CN101296968B - 二硫醇封端的聚硫醚聚合物及其制备和应用的方法 - Google Patents
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Abstract
本发明公开了一种二硫醇封端的聚硫醚聚合物，及其制备和应用的方法。
Description
技术领域
本发明涉及二硫醇封端的聚硫醚聚合物。本发明还涉及这些聚合物的制备和应用的方法。
背景技术
由于通过交联而具有的抗燃料的性质，已知巯基封端的含硫聚合物非常适用于航天密封剂。具有充足的硫含量以展示这种所需性能的商购聚合物材料为例如在U.S.专利No.2466963中描述的聚硫化物聚合物，以及例如在U.S.专利No.4366307中描述的含有烷基侧链的聚硫醚聚合物。用于本文中的材料在室温下同样具有液态的所需性能。
更加难以获得的航天密封剂的另一项期望性能组合是将长应用时间或“贮存期”(密封剂持续可使用的时间)和短固化时间(达到预定强度需要的时间)结合起来。航天密封剂同样需要耐高温性。在室温下为液态、具有低、具有优异的贮存期和/或优异性能特性的低Tg的组合物是航天应用中所需要的。
发明内容
本发明涉及一种式(I)的二硫醇封端的聚硫醚聚合物：
其中，每个R1是相同的，且由式(II)表示：
X为O或S；a为2-6；b为1-5；c为2-10；n为1或更大；且R2是除了二乙烯基醚残基之外的二烯烃残基，三烯烃残基或具有末端离去基团的有机化合物残基。
式(I)聚合物的制备和应用方法同样也在本发明的范围之内。
具体实施方式
本发明涉及一种式(I)的二硫醇封端的聚硫醚聚合物：
其中，每个R1是相同的，且由式(II)表示：
X为O或S；a为2-6；b为1-5；c为2-10；n为1或更大；且R2是除了二乙烯基醚残基之外的二烯烃残基、三烯烃残基或具有末端离去基团的有机化合物残基。“二烯烃残基”、“三烯烃残基”以及“具有末端离去基团的有机化合物残基”将分别理解为在二烯烃、三烯烃或具有离去基团的化合物反应时保留的部分。在某些实施方式中，X是O且a、b和c全都是2，n是1，且R2是乙烯基环己烯残基。
本发明的聚硫醚聚合物在常温常压下为液体、具有低Tg以及具有优异的抗燃料性。在此使用的术语“常温常压”是指约77℉(25℃)和一个大气压。“低Tg”指玻璃化转变温度在-50℃或以下。在本发明某个实施方案中，Tg为-55℃或更低，例如-60℃或更低或甚至-70℃或更低。低Tg表明在固化的配制物中优异的低温韧性，其可以通过已知的方法，例如航天材料规范(AMS)3267§4.5.4.7，航天材料规范(AMS)8802B§(AS 5127/17.6)以及军用规格(MI L-S)MIL-S-29574中描述的那些测定，以及通过与ASTM D 522-88中描述的那些类似的方法测定。典型地，良好的低温韧性意味着对基材附着力没有减少，无开裂，无龟裂等。本发明的聚硫醚聚合物在固化时也可显示非常所需的耐燃料特性。聚合物耐燃料性的一个量度是长时间置于燃料中之后它们的体积溶胀百分比，可通过使用与ASTM D 792或AMS 3269中所述那些相同或相似的方法来对其进行定量测定。在某些实施方式中，本发明的聚硫醚聚合物当固化时，在140℉(60℃)和常压下浸入1类喷射参比流体(JRF)中1周后体积溶胀百分比为25％或以下。在某些实施方式中，体积溶胀百分比为20％或以下。
本发明的聚硫醚聚合物可具有200-8000，比如，200-4000或200-520的数均分子量。
本发明的聚硫醚聚合物为多官能的，即它们具有两个或两个以上官能团。最少两个官能团为末端硫醇基团。也可通过R1和/或R2部分来进行官能化。例如，如果R2为三烯烃残基，聚硫醚的官能度可能大于2。这些聚合物可通过2摩尔的式(III)的化合物与1摩尔二烯烃，三烯烃或其他具有末端离去基团的有机化合物反应获得：
HS-R1-SH (III)
