CN106084173A - 粘土-聚氨酯复合材及其制备方法 - Google Patents
粘土-聚氨酯复合材及其制备方法 Download PDFInfo
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明涉及粘土‑聚氨酯复合材及其制备方法。一种粘土‑聚氨酯复合材，由包括具有氨基的粘土、多元醇系化合物与多元异氰酸酯系化合物的第一混合物经聚合反应所制得；该具有氨基的粘土由包括粘土及式(I)所示的季铵盐的第二混合物所形成；式(I)中，R1至R4为如说明书与权利要求项中所定义者。在该粘土‑聚氨酯复合材中，该粘土可均匀分散于聚氨酯中，且该粘土‑聚氨酯复合材的粘土含量高，后续应用时可提供较佳的阻隔效果及尺寸稳定性。
Description
技术领域
本发明涉及一种粘土-聚氨酯复合材，特别是涉及一种由包括具有氨基的粘土、多元醇系化合物与多元异氰酸酯系化合物的第一混合物经聚合反应所制得的粘土-聚氨酯复合材。
背景技术
由于高分子材料具有相当优越的机械性质，所以被广泛的应用在建筑材料、机械零件或电路板等，但是，高分子材料遇火受热容易燃烧，继而引发火灾，因此，业界皆希望改善高分子材料容易燃烧的缺点，同时也极欲寻求可与高分子材料并用的难燃剂。由于无机粘土具有优良的机械性质、耐热性、耐化学腐蚀性与低膨胀系数等的优点，因此，无机粘土与高分子材料组成的复合材料被广为研究。然而，因无机粘土属于亲水性物质，与亲油性高分子材料的相容性差，使得复合材料整体的特性无法有效提升。
中国台湾专利公开号201300342揭示一种具有较佳的机械性质及高阻气性的有机-无机复合材料。该有机-无机复合材料由聚合单体组成与改质型反应单体进行缩聚反应而得；该改质型反应单体具有由无机粘土与式(a)所示的季铵盐类化合物进行阳离子交换后而得的结构；
Ra及Rb分别包括至少一羟基(-OH)或异氰酸基(-NCO)的官能团，Rc为C12至C18的烷基，且Rd为C1至C3的烷基。在该中国台湾专利公开案的说明书第7页第5行揭示该改质型反应单体为具有无机粘土-铵盐结构的聚酯高分子，而该具有无机粘土-铵盐结构的聚酯高分子是由无机粘土-铵盐结构与聚酯高分子进行酯交换反应而制得。在该说明书第8页第13行揭示聚合单体组成例如制作聚乙烯对苯二甲酸酯(polyethylene terephthalate)用的苯二甲酸及乙二醇等单体、制作聚氨基甲酸酯(polyurethanes)用的多元醇及二异氰酸酯等单体，或制作环氧树酯用的环氧化合物等单体。
虽然在该有机-无机复合材料中无机粘土可均匀地分散于有机高分子中，但，制备该有机-无机复合材料所耗费的时间至少24小时以上，且制备该改质型反应单体时，该无机粘土-铵盐结构的用量若大于10wt％，则会使得制备过程中的粘度过高，不利于操作，因此，为避免粘度过高，该无机粘土-铵盐结构的用量将会受限，使得后续所获得的有机-无机复合材料中无机粘土-铵盐结构的含量无法大于5wt％，因而导致有机-无机复合材料中有机成分过多，而无法呈现无机成分的特性，继而影响后续应用时所需提供的效果(如尺寸稳定性或耐燃效果)。再者，为避免影响后续应用时所需提供的效果，势必需将有机-无机复合材料用量提高，则会导致成本过高。
鉴于上述，改良有机-无机复合材料以缩短制备时间且有效提高无机粘土-铵盐结构的含量，继而提升后续应用的效果，是此技术领域相关技术人员可再突破的课题。
发明内容
本发明的第一目的在于提供一种具有高含量粘土且该粘土可均匀分散于聚氨酯中的粘土-聚氨酯复合材。
本发明粘土-聚氨酯复合材，由包括具有氨基的粘土、多元醇系化合物与多元异氰酸酯系化合物的第一混合物经聚合反应所制得；该具有氨基的粘土由包括粘土与式(I)所示的季铵盐的第二混合物所形成；
式(I)中，R1至R4各自表示具有氨基的基团或C2至C18的烷基，条件是R1至R4中至少两者为具有氨基的基团；X表示维持式(I)所示的季铵盐电中性的反离子。
本发明的第二目的，即为提供一种反应时间短的制备粘土-聚氨酯复合材的方法。
本发明制备粘土-聚氨酯复合材的方法，包含以下步骤：
提供具有氨基的粘土；该具有氨基的粘土由包括粘土与式(I)所示的季铵盐的第二混合物所形成；
式(I)中，R1至R4各自表示具有氨基的基团或C2至C18的烷基，条件是R1至R4中至少两者为具有氨基的基团，X表示维持式(I)所示的季铵盐电中性的反离子；
