CN104387556A - 用于一步法中聚氨酯产品配方的单组分异氰酸酯预聚体混合物及其应用 - Google Patents

用于一步法中聚氨酯产品配方的单组分异氰酸酯预聚体混合物及其应用 Download PDF

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CN104387556A
CN104387556A CN201410653300.XA CN201410653300A CN104387556A CN 104387556 A CN104387556 A CN 104387556A CN 201410653300 A CN201410653300 A CN 201410653300A CN 104387556 A CN104387556 A CN 104387556A
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prepolymer
mixture
alcohol
isocyanate
stage method
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普利兹麦斯洛多米奇
马略克巴斯
汤姆斯珀鲁斯
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SELENA LABS SP Z OO
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Abstract

本发明公开了一种用于一步法中聚氨酯产品配方的单组分异氰酸酯预聚体混合物及其应用。在该混合物中，一元甲叉二苯基二异氰酸酯（MDI）在混合物中的含量不超过总重量的3％，优选低于2％，更优选低于1％，该预聚物包括：单官能醇、异氰酸酯组分或异氰酸酯混合物组分、促进剂、催化剂、稳定剂、一种或多种多元醇，所述单官能醇由乙二醇醚或丙二醇醚构成。本发明还提供了一种基于该预聚物制备单组分聚氨酯泡沫的方法。本发明无需使用额外的预聚物，无需加热初始的基底，即叔醇，这是由于预聚物混合物的制备较快，问题较少，且成本低廉。