其中R1如前所述。可以使用任何适合的二烯烃、三烯烃或其他有机化合物，包括环脂族、脂族以及芳族二烯烃和三烯烃。二烯烃不是二乙烯醚。一种特别适合的二烯烃为乙烯基环己烯，例如4-乙烯基-1-环己烯，其理解为具有下述分子式(IV)：
理解当二烯烃为4-乙烯基-1-环己烯时，本发明的聚合物具有下述结构(V)：
其他适合的化合物包括三烯丙基氰尿酸酯和二或三卤化物例如二氯代烷烃和三氯代烯烃。
在某些实施方式中，式(III)为二巯基二氧杂辛烷(DMDO)。
在本发明某些实施方式中，比如当式(III)为DMDO而且二烯烃为乙烯基环己烯时，得到可用于降低组合物粘度的聚硫醚聚合物；采用此方式，本发明的化合物可作为反应性稀释剂。这提供了明显优于现有技术的优点；使用本发明聚合物的组合物在不使用溶剂下就具有低粘度。因此，根据本发明在使用溶剂的情况下溶剂的使用量可以达到最小。不使用和/或最小量使用溶剂对环境影响具有明显的好处，这是因为在溶剂蒸发时仅有少量或没有溶剂被“闪蒸”出，相比其他具有更高溶剂含量的组合物，本发明组合物的处理得到了改进。另外，在组合物中使用本发明的聚合物可以减缓组合物的固化，这可以提供更长的贮存期和/或将组合物涂覆在基材上的更长时间。因此，本发明进一步涉及包括上述聚硫醚聚合物的组合物。
除上述聚硫醚聚合物之外，本发明的组合物还包括一种或多种附加含硫化合物，固化剂和一种或多种另外添加剂。“含硫化合物”以及类似术语指其中至少一个组分中含有硫分子的任何化合物或化合物的混合物。例子可包括本领域中已知的那些，例如聚硫化物和/或聚硫醚，例如可从Akzo Noble公司商购的名为THIOPLAST和从Toray公司商购的名为THIOKOL LP的那些聚硫化物，以及如美国专利NOs.6,172,179；5,912,319和4,609,762中所述的那些聚硫醚。在某些实施方案中，含硫化合物包括聚合物共混物，其含有聚硫化物组分和聚硫醚组分，比如在美国申请系列No.10/935,857中所述，该文献在此引入作为参考。认识到本发明的聚合物自身是含硫化合物，且在本发明中组合物中使用而不再使用任何其他含硫化合物。术语“固化剂”指可入加入到本发明组合物中以加速含硫化合物固化或胶凝时间的物质。“固化”和类似术语指组合物达到通过ASTM D2240测定的30硬度计“A”固化硬度的点。可以使用任何合适的固化剂。在某些实施方案中，固化剂包括氧化物，其可以使末端硫醇基团氧化以形成二硫键。合适的固化剂包括，例如，二氧化铅，二氧化锰，二氧化钙，过硼酸钠一水合物，过氧化钙，过氧化锌，重铬酸盐和环氧类。
本发明的组合物中也可使用各种添加剂例如填料，粘合促进剂和增塑剂。本发明组合物中使用的填料，特别是用于航天用途时，包括那些现有技术中常用的填料，例如炭黑，碳酸钙(CaCO3)，二氧化硅，尼龙，微球体等。在一个实施方案中，组合物包括基于组合物总重量的10-70wt％选定填料或填料组合，如10-50wt％。
可以使用一种或多种粘合促进剂。合适的粘合促进剂包括酚醛类例如从Occidental Chemicals公司获得的METHYLON酚醛树脂，和/或有机硅烷，例如环氧，硫基或氨基官能的硅烷例如从OSiSpecialties获得的A-187和A-1100。在一个实施方案中，粘合促进剂的使用量基于配方总重量为0.1-15wt％。
组合物中可使用增塑剂，其通常重量范围为基于配方总重量为1-8wt％。可用的增塑剂包括邻苯二甲酸酯，氯化石蜡和氢化三联苯。
组合物还可含有一种或多种有机溶剂，例如乙酸乙酯，其通常用量基于配方总重量为0-15wt％，例如低于15wt％或低于10wt％。
本发明的组合物也可任选地含有其他标准添加剂，例如颜料，触变胶，抑制剂，催化剂和屏蔽剂。
可用的颜料包括本领域中的常规颜料，例如炭黑和金属氧化物。颜料的存在量基于组合物的总重量为0.1-10wt％。
触变胶，例如煅烧的二氧化硅或炭黑的使用量基于组合物的总重量为0.1-5wt％。
