CN104220481A - 用于聚氨酯的聚酯多元醇 - Google Patents
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Abstract
本发明涉及适用于生产聚氨酯的聚酯多元醇,所述聚酯多元醇具有ABA结构,其中A代表丙交酯低聚物和B代表引发剂。本发明的特征是所述引发剂包括含具有18或更多碳原子的长链二羧酸组分、优选二聚酸的反应产物。这些组分显示出疏水特性。本发明还涉及生产这种聚酯多元醇的方法。本发明进一步涉及含前述聚酯多元醇的聚氨酯以及这些聚氨酯作为具有高韧度弹性体的用途。据认为所述韧度源于所述多元醇结构中所述引发剂的疏水特性和所述丙交酯部分的亲水特性的组合。本发明的聚丙交酯-聚氨酯弹性体的强度可以通过向所述弹性体材料中加入碳二亚胺进一步改进。
Description
技术领域
本发明涉及适用于生产聚氨酯的聚酯多元醇,所述聚酯多元醇具有ABA结构,其中A代表丙交酯低聚物和B代表引发剂。本发明还涉及生产所述聚酯多元醇的方法。本发明进一步涉及包含前述聚酯多元醇的聚氨酯组合物和所述聚氨酯组合物作为具有高韧度弹性体的用途。
背景技术
在首段中提到的聚酯多元醇本身可由公布的国际专利申请WO2008/037773-A1已知。更具体地,该出版物公开了具有ABA结构的聚酯多元醇,其中引发剂部分B源自二胺如4,4'-二氨基二苯甲烷或源自二醇如1,4-丁二醇。在多元醇结构中丙交酯低聚物部分A的长度基本上为20-140个丙交酯单元。此外,在多元醇结构两端的低聚物长度基本上是相同的。由该聚酯多元醇获得的聚氨酯显示出提高的玻璃化温度和改进的机械特性。
申请人已经发现已知聚氨酯的韧度对于很多应用来说太低。材料的韧度被理解为材料吸收能量和无破碎塑性变形的能力。所述韧度可以依据材料的应力应变曲线或负载伸长率曲线确定,和用MPa表示。
发明内容
本发明目的在于提供不具有在上述专利出版物中公开的已知多元醇的缺点的聚酯多元醇。更具体地,本发明目的在于提供具体种类的包含丙交酯的聚酯多元醇,当包含在聚氨酯中时所述聚酯多元醇给予该聚氨酯高韧度。该韧度应该优选为50MPa以上,更优选为75MPa以上,和最优选为100MPa以上。此外,在一段时间内本发明材料的韧度以及它的断裂伸长率应该更稳定。本发明目的进一步在于提供包含含丙交酯的聚酯多元醇的一类聚氨酯。
这些和其它目的用适用于生产聚氨酯的聚酯多元醇实现,所述聚酯多元醇具有ABA结构,其中A代表丙交酯低聚物和B代表引发剂,根据本发明所述聚酯多元醇的特征在于引发剂包括含具有18或更多碳原子的长链二羧酸组分的反应产物。
含至少18个碳原子的长链烷烃组分为所述反应产物的疏水特性做出高度贡献。尤其是当烷烃链很难支化或完全未支化时。这种长链组分倾向于非极性的,因此优选类似的中性和非极性分子。在这种长链烷烃组分中,链中(几乎)所有的碳原子都连接到两个其它的碳原子上。链端上的碳原子可以仅连接到一个其它的碳原子上,而链上少数碳原子可以连接到三个或甚至四个其它的碳原子上。满足这些特性的烷烃组分呈现出疏水特性。
本发明是基于发明人所获得的见解,即使用具有ABA结构(其中引发剂B具有疏水特性)的含丙交酯的聚酯多元醇将增加基于这种多元醇生产的聚氨酯的韧度。不受理论所限制,发明人认为在具有ABA结构的聚酯多元醇中亲水的(丙交酯基)部分和疏水的(引发剂基)部分的组合对包含这种多元醇的所述聚氨酯的改进韧度特性是至关重要的。