Description

用于一步法中聚氨酯产品配方的单组分异氰酸酯预聚体混合物及其应用
技术领域
本发明涉及一步法中用于聚氨酯产品配方的单组分异氰酸酯预聚物及其制备单组分聚氨酯泡沫的方法。
背景技术
聚氨酯预聚物具有大量不同的工业用途，目前市面上也已经制备了大量含有挥发性异氰酸酯单体的体系，例如甲叉二苯基二异氰酸酯（MDI）体系，其主要用于泡沫、粘合剂、底涂剂、汽车消声系统、弹性元件和部件等的制备。目前，在工业范围内，人们也在关注减少挥发性异氰酸酯单体暴露的危险，因为其对人的健康是有害的。
因此，需要降低前体和聚氨酯预聚物中异氰酸酯单体的浓度，现有技术已知的一个方案是使用蒸馏技术，例如刮膜蒸发器将挥发性异氰酸酯单体从预聚物体系中移除。参见Anderson et al，专利号为 US5441808的美国专利，第6栏，第29-34行，该方案需要额外的操作单元，投资成本和制备该预聚物的操作成本比较高。现有技术已知的另一方案包括用两步法制备预聚物，其中，在第一步骤中，多元醇与具有不同反应活性异氰酸酯基团的不对称的异氰酸酯反应，多元醇优选与活性较高的基团反应。该方法持续至理论量的反应性较高的异氰酸酯与多元醇反应完，然后反应产物与反应性更高的对称异氰酸酯反应，从而构成预聚物。该两步法也需要额外的操作单元，额外的步骤和用于处理第二异氰酸酯所需的额外成本会增加该方案的成本。参见Bolte et al，专利号为US6515164的美国专利和Bauriedel，专利号为US4623709的美国专利，引用作为参考。该方法需要确定非常准确的处理条件，这是由于链的增长会降低与目前预聚物粘度相关的弹性，且能使专家不用调整就能达到其目标性质。欧洲专利申请EP2481764公开了单官能醇在预聚物组合物中的用途，其分子量至少为130 g/mol，且为石蜡结构，优选为2-乙基己醇。上述专利申请中，第一步形成了两个组分。组分A制备方法如下：在室温下加入如下成分混合搅拌20分钟：蓖麻油、乙二醇、二吗啉二乙基醚（DMDEE）、磷酸三（2-氯丙基）酯（TCPP）和硅氧烷表面活性剂（Tegostab B8870）；组分B制备方法如下：在室温下分别加入如下成分混合搅拌35分钟：粗MDI（Supersec 5025）和2-乙基己醇，两物质一旦混合，就加入NCO（异氰酸酯基团）封端的甲苯二异氰酸酯（TDI）预聚物，然后混合，接着将组分A和B加入有阀门的容器中，注入发泡剂（porophors，即blowing  agents）。在下个阶段，振荡该容器2-3分钟。上述方法为两步法制备具有低MDI的泡沫（OCF），然而，其相对复杂。由于MDI含量较低，成为了NCOI预聚物溶剂，泡沫粘度提高。国际专利申请PCT/PL2013/050002讨论了一步法中用于制备聚氨酯产品的单组分异氰酸酯预聚物，其单体甲叉二苯基二异氰酸酯（MDI）在所述混合物中的含量不超过包含如下物质的总重量的3％，四官能醇、异氰酸酯组分或异氰酸酯组分混合物、促进剂、催化剂、稳定剂和一种或多种多元醇。所述预聚物混合物使用了叔醇，在其用于该方法之前，需要在其用于初始反应器之前先熔化。鉴于该预聚物是通过常规技术，使用标准，市售的异氰酸酯单体体系制备，因此聚氨酯预聚物需要含有低浓度的异氰酸酯单体，也需要其含有该预聚物的组合物和泡沫体系。此外，需要提供一种预聚物，其无需额外的分离单元操作或复杂的方法步骤，而是由于它们的放热性质而分开，上述方法甚至在制备用于预聚物配方反应的基底的步骤，即熔融叔醇的步骤中，会在容器中引起过量的压力。另外，需要减少昂贵的化合物，例如甲苯二异氰酸酯（TDI）预聚物，节约成本。此外，所得预聚物和泡沫需要具有最终泡沫的标准收率。
发明内容
为了解决上述现有技术中存在的问题，本发明的第一个目的在于提供一种一步法中用于制备聚氨酯产品配方的单组分异氰酸酯预聚体混合物，其中，一元甲叉二苯基二异氰酸酯（MDI）在混合物中的含量不超过总重量的3％，优选低于2％，更优选低于1％，该预聚物包括：
-单官能醇，
-异氰酸酯组分或异氰酸酯混合物组分，
-促进剂，
-催化剂，
-稳定剂，
-一种或多种多元醇，
其特征在于，所述单官能醇包括乙二醇醚或丙二醇醚，所述单官能醇更适合选自如下：2-甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇、2-异丙氧基乙醇、2-丁氧基乙醇、2-苯氧基乙醇、2-苄氧基乙醇、2-（2-甲氧基乙氧基）乙醇、2-（2-乙氧基乙氧基）乙醇、2-（2-丁氧基乙氧基）乙醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丙氧基-2-丙醇、5-甲基-4,7-二氧杂-2-庚醇、5-甲基-4,7-二氧杂-2-癸醇、2-（2-丁氧基甲基乙氧基）甲基乙氧基）丙醇、1-丁氧基-2-丙醇、1-（2-丁氧基-1-丙氧基）-2-丙醇、[2-（2-甲氧基丙氧基）丙氧基]丙醇。
所述促进剂包括选自如下的气体：二甲醚、异丁烷和丙烷或其气体形式的混合或它们的混合物，其量为10％-40％（重量百分比），优选为14％-30％，更优选为18％-24％。
所述催化剂的含量为0.1％-2％（重量百分比），优选为0.2％-1.5％，更优选为0.3％-1％。