本发明的某些组合物包括，基于组合物的总重量计，1-30wt％，例如5-20wt％本发明硫醇封端的聚硫醚聚合物；20-70wt％，例如35-50wt％的不同于本发明聚合物的含硫化合物；1-50wt％，例如5-25wt％或10wt％的固化剂；以及10-50wt％，例如5-30wt％或25wt％的其他添加剂。对于本发明聚合物仅为含硫化合物的组合物，这些重量百分比要相应地调整。
本发明的组合物通常包装成双组分或“2K”体系。一种组分包括本发明的聚硫醚聚合物，和任选的其他含硫化合物，并且还可含有一种或多种各类添加剂，例如填料，补充剂，粘合促进剂，促进剂和/或抑制剂；第二种组分通常包含固化剂，并且也可含有一种或多种各类添加剂，例如增塑剂，填料，促进剂，和/或抑制剂。将两种组分在使用前立即混合。例如，两种组分可以在特别订制的盒/棒系统，例如从PRC-DeSoto International，Inc.公司商购的SEMKIT混合。或者，组分也可混合在一起，并将混合物保持在低于固化剂反应性的温度。“反应性”指能够发生化学反应，并且包括反应物从部分到完全的任何程度的反应。低于-40℃的储藏温度通常适于抑制或阻止固化剂和聚硫醚聚合物组分之间的反应。
本发明中组合物的特别合适的用途是在所有级别的密封剂中。本发明的密封剂指含任何上述硫醇封端的聚硫醚聚合物的密封剂。“密封剂”及类似术语指具能抵抗例如湿气和/或温度的大气条件，和/或至少部分阻碍例如水，燃料和/或其他液体和气体的物质传输的组合物。而且，密封剂通常具有粘结性。通常根据粘度对密封剂进行分级。A级密封剂通常具有100-400泊的粘度。由于这些密封剂通常为刷涂涂覆，因此该级密封剂被认为是“刷涂层”。B级密封剂通常具有6000-18000泊的粘度，且通常用挤出枪或刮刀涂覆。这类密封剂可以在圆角密封上使用，且通常用作燃料箱密封剂。C级密封剂粘度通常在A级和B级之间，例如为1000-4000泊。C级密封剂可通过多种方式涂覆，例如刷，辊，或挤出枪，和也可用于“接合密封(fayseal)”。相应地，本发明进一步涉及一种含有上述任意组合物的密封剂。
本发明中的组合物可涂覆于多种基材上，例如，钛、不锈钢、铝，和其涂底漆的、有机涂覆的和铬酸盐形式，环氧类，聚氨酯，石墨，玻璃纤维复合材料，KEVLAR，丙烯酸类和聚碳酸酯。如上所述，本发明的组合物特别适用于航天用途，比如航天密封剂和燃料箱、机身和其他类似物的衬里。本发明的航天密封剂材料可展示出包括耐高温性、耐燃料性和/或弯曲强度的特性。此处叙述的配制物也可非常适于其中温度极端化，化学苛刻的环境和/或经历机械振动的用途。本配制物也可在航天领域之外使用。
本发明中的聚合物通常是未胶凝化的，也就是说聚合物共混物具有可以测量的特性粘度。本发明的固化配制物通常具有航天应用所需的良好低温韧性，这是由于该配制物可以经受多变的环境条件，例如温度和压力，以及物理条件，比如接合收缩和膨胀和/或振动。
这里所述的粘度是根据ASTM D-2849段落79-90使用布氏粘度计在约25℃温度和约760毫米汞柱的压力条件下测定的。
本发明进一步涉及对孔洞进行密封的方法，该方法包括用此处所述的任意密封剂涂覆到与孔洞相关的表面。如果需要可以在密封剂之前先在表面上涂覆粘合促进剂。“孔洞”指空洞、缝隙、裂缝或其他开口。在某些实施方案中，孔位于航空器或航天飞行器上。
除非有特别说明，作为在此使用的所有数字例如表达值、范围、数量或者百分数的那些都可理解为以“约”为前缀，即使这个词没有出现。列举的所有数值范围都计划包含其中所有子范围。复数包括了单数，并且反之亦然。例如，当此处引用了“一种”聚硫醚聚合物时，可以使用一种或多种聚硫醚聚合物，其中至少一种在本发明中。类似地，在本发明的组合物中可以使用一种或多种含硫化合物，一种或多种固化剂和/或一种或多种任意种类添加剂。另外，作为在此使用的术语“聚合物”的意思是指预聚物、低聚物以及均聚物和共聚物；前缀词“聚”指两个或以上。
实施例
下述实施例用于解释发明，而不应该解释为对发明的任何形式的限制。
实施例1