所发明的聚酯多元醇的另一个有意义实施方案具有特殊的特征,即长链二羧酸组分基本上(即大于80wt.%)由二聚酸组成。在本发明的实际实施中包含这种二聚酸的聚酯多元醇是尤其有用的。术语“二聚酸”指公知种类的二羧酸(或它们的酯)。在反应状态中,这些二聚酸对所述引发剂的疏水特性做出高度贡献。通常通过二聚长度为16-24个碳原子的不饱和长链脂肪族一元羧酸成为二聚体而生产这种二聚酸。据认为通过包括环加成反应、自由基和碳正离子机理的可能机理进行二聚作用。所述二聚酸材料通常包含26-44个碳原子。
特别地,实例包括源自C18和C22不饱和一元羧酸(或它们的酯)的二聚酸(或它们的酯),二者分别产生C36和C44二聚酸(或酯)。源自C18不饱和酸(包括酸如亚油酸和亚麻酸)的二聚酸是特别公知的(得到C36二聚酸)。例如,所谓的DELTA9,11和DELTA9,12亚油酸可能二聚为环状不饱和结构。这是唯一可能的结构。包括非环状结构的其它结构也可以形成。所述二聚酸产品一般还包含一定比例的三聚酸(当使用C18原料酸时为C54酸)、可能甚至更高的低聚物和还有少量的单体酸。
一些不同等级的二聚酸是可商购的,它们主要区别在于单体酸和三聚酸馏分含量及不饱和度。C36二聚脂肪酸可以以商品名PripolTM由Croda Ltd商购。这种Pripol组合物包含在本发明的实施中作为所述引发剂的疏水部分特别有用的支化C36二聚脂肪酸。大多数常见的Pripol等级的二聚体含量约为80wt.%。优选二聚体含量95wt.%或更多的等级,因为这些等级包含较少的支化产品。
另外有意义的是,本发明实施方案的特征在于反应产品还包含短链二羧酸组分。这种组分的分子量最通常为小于500g/mol。对于这种组分适合的二羧酸包括例如琥珀酸、间苯二甲酸、邻苯二甲酸、对苯二甲酸、癸二酸、十二烷二酸和壬二酸或它们的混合物。在所有可能的二羧酸中,化合物己二酸是优选的。也可以使用这些二羧酸的二烷基酯或酸酐。短链二羧酸组分(a)和长链二羧酸组分(b)的量之比a/b(都按质量计)优选为5-70,更优选为10-60,和最优选为30-55。在这些范围内,可以优化韧度值到最高值。
另一个有意义的实施方案涉及聚酯多元醇,其特征在于反应产物还包括线性烷二醇。适合的醇类包括例如乙二醇、丙二醇、1,3-丙二醇、二乙二醇、二丙二醇、1,4-丁二醇、新戊二醇、1,9-壬二醇、1,10-癸二醇或1,12-十二烷二醇或它们的混合物。在所有的线性烷二醇中,化合物1,6-己二醇是优选的。所述线性烷二醇在聚酯多元醇中的存在量可以优选为总组分重量的5-70wt.%,更优选为30-55wt.%,和最优选为20-35wt.%。在这些范围中,可以优化与晶体相关的特性。
本发明聚酯多元醇的另一个实施方案的特征在于多元醇的丙交酯低聚物部分包括4-16个乳酰单元。这意味着每个多元醇单元具有一个连接到两个相对短的乳酰低聚物单元的引发剂单元,每个乳酰低聚物单元包含至少两个乳酰单元。由于在生产聚酯多元醇过程中开环聚合,环状丙交酯被开环,和因此转化成包含两个乳酰单元的线性分子。因此,选择反应条件使两个相对短链的乳酰单元连接到所述引发剂上。最短的可能链由两个乳酰单元组成,在开环后对应单个丙交酯单元。在实践中,连接到单个引发剂上的两个乳酰低聚物不需要具有相同数量的乳酰单元。然而,两个低聚物的总长度通常小于16个乳酰单元。在实践中,这意味着在所述聚酯多元醇中丙交酯的量为10-70wt.%,以多元醇的总重量计。这个范围优选为15-50wt.%。
使用的所述丙交酯是可以商购的。通常这种丙交酯通过PLA低聚物的解聚作用制备。丙交酯可以存在于三种不同的具有非对映异构关系的几何结构中。这些不同的结构可以区别为R,R-丙交酯(或D-丙交酯)、S,S-丙交酯(或L-丙交酯)和R,S-丙交酯(或内消旋丙交酯)。等量D-丙交酯和L-丙交酯的混合物通常称为外消旋丙交酯。在本发明的范围内,可以使用所述三种纯丙交酯(仅由一种非对映异构体组成)以及两种或更多种纯丙交酯的混合物。