提供多元醇系化合物与多元异氰酸酯系化合物，并与该具有氨基的粘土混合，形成第一混合物，并进行聚合反应。
较佳地，以该粘土-聚氨酯复合材的总量为100wt％计，该粘土的含量范围为10wt％以上。更佳地，以该粘土-聚氨酯复合材的总量为100wt％计，该粘土的含量范围为10wt％至60wt％。
较佳地，该多元醇系化合物选自于乙二醇、丙二醇、丁二醇、1,3-丁二醇、新戊二醇、聚醚多元醇、聚酯多元醇，或它们组合。该聚醚多元醇例如但不限于聚丙二醇、聚四氢呋喃二醇、聚四甲基醚二醇，或聚丙二醇-聚四氢呋喃二醇共聚物等。该聚酯多元醇例如但不限于聚碳酸酯多元醇。较佳地，以该具有氨基的粘土的总量为100重量份计，该多元醇系化合物的使用量范围为100重量份至1,000重量份。
较佳地，该多元异氰酸酯系化合物选自于甲苯二异氰酸酯(toluenediisocyanate)、二苯基亚甲基二异氰酸酯(methylenediphenyl diisocyanate)、六亚甲基二异氰酸酯(hexamethylene diisocyanate)、4,4-二环己基亚甲基二异氰酸酯[4,4-methylene bis(isocyanatocyclohexane)]、异佛尔酮二异氰酸酯(isophorone diisocyanate)，或它们组合。较佳地，以该具有氨基的粘土的总量为100重量份计，该多元异氰酸酯系化合物的使用量范围为10重量份至1,000重量份。
该聚合反应的操作温度范围为55℃至100℃。该聚合反应的操作时间范围为1小时至12小时。
该第一混合物还包括溶剂。该溶剂可单独或混合使用，且该溶剂例如但不限于N,N-二甲基乙酰胺(N,N-dimethylacetamide)、乙酸乙酯(ethyl acetate)、乙酸丁酯(butyl acetate)、甲基异丙酮(methyl isopropyl ketone)、丙酮(acetone)、异丙醇、异丁醇、甲苯、二甲基甲酰胺(dimethylformamide)、二丙酮醇(diacetonealcohol)、二甲基亚砜(dimethyl sulfoxide)，或丁酮。
该粘土与式(I)所示的季铵盐可通过离子交换(ion exchange)反应或高温活化(activation)处理形成具有氨基的粘土。举例来说，该粘土为钠型蒙脱土时，该钠存在于蒙脱土层间，该式(I)所示的季铵盐通过离子交换反应，置换蒙脱土层间的钠，而插层到钠型蒙脱土的层间，以使钠型蒙脱土被改质并扩大层间距。又如，该粘土为高岭土时，将其置于高温下，使其层间距扩大，同时，引入该式(I)所示的季铵盐，而插层到高岭土的层间，以使高岭土被改质并再次扩大层间距。
较佳地，该粘土的平均层间距范围为以上。较佳地，该粘土选自于蒙脱土、云母、高岭土、矾石、蛭石(vermiculite)，或它们组合。该蒙脱土例如但不限于钠型蒙脱土或钙型蒙脱土等。该云母例如但不限于绢云母(sericite)等。该矾石例如但不限于硅矾石等。
较佳地，该具有氨基的基团选自于氨基、-C2H4NH2或较佳地，该式(I)所示的季铵盐选自于二烷基二(氨基亚乙基)季铵盐，且该烷基为C2至C18。较佳地，以该粘土的总量为100重量份计，该式(I)所示的季铵盐的使用量范围为1重量份至99重量份。
本发明的有益效果在于：在粘土-聚氨酯复合材中，粘土可均匀分散于聚氨酯中，且该粘土-聚氨酯复合材具有高含量的粘土，后续应用时可提供较佳的阻隔效果及尺寸稳定性。
具体实施方式
本发明将就以下实施例来作进一步说明，但应了解的是，所述实施例仅为示例说明用，而不应被解释为本发明实施的限制。
<<实施例1>>粘土-聚氨酯复合材
将100克的钠型蒙脱土(厂牌：Nanocor,Inc.；型号：PGW)与27克的十八烷基乙基二(氨基亚乙基)季铵盐(厂牌：中日合成化学)。于70℃下进行8小时的离子交换反应，即可获得127克的具有氨基的粘土。
将150克分子量为2,000的聚酯多元醇(厂牌：三芳化学工业股份有限公司；型号：PBA2000)、14.6克的乙二醇、5.3克的丙二醇、0.09克的四丁基锡催化剂、30克的上述具有氨基的粘土、92.3克的二苯基亚甲基二异氰酸酯及887克的N,N-二甲基乙酰胺于60±5℃下聚合8小时，即可获得粘土-聚氨酯复合材。以该粘土-聚氨酯复合材的总量为100wt％，该钠型蒙脱土的含量为10wt％。
<<实施例2>>粘土-聚氨酯复合材