将1，8-二巯基-3，6-二氧杂辛烷(616.95克，3.38摩尔，CAS#14970-87-7)加入到装有机械搅拌器、温度计和两个通气装置(一个用来通入氮气，另外一个用来出气)的1升四颈圆底烧瓶中。烧瓶中充满氮气，将内容物加热至32℃。
将4-乙烯基环己烯(183.05克，1.69摩尔，CAS#100-40-3)在3小时，15分钟内加入至搅拌二硫醇中。加入过程中会发生温和放热，但温度保持在42-45℃。反应混合物在55℃加热3小时。在55-60℃下每间隔2小时分别加入五份(每份140克)自由基引发剂(VAZO-52(2，2′偶氮双)2，4-二甲基戊腈CAS#4419-11-8，从DuPont公司商购)中的一份。反应混合物在70-75℃/7-8毫米汞柱下抽空2小时以获得澄清无色的产品。产量：800克(100％)；硫醇当量：238(理论值：236)；粘度：1.331泊。
实施例2
在真空度为27英寸汞柱或更高的条件下，通过将表1中所列的组分在双轴cowles型间歇混合机混合直至均匀，制得B级密封剂。组分A和B以重量比100∶12混合以制得最终的密封剂。
表1
组分A
1根据美国专利No.4,623,711制得(分子量大约为2200)。
2根据美国专利No.4,623,711制得(分子量大约为2500)。
3THIOKOL LP-55聚硫化物聚合物，由Toray Fine Chemicals商购。
4根据美国专利No.6,172,179制得(分子量大约为3000)。
5ORGASOL，由Atofina商购。
6EXPANCEL，由Akzo商购。
7由OSi商购。
8由OSi商购。
表1(续)
组分B
| 组分 | 重量百分比 |
| MnO2 | 55 |
| 增塑剂9 | 38 |
| 硬脂酸 | 0.6 |
| 硬脂酸钠 | 0.7 |
| 分子筛粉末10 | 0.7 |
| 双亚戊基/秋兰姆/聚硫化物混合物11 | 5.0 |
9部分氢化三联苯(HB-40)，由Solutia商购。
103埃的碱金属硅酸铝粉末，由UOP商购。
11Akrochem促进剂DPTT粉末，由Akrochem商购。
如表2所示，样品2的密封剂根据BMS 5-142目标规范的要求进行测试后性能良好。
表2
| 测试性能 | 要求 | 样品2 |
| 粘度(泊) | 6000-13000 | 8400 |
| 比重(最大) | 1-10 | 1.04 |
| 不挥发的含量，％最小 | 90-0 | 96 |
| 流程(英寸) | 0.10-0.50 | 0-10 |
| 1小时后涂覆时间，g/min(最小) | 15 | 48 |
| 不粘时间，小时(最大) | 12 | ＜2 |
| 24小时后固化率(最小) | 30 | 346小时 |
| 失重率％(最大) | 16.0 | 7.26 |
| 韧性 | 无裂痕，龟裂或脱层 | 通过 |
| 干拉伸强度psi(最小) | 150 | 210 |
| III类*浸没拉伸强度psi(最小) | 150 | 225 |
| 干伸长率％(最小) | 150 | 220 |
| III类浸没伸长率％(最大) | 150 | 220 |
| 水气及燃料稳定性％(最大)蒸馏水，5天120℉III类*，5天120℉ | 20.05.0 | 19.32.34 |
*喷射参比流体TT-S-735A III类
样品2还具有良好的剥离强度，并且在采用同样的规范测试时显示了耐烃流体性。
为了以说明为目的，上面描述了本发明中特别的实施方式，对于那些本领域技术人员来说，明显可以对本发明进行众多细节改变，而不背离所附权利要求中定义的发明。
Claims (8)
1.一种组合物，含有式(I)的二硫醇封端的聚硫醚聚合物：
其中，每个R1是相同的，且由式(II)表示：
X为O或S；a为2-6；b为1-5；c为2-10；n为1或更大；且R2是除了二乙烯基醚残基之外的二烯烃残基、三烯烃残基或具有末端离去基团的有机化合物残基，其特征在于该组合物进一步含有包括聚硫化物和聚硫醚的聚合物共混物。