特别有意义的进一步实施方案涉及本发明的聚酯多元醇,其特征在于聚酯多元醇的摩尔质量为800-4000g/mol。在摩尔质量低于下限值800的情况下,所制备的多元醇的缺点是使用这些多元醇的聚氨酯的柔韧性变得相当低,这是不希望的。在聚酯多元醇的摩尔质量高于上限值4000的情况下,所制备的预聚物的缺点是使用这些多元醇的聚氨酯的硬度变低,这也是不希望的。为了以高确定性避免这两个缺点,优选聚酯多元醇的摩尔质量为1000-3500。
本发明还涉及生产聚酯多元醇的方法。根据本发明,该方法特征在于一定量具有18或更多碳原子的长链二羧酸和二醇在反应混合物中组合,之后混合物的温度升至高于200℃以引发反应,和在所述酸和所述二醇之间的反应结束后向所述反应混合物中加入丙交酯和催化剂。
对于实施根据本发明方法来说,在酸和二醇之间的反应结束后添加丙交酯和催化剂是至关重要的。如果在反应开始时添加丙交酯和催化剂,则形成所谓的随机聚酯多元醇。包含这种多元醇的聚氨酯不会呈现出有意义的高韧度效果。为了保证在酸和二醇的反应中形成的引发剂具有羟基端基,一定量的二醇应该(少量)加入反应混合物中。为了优化最终聚氨酯的希望特性,反应混合物可能还包含其它酸和醇,例如一元酸和三元酸以及一元醇和三元醇。
作为催化剂,可以使用用于丙交酯聚合的常见催化剂,如S(II)-化合物。所述化合物Sn(II)-辛酸盐被证明在根据本发明生产聚酯多元醇的过程中是优异的催化剂。
本发明方法的一个有意义实施方案的特征在于反应混合物还包含短链二羧酸,优选为己二酸。添加这种酸可以改进最终聚氨酯的结晶度。
本发明方法的另一个有意义实施方案的特征在于二醇是1,6-己二醇。在本发明的多元醇中,这种二醇的存在为最终聚氨酯提供额外结晶度的优点。
本发明有意义的聚氨酯组合物的特征在于组合物聚合物还包含碳二亚胺。添加这种碳二亚胺明显增加聚丙交酯-聚氨酯共聚物的强度,但没有延伸率的损失。此外,还改进了包含碳二亚胺的聚丙交酯-聚氨酯共聚物的断裂伸长率。在所述共聚物中碳二亚胺的量为所述聚丙交酯-聚氨酯共聚物的0.1-5wt.%。添加碳二亚胺的量大于5wt.%可能导致前述共聚物的有利特性不希望的减少。添加碳二亚胺的量小于0.1wt.%可能使添加化合物效果太低。在所述共聚物中碳二亚胺的量为0.2-2wt.%的情况下,可以达到这两种情况之间的优化折中。
本发明还涉及包含如上所述聚酯多元醇的聚氨酯组合物。这种聚氨酯组合物可以以很大的优势用作具有至少50MPa、优选75MPa和更优选100MPa的韧度的弹性体。
附图说明
本发明将通过若干实验和附图更详细地进行说明,其中
图1给出包含聚酯多元醇的三种聚氨酯的应力应变曲线,其中一种是本发明,
图2给出包含聚酯多元醇的三种聚氨酯的机械数据表,
图3的图线作为时间函数给出(碳二亚胺改性的)聚丙交酯-聚氨酯共聚物的强度,和
图4的图线作为时间函数给出(碳二亚胺改性的)聚丙交酯-聚氨酯共聚物的断裂伸长率。
具体实施方式
两种含丙交酯的聚酯多元醇的生产描述如下,其中一种是本发明,但另一种不是本发明。
不是本发明聚酯多元醇的聚酯多元醇A制备如下。在装配有搅拌器、温度计、气体入口和冷凝器的反应器中,加入50份PRIPOL1006、50份乙二酸、62.3份1,6-己二醇,52.45份L-丙交酯(B3)和0.05份作为聚合催化剂的辛酸锡。在氮气环境中在正常压力下温度升至220-230℃。使所述混合物反应,和从系统中除去形成的水。实施酯化反应直到获得希望的酸值和羟基值。获得的聚酯多元醇的评估结果为酸值<1mgKOH/g和羟基值为55mgKOH/g。当所有组分初始混合和反应后,获得了随机聚酯多元醇。
