钠每摩尔碱性催化剂。
本发明方法以超过90%收率,优选超过93%收率,更优选超过95%收率,最优选超过97%的收率生产线型硅氧烷类化合物。
本发明方法能够以高于已知方法的收率生产线型硅烷醇封端低聚物。本发明方法提供较快反应速率,而且由于采用均相催化剂体系故消除了现有技术所要求的过滤步骤。本发明方法产生的环状副产物比现有技术少,因此免除对高真空蒸馏的需要。
实施例
下面的实施例旨在给本领域技术人员提供有关本文要求保护的物质组合物和方法如何制造和评估的全面说明,而不拟对本发明人就其发明范围划定限制。尽管就数字(例如,数量和温度等)而言已力求准确,但某些错误和偏差在所难免。除非另行指出,份数指重量而言;温度以℃为单位。
实例1
在1000mL备有冷凝器、机械搅拌器和加料漏斗的反应器中加入丙酮(987g)、水(50g)和D3(444g,2mol)。反应混合物加热到70℃。当温度达到稳定时,加入0.042g(0.0018mol)氢氧化锂以开始反应。D3的转化情况用气相色谱术跟踪。反应在D3转化率超过95%时的一点终止。氢氧化锂通过在烧瓶中加入固体二氧化碳(2g)而被中和。反应冷却至50℃,并以100g水洗涤。从烧瓶中去掉水层。随后,慢慢加上真空以赶出丙酮和残留D3。生成的硅烷醇封端低聚硅氧烷(收率超过93%)采用气相色谱术进行分析。
实例2
在采用500mL备有冷凝器和机械搅拌器的烧瓶的实验中,加入D3(150g)、丙酮(36g)和水(20g)。反应混合物加热到61.5~62℃。温度稳定以后,加入175ppm氢氧化钾,以总重量为基准。定期取样,以便利用气相色谱术跟踪反应。加入二氧化碳将样品中和。反应继续进行6h,此时加入磷酸二氢钠一水合物(0.2g)以便中和并缓冲反应混合物。反应用水洗3遍。通过在杯子中放一薄层样品,待残留丙酮蒸发,然后实施FTIR分析来确定硅烷醇含量。反应4h后的D3+D4含量经测定为5.67%;硅烷醇含量为7.14%。反应6h后D3+D4含量经测定为5.66%;硅烷醇含量为约6.95%。
现有技术实例
在500mL备有搅拌器和冷凝器的反应容器中加入84g甲基三聚体、43g丙酮和13g水。加入2.5g Filtrol 20作为催化剂。在回流下加热16h。G.C.分析表明三聚体含量小于5%。加入0.2g氧化镁以中和Filtrol 20。再搅拌2h。停止搅拌,待批料分层30min。分离并丢掉底下的水层。冷却至室温。加入1g Celite 545,搅拌10min。过滤去掉所有固体。将滤液倒回到500mL备有搅拌器和抽真空能力的烧瓶中。慢慢将真空加到100mm汞柱。然后将批料加热到120℃。真空汽提直至D3含量和D4含量之和按GC分析小于5%。离析出80g产物,折合93%的收率。
上面已特别就本发明优选实施方案详细描述了本发明,但是要知道,在本发明精神和范围内还可进行各种各样变化和修改方案。
Claims (19)
1. 一种生产线型硅烷醇封端硅氧烷类化合物的方法,包含:
a)具有下列通式的六有机环三硅氧烷在包含水与挥发性极性非质子传递有机溶剂的混合物的溶剂中在催化数量的强碱存在下进行开环聚合:
D3=(R1R2SiO)3
其中R1和R2独立地选自1~40个碳原子的一价基团;以及
b)用多元酸的部分中和盐中和该催化数量的强碱,其中pH范围介于6~8;
其中挥发性极性非质子传递溶剂是酮。
2. 权利要求1的方法,还包括除去挥发性极性非质子传递有机溶剂的步骤。
3. 权利要求1的方法,其中酮是丙酮。
4. 权利要求3的方法,其中多元酸的部分中和盐是碱金属盐。
5. 权利要求4的方法,其中多元酸的部分中和盐是钾盐。
6. 权利要求4的方法,其中多元酸的部分中和盐是钠盐。
7. 权利要求5的方法,其中R1是甲基。
8. 权利要求6的方法,其中R1是甲基。
9. 权利要求4的方法,其中R1是3,3,3-三氟丙基。
10. 一种生产线型硅烷醇封端硅氧烷类化合物的方法,由下列步骤构成:
a)具有下列通式的六有机环三硅氧烷在包含水与挥发性极性非质子传递有机溶剂的混合物的溶剂中在催化数量强碱存在下进行开环聚合:
D3=(R1R2SiO)3
其中R1和R2独立地选自1~40个碳原子的一价基团;和
用多元酸的部分中和盐中和该催化数量的强碱,其中pH范围介于6~8。
11. 权利要求10的方法,还包括除去挥发性极性非质子传递有机溶剂的步骤。
12. 权利要求11的方法,其中挥发性极性非质子传递溶剂是酮。
13. 权利要求12的方法,其中酮是丙酮。
14. 权利要求13的方法,其中多元酸的部分中和盐是碱金属盐。