将100克的钠型蒙脱土(厂牌：Nanocor,Inc；型号：PGW)与27克的十八烷基乙基二(氨基亚乙基)季铵盐(厂牌：中日合成化学)，于70℃下进行8小时的离子交换反应，即可获得127克的具有氨基的粘土。
将150克分子量为500的聚碳酸酯多元醇[厂牌：宇部兴产株式会社(UbeIndustries,Ltd)；型号：UH500]、0.06克的四丁基锡催化剂、62克的上述具有氨基的粘土、69.4克的二苯基亚甲基二异氰酸酯及545克的N,N-二甲基乙酰胺于80±5℃下聚合2小时，并确认二苯基亚甲基二异氰酸酯完全反应无残留，接着，加入3克的乙二醇及26.4克的二苯基亚甲基二异氰酸酯于60±5℃下聚合4小时，即可获得粘土-聚氨酯复合材。以该粘土-聚氨酯复合材的总量为100wt％，该钠型蒙脱土的含量为20wt％。
<<比较例1>>有机-无机复合材料
参阅台湾专利公开号20130034255中实施例1所揭示的有机-无机复合材料。以该有机-无机复合材料的总量为100wt％，该粘土的含量为3wt％。
<<应用例1>>
将10克实施例1的粘土-聚氨酯复合材与90克的邻甲酚酚醛环氧树脂(厂牌：南亚塑胶公司；型号：NPCN-704)混合，形成复合材料。以该复合材料总量为100wt％计，该钠型蒙脱土的含量为1.0wt％[(10wt％×10)×100％/(90+10)]。
<<应用例2>>
将15克实施例2的粘土-聚氨酯复合材与85克的邻甲酚酚醛环氧树脂(厂牌：南亚塑胶公司；型号：NPCN-704)混合，形成复合材料。以该复合材料总量为100wt％计，该钠型蒙脱土的含量为3.0wt％[(20wt％×15)×100％/(15+85)]。
<<比较应用例1>>
将10克比较例1的有机-无机复合材料与90克的邻甲酚酚醛环氧树脂(厂牌：南亚塑胶公司；型号：NPCN-704)混合，形成复合材。以该复合材总量为100wt％计，该粘土的含量为0.3wt％[(3wt％×10)×100％/(10+90)]。
<<检测项目>>
分散性测量：使用X光粉末绕射仪(厂牌：西德BRUKER；型号：D8AXRD)，测量实施例1及2的粘土-聚氨酯复合材与比较例1的有机-无机复合材料的层间距(d-spacing，单位：nm)。该层间距的数值越大，则代表分散性效果越好。
尺寸稳定性测量：使用热膨胀系数仪(厂牌：尧富精密科技股份有限公司；型号：UF-COE-1000)依据ASTM E831标准手法，测量热膨胀系数(单位：μm/m-℃)。将邻甲酚酚醛环氧树脂(厂牌：南亚塑胶公司；型号：NPCN-704)制成标准片，测量热膨胀系数(A1)。将应用例1及2的复合材料与比较应用例1的复合材制成与标准片相同尺寸，并进行测量，并计算出热膨胀系数(A2)。该热膨胀系数变异率的计算方式：|[(A1-A2)×100]︱/A1。该热膨胀系数变异率的数值越大，则代表尺寸稳定性的效果愈好。
阻隔效果测量：使用水气穿透率测定仪(厂牌：Systech Instruments Ltd；型号LYSSY L80-5000)，测量水蒸气穿透率(Water Vapor Transmission Rate，简称WVTR；单位：g/m2-天)。将由邻甲酚酚醛环氧树脂(厂牌：南亚塑胶公司；型号：NPCN-704)制得的标准片置于样品槽中，并分隔出两个空间，于其中一空间做为干燥室，另一空间做为潮湿室并将温度及相对湿度分别控制在25℃及40％。此时，潮湿室中的水气会逐渐扩散至干燥室，并通过标准片，通过的水气会与干燥室原有的干燥气体混合，一起被带到红外线感应器，通过测量所得的红外线能量数据，并将其转换成电子信号，继而计算出标准片的水蒸气穿透率(B1)。将应用例1及2的复合材料与比较应用例1的复合材制成与标准片相同尺寸，并依上述方式进行测量，并计算出水蒸气穿透率(B2)。该水蒸气穿透率变异率的计算方式：|[(B1-B2)×100]︱/B1。该水蒸气穿透率变异率的数值越大，则代表水气阻隔效果越好。
阻隔效果测量：使用氧气穿透率试验机(厂牌：MOCON；型号：OX-TRANModel 2/21)，并依据ASTM D-3985手法，测量氧气穿透率(OxygenTransmission Rate，简称OTR；单位：cc/m2-天)。使用由邻甲酚酚醛环氧树脂(厂牌：南亚塑胶公司；型号：NPCN-704)制得的标准片，测量出氧气穿透率(C1)。将应用例1及2的复合材料与比较应用例1的复合材制成与标准片相同尺寸，并进行测量，并计算出氧气穿透率(C2)。该氧气穿透率变异率的计算方式：|[(C1-C2)×100]︱/C1。该氧气穿透率变异率的数值越大，则代表氧气阻隔效果越好。