2.权利要求1的组合物，其中X为O；a为2；b为2；c为2；n为1，且R2是乙烯基环己烯残基。
3.一种含有权利要求1或2的组合物和固化剂的密封剂。
4.权利要求3的密封剂，其中固化剂为MnO2。
5.权利要求3的密封剂，其中粘度为1-2000Pas(10-20000泊)。
6.一种制备权利要求1或2的组合物的方法，包括将2摩尔式(II)的化合物
和1摩尔的二烯烃、三烯烃或具有末端离去基团的有机化合物混合，以及加入包括聚硫化物和聚硫醚的聚合物共混物。
7.一种密封孔洞的方法，包括将权利要求3的密封剂涂覆到与所述孔洞相关的表面。
8.权利要求7的方法，其中该表面是航空器或航天飞行器的表面。
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| CN102432880B (zh) * | 2011-09-09 | 2013-06-19 | 北京航空航天大学 | 一种水溶性聚硫醚及合成方法 |
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| Publication number | Publication date |
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| JP2009513790A (ja) | 2009-04-02 |
| EP1940918B1 (en) | 2011-02-09 |
| RU2391357C2 (ru) | 2010-06-10 |
| RU2008121225A (ru) | 2009-12-10 |
| HK1173169A1 (zh) | 2013-05-10 |
| US20100036063A1 (en) | 2010-02-11 |
| KR100996757B1 (ko) | 2010-11-25 |
| WO2007050725A1 (en) | 2007-05-03 |
| CN101296968A (zh) | 2008-10-29 |
| ATE497984T1 (de) | 2011-02-15 |
| AU2006306139A1 (en) | 2007-05-03 |
| US20070096396A1 (en) | 2007-05-03 |
| CA2627040C (en) | 2011-04-05 |
| CA2627040A1 (en) | 2007-05-03 |
| BRPI0619332B1 (pt) | 2017-12-19 |
| CN102585501B (zh) | 2014-07-30 |
| US8076420B2 (en) | 2011-12-13 |
| ES2358278T3 (es) | 2011-05-09 |
| AU2006306139B2 (en) | 2010-07-01 |
| DK1940918T3 (da) | 2011-05-16 |
| CN102585501A (zh) | 2012-07-18 |
| EP1940918A1 (en) | 2008-07-09 |
| BRPI0619332A2 (pt) | 2011-09-27 |
| JP4937267B2 (ja) | 2012-05-23 |
| KR20080046748A (ko) | 2008-05-27 |
| BRPI0619332B8 (pt) | 2018-02-27 |
| HK1122583A1 (en) | 2009-05-22 |
| US20110060091A1 (en) | 2011-03-10 |
| US7858704B2 (en) | 2010-12-28 |
| DE602006020056D1 (de) | 2011-03-24 |
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