具有改性有机硅氧烷的化学组合物的稳定剂选自聚硅氧烷二醇共聚物（例如Air Products的Dabco DC198或DC193）、非水解聚硅氧烷二醇共聚物（例如Air Products的DC5000）、聚硅氧烷乙二醇共聚物（例如Momentive的Niax L-6164）、聚甲基硅氧烷乙二醇共聚物（例如Momentive的Niax L-5348）、聚醚-聚硅氧烷共聚物（例如Evonik的Tegostab B8870）、聚二甲基硅氧烷聚醚共聚物（例如Evonik的Tegostab B8526）、聚醚共聚物（例如Evonik的Tegostab B8951或B84702）、聚醚改性聚硅氧烷共聚物（例如Evonik的Tegostab B8871）及其衍生物和它们的混合物。
更优选的NCO：OH（其中，NCO是异氰酸酯基团，OH是羟基）的摩尔比例为1-3，优选为1.5-2.7，更优选为1.9-2.5。更优选该混合物含有氯代石蜡，优选量为5％-70％（重量百分比）的C14-C17中链，优选为10％-50％，更优选为18％-40％，或优选量为10％-70％的长链C18-C20氯代石蜡，优选为30％-60％，更优选为40％-50％。更优选该混合物含有分子量为400-1000的三官能醇，优选一种或多种分子量为400-2000的二官能多元醇。
本发明的第二个目的是提供一种制备单组分聚氨酯泡沫的方法，其特征在于包括如下步骤：
-准备称量容器，
-将上述得到的预聚物转移至容器中，优选将促进剂保持在容器外，
-关闭称量容器，优选将促进剂加入容器中。
与现有技术相比，本发明的有益效果在于：
本发明涉及单组分泡沫（OCF），其含有微量的单体二异氰酸酯（2,2’-甲叉二苯基异氰酸酯、2,4’-甲叉二苯基异氰酸酯和4,4’-甲叉二苯基异氰酸酯）。本发明可以使用常见的市售异氰酸酯、多元醇，稳定剂作为OCF配方。本发明与现有技术的方案相比，唯一的差别在于无需使用额外的预聚物，无需加热初始的基底，即叔醇，这是由于预聚物混合物的制备较快，问题较少，且成本低廉。
具体实施方式
以下通过具体实施例来对本发明作进一步详细的说明。
在如下实施例1-4的试样中，首先加入三官能聚醚多元醇，来制备多元醇混合物，加入分子量为400-1000的三官能聚醚多元醇；加入分子量为400-2000的双官能多元醇聚醚；加入C14-C17的中链或C18-C20的长链氯代石蜡或它们的混合物；加入单元醇1-甲氧基-2-丙醇（市售的Dowanol PM（DOW））；加入稳定剂，优选为稳定剂的混合物，例如选自：Dabco DC198（AirProducts）、DC193（AirProducts）、DC5000（AirProducts）、DC5357（AirProducts）、Niax L-6164（Momentive）、Niax L-5348（Momentive）、Tegostab B84702（Evonik）、Tegostab B8870（Evonik）、Tegostab B8526（Evonik）、Tegostab B8951（Evonik）、Tegostab B8871（Evonik）；加入催化剂（由Jeffcat DMDLS购得，化学名：2,2’-二吗啉二乙醚）。
然后，在能防止湿气的密闭容器中，在室温下搅拌该多元醇混合物10分钟，将该多元醇混合物和用工业方法制造的二苯基二异氰酸酯加入单用途压力容器中，该异氰酸酯的NCO含量为31%（重量比），可以使用市售的Desmodure 44V70L（Bayer）或Lupranat M70（Basf）或它们的混合物。在压力容器中通入二甲醚和异丁烷，然后振荡，直至多元醇与异氰酸酯完全混合，单体含量为全部组合物的1 %（重量百分比）以下。
实验结果如下表所示：
  实施例1 实施例2 实施例3 实施例4
单体和甲叉二苯基异氰酸酯均匀混合物（Desmodure 44V70L/ Lupranat M70） 196 196 196 196
聚醚多元醇（Rokopol G1000） 46 46 46 46
聚醚多元醇三醇（分子量400-1000） 27 27 27 27
聚醚多元醇三醇（分子量400-2000） 12 12 12 12
1-甲氧基-2-丙醇 24 24 24 24
稳定剂 12 18 12 18
C14-C17中链氯代石蜡 483     198
C18-C20长链氯代石蜡   477 483 279
催化剂 4 4 4 4
丙烷 32 32 32 32
异丁烷 74 74 74 74
二甲醚 90 90 90 90
总计 1000 1000 1000 1000
OCF泡沫中最重要的因素是压力容器中预聚物的粘度。已知单体MDI是NCO预聚物的良溶剂，然而其在公开的发明中的含量低于1%。因此，低单体含量的泡沫具有更高的粘度。为了改变压力容器中泡沫预聚物的粘度，重要的是添加限定比例的促进剂，尤其是二甲醚DME，二甲醚与异丁烷和丙烷混合物的比例为1：1.17。在低单体含量的泡沫中，泡沫收率较低，这是由于含有NCO基团的自由单体量较少，且CO2产生受限，这可以通过加入发泡剂来弥补。
在本发明中，可以使用中链氯代石蜡和长链氯代石蜡或它们的混合物。由于环保因素，优选使用长链氯代石蜡，术语“长链”可以理解为超过17个碳原子的链。
还有一个重要的因素是低比例的NCO：OH，其为1-3，优选为1.5-2.7，更优选为1.9-2.5。低比例的NCO：OH是非常重要的，其能使所得单体含量低于3%，优选低于2%，更优选低于1%。乙二醇醚取代的叔醇能降低混合物制备时间的20%，能节约能量消耗的15%。因此，该方法更快且更节能。
需要说明的是，以上实施例仅供说明本发明之用，而非对本发明的限制，有关技术领域的技术人员，在不脱离本发明的精神和范围的情况下，所作出各种变换或变型，均属于本发明的范畴。