15. 权利要求14的方法,其中多元酸的部分中和盐是钾盐。
16. 权利要求14的方法,其中多元酸的部分中和盐是钠盐。
17. 权利要求15的方法,其中R1是甲基。
18. 权利要求16的方法,其中R1是甲基。
19. 权利要求14的方法,其中R1是3,3,3-三氟丙基。
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US26391101P | 2001-01-24 | 2001-01-24 | |
US60/263,911 | 2001-01-24 | ||
US10/055,199 | 2002-01-23 | ||
US10/055,199 US6433204B1 (en) | 2001-01-24 | 2002-01-23 | Process for making silanol stopped oligomeric materials |
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JP2012140391A (ja) * | 2011-01-06 | 2012-07-26 | Shin-Etsu Chemical Co Ltd | 両末端にシラノール基を有する低分子量直鎖状オルガノポリシロキサンの製造方法 |
CN104004009B (zh) * | 2014-03-18 | 2016-06-29 | 杭州洛科曼有机硅有限公司 | 一种聚二甲基硅二醇的合成方法 |
CN112625241A (zh) * | 2020-10-12 | 2021-04-09 | 湖北兴瑞硅材料有限公司 | 一种低粘度羟基硅油的合成方法 |
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- 2002-01-23 KR KR10-2003-7009716A patent/KR20030094237A/ko active IP Right Grant
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US4267298A (en) * | 1979-11-09 | 1981-05-12 | General Electric Company | Process for preparing M-stopped silicone fluids from silanol fluids |
US4287353A (en) * | 1979-11-09 | 1981-09-01 | General Electric Company | Process for synthesizing silanol chain-stopped fluorosiloxane fluids |
US4281146A (en) * | 1979-12-26 | 1981-07-28 | General Electric Company | Method of neutralizing a halogen silicone compound |
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WO2002092607A1 (en) | 2002-11-21 |
US20020099233A1 (en) | 2002-07-25 |
WO2002092607A8 (en) | 2004-07-15 |
JP4147115B2 (ja) | 2008-09-10 |
ES2296980T3 (es) | 2008-05-01 |
CN1487945A (zh) | 2004-04-07 |
KR20030094237A (ko) | 2003-12-11 |
EP1358191A1 (en) | 2003-11-05 |
JP2004536170A (ja) | 2004-12-02 |
DE60224362T2 (de) | 2008-12-18 |
DE60224362D1 (de) | 2008-02-14 |
EP1358191B1 (en) | 2008-01-02 |
ATE382625T1 (de) | 2008-01-15 |
US6433204B1 (en) | 2002-08-13 |
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