表1
综上所述，在该粘土-聚氨酯复合材中，该粘土可均匀分散于聚氨酯中，且该粘土-聚氨酯复合材具有高含量粘土，后续应用时可提供较佳的阻隔效果及尺寸稳定性，所以确实能达成本发明的目的。
Claims (7)
1.一种粘土-聚氨酯复合材，其特征在于，由包括具有氨基的粘土、多元醇系化合物与多元异氰酸酯系化合物的第一混合物经聚合反应所制得，其中，所述具有氨基的粘土由包括粘土与式(I)所示的季铵盐的第二混合物所形成；
式(I)中，R1至R4各自表示具有氨基的基团或C2至C18的烷基，条件是R1至R4中至少两者为具有氨基的基团；X表示维持式(I)所示的季铵盐电中性的反离子。
2.根据权利要求1所述的粘土-聚氨酯复合材，其特征在于，所述多元醇系化合物选自于乙二醇、丙二醇、丁二醇、1,3-丁二醇、新戊二醇、聚醚多元醇、聚酯多元醇，或它们的组合。
3.根据权利要求1所述的粘土-聚氨酯复合材，其特征在于，所述多元异氰酸酯系化合物选自于甲苯二异氰酸酯、二苯基亚甲基二异氰酸酯、六亚甲基二异氰酸酯、4,4-二环己基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯，或它们的组合。
4.根据权利要求1所述的粘土-聚氨酯复合材，其特征在于，以所述具有氨基的粘土的总量为100重量份计，所述多元醇系化合物的使用量范围为100重量份至1,000重量份。
5.根据权利要求1所述的粘土-聚氨酯复合材，其特征在于，以所述具有氨基的粘土的总量为100重量份计，所述多元异氰酸酯系化合物的使用量范围为10重量份至1,000重量份。
6.根据权利要求1所述的粘土-聚氨酯复合材，其特征在于，以所述粘土的总量为100重量份计，式(I)所示的所述季铵盐的使用量范围为1重量份至99重量份。
7.一种制备粘土-聚氨酯复合材的方法，其特征在于包含以下步骤：
提供具有氨基的粘土，并由包括粘土与式(I)所示的季铵盐的第二混合物所形成，
式(I)中，R1至R4各自表示具有氨基的基团或C2至C18的烷基，条件是R1至R4中至少两者为具有氨基的基团，X表示维持式(I)所示的季铵盐电中性的反离子；
提供多元醇系化合物与多元异氰酸酯系化合物，并与所述具有氨基的粘土进行聚合反应。
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| CN1374346A (zh) * | 2001-03-14 | 2002-10-16 | 中国科学院化学研究所 | 一种含纳米蒙脱土复合物及其制备方法 |
| CN1375524A (zh) * | 2001-03-21 | 2002-10-23 | 中国科学院化学研究所 | 一种含蒙脱土纳米复合材料及其制备方法 |
| CN102850510A (zh) * | 2011-06-27 | 2013-01-02 | 永捷高分子工业股份有限公司 | 有机-无机复合材料及其制作方法 |
-
2015
- 2015-04-29 TW TW104113750A patent/TW201638213A/zh unknown
- 2015-09-02 CN CN201510553469.2A patent/CN106084173A/zh active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374346A (zh) * | 2001-03-14 | 2002-10-16 | 中国科学院化学研究所 | 一种含纳米蒙脱土复合物及其制备方法 |
| CN1375524A (zh) * | 2001-03-21 | 2002-10-23 | 中国科学院化学研究所 | 一种含蒙脱土纳米复合材料及其制备方法 |
| CN102850510A (zh) * | 2011-06-27 | 2013-01-02 | 永捷高分子工业股份有限公司 | 有机-无机复合材料及其制作方法 |
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| TWI519599B (zh) | 2016-02-01 |
| TW201638213A (zh) | 2016-11-01 |
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