Claims (9)

1.一种用于一步法中聚氨酯产品配方的单组分异氰酸酯预聚体混合物，其中，一元甲叉二苯基二异氰酸酯在混合物中的含量不超过总重量的3％，该混合物包括：
-单官能醇，
-异氰酸酯组分或异氰酸酯混合物组分，
-促进剂，
-催化剂，
-稳定剂，
-一种或多种多元醇，
其特征在于，所述单官能醇包括乙二醇醚或丙二醇醚，优选自 2-甲氧基乙醇、2-乙氧基乙醇、2-丙氧基乙醇、2-异丙氧基乙醇、2-丁氧基乙醇、2-苯氧基乙醇、2-苄氧基乙醇、2-（2-甲氧基乙氧基）乙醇、2-（2-乙氧基乙氧基）乙醇、2-（2-丁氧基乙氧基）乙醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丙氧基-2-丙醇、5-甲基-4,7-二氧杂-2-庚醇、5-甲基-4,7-二氧杂-2-癸醇、2-（2-丁氧基甲基乙氧基）甲基乙氧基）丙醇、1-丁氧基-2-丙醇、1-（2-丁氧基-1-丙氧基）-2-丙醇、[2-（2-甲氧基丙氧基）丙氧基]丙醇。
2.如权利要求1所述的一步法中用于聚氨酯产品配方的单组分异氰酸酯预聚物，其特征在于，所述促进剂包括选自如下的气体：二甲醚、异丁烷和丙烷或其气体形式的混合或它们的混合物，其量为10％-40％（重量百分比），优选为14%-30%，尤其优选为18%-24%。
3.如权利要求1所述的一步法中用于聚氨酯产品配方的单组分异氰酸酯预聚物，其特征在于，所述催化剂的含量为0.1％-2％（重量百分比），优选为0.2％-1.5％，更优选为0.3％-1％。
4.如权利要求1所述的一步法中用于聚氨酯产品配方的单组分异氰酸酯预聚物，其特征在于，所述稳定剂选自聚硅氧烷二醇共聚物、非水解聚硅氧烷二醇共聚物、聚硅氧烷聚氧烷基共聚物、聚甲基硅氧烷聚聚氧烷基共聚物、聚醚-聚硅氧烷共聚物、聚二甲基硅氧烷聚醚共聚物、聚醚共聚物、聚醚改性聚硅氧烷共聚物及其衍生物和它们的混合物。
5.如权利要求1-4中任一项所述的一步法中用于聚氨酯产品配方的单组分异氰酸酯预聚物，其特征在于，异氰酸酯基团与羟基的摩尔比例为1-3，优选为1.5-2.7，更优选为1.9-2.5。
6.如权利要求1-4中任一项所述的一步法中用于聚氨酯产品配方的单组分异氰酸酯预聚物，其特征在于，该预聚物还含有氯代石蜡，优选为5％-70％（重量百分比）的C14-C17中链，优选为10％-50％，更优选为18％-40％，或者优选为10％-70％的长链氯代石蜡，优选为30％-60％，更优选为40％-50％。
7.如权利要求1-4中任一项所述的一步法中用于聚氨酯产品配方的单组分异氰酸酯预聚物，其特征在于，该预聚物还含有分子量为400-1000的三官能醇，优选一种或多种分子量为400-2000的二官能多元醇。
8.一种制备单组分聚氨酯泡沫的方法，其特征在于包括如下步骤：
-准备称量容器，
-将权利要求1-7中任一项所述的预聚物放至容器中，
-关闭称量容器，进行混合。
9.如权利要求8所述的制备单组分聚氨酯泡沫的方法，其特征在于，在称量结束再将促进剂放入容器中。
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CN111303376B (zh) * 2020-02-17 2022-02-18 成都高端聚合物科技有限公司 压力罐装可表面喷涂单组分聚氨酯泡沫及制备方法、应用

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US9738747B2 (en) 2017-08-22
US20150197596A1 (en) 2015-07-16
EA033967B1 (ru) 2019-12-13
PL235304B1 (pl) 2020-06-29
EA201401232A1 (ru) 2015-07-30
EP2894181A1 (en) 2015-07-15
BR102014029745A2 (pt) 2015-09-15

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