作为本发明聚酯多元醇的聚酯多元醇B制备如下。在装配有搅拌器、温度计、气体入口和冷凝器的反应器中,加入50份PRIPOL1006、50份乙二酸和62.3份1,6-己二醇。在氮气环境中在正常压力下温度升至220-230℃。使所述混合物反应,和从系统中除去形成的水。实施酯化反应直到获得希望的酸值和羟基值。获得的聚酯多元醇的评估结果为酸值<1mgKOH/g和羟基值为75mgKOH/g。随后温度降至160℃,之后加入52.45份L-丙交酯(B3)和0.05份作为聚合催化剂的辛酸锡。实施反应直到获得希望的酸值和羟基值。获得的聚酯多元醇的评估结果为酸值<1mgKOH/g和羟基值为55mgKOH/g。在其它组分的反应基本完成后加入丙交酯以形成亲水性引发剂时,获得的最终反应产物是类型ABA的聚酯多元醇,其中A代表乳酰低聚物和B代表引发剂。
由聚酯多元醇A和聚酯多元醇B两者制备聚氨酯弹性体组合物如下。在杯子中混合100份所述多元醇、11.2份1,4-丁二醇和46.5份二苯甲烷二异氰酸酯(MDI)。如此获得的混合物脱气、慢慢倒入模具中和在110℃下固化20小时以形成拉伸强度哑铃。在冷却至室温后,固化的哑铃从模具中移出和评价它们的物理和化学特性。为了对比的目的,获得可商购的聚氨酯组合物(C)。该聚氨酯组合物包含具有半结晶结构的聚酯多元醇。
图1给出的谱图描述了前面描述的三种聚氨酯哑铃的测量的应力应变曲线。在ISO527-2标准定义的条件下,在Instron3366设备上记录这些测量的曲线。在这些曲线中,负载L(牛顿)作为哑铃带延伸率E(百分比)的函数测量。
从图1中可以确定,到目前为止,本发明的包含具有ABA结构的含丙交酯的聚酯多元醇的聚氨酯组合物(类型B)的韧度(用MPa表示)最大,其中引发剂组分和丙交酯(或乳酰)组分随机分布在多元醇中的所述包含丙交酯的聚氨酯组合物(类型A)的韧度较低,包含半结晶的聚酯多元醇的聚氨酯组合物(类型C)的值最低。
图2的表格总结了基于三种不同聚酯多元醇的聚氨酯的不同机械特性。由这个表可以总结出,相比于其它两种不是本发明的聚氨酯,在所有描述的特性中,本发明的具有ABA结构的聚酯多元醇是最好的。因此,肖氏硬度A(根据ISO868标准测量)、拉伸强度(用N表示)、杨氏模量(用MPA表示,根据ISO527-2标准测量)和韧度均是最高的。
由本发明的聚酯多元醇B制备未改性聚氨酯组合物弹性体和碳二亚胺改性聚氨酯组合物弹性体两者如下。在杯子中,完全混合100份多元醇和11.2份1,4-丁二醇(BDO,链增长剂)和脱气。随后向所述混合物中添加46.5份二苯甲烷二异氰酸酯(MDI,Lupranat MIP)以获得未改性弹性体。为了获得碳二亚胺改性弹性体,2份Bioadimide100(碳二亚胺)与46.5份MDI一起添加到所述混合物中。如此获得的混合物再次脱气,慢慢倒入模具中和在110℃下固化20小时以形成拉伸强度哑铃。冷却至室温后,固化的哑铃从模具中取出,在水中放置一段时间和随后评价它们的物理和化学特性。
为了所生产的弹性体的拉伸测试,如前文所述生产的两个系列的哑铃(分别为改性和未改性)在40℃下放置在水中50天。在这期间,每天取出每个系列的若干哑铃,在23℃下干燥7天和随后测量它们的若干拉伸特性。
图3的图线作为时间(t用天表示)函数给出干燥哑铃的最大负载(N用MPa表示)。所述最大负载定义为哑铃断裂的负载。虚线代表由未改性弹性体材料制备的系列哑铃。实线代表由碳二亚胺改性弹性体材料制备的系列哑铃。图3清楚地表明用碳二亚胺改性的聚丙交酯-聚氨酯共聚物材料使得强度明显增加。因此,可以用于这种改性弹性体的最大负载比可以用于未改性弹性体的负载明显更大。
图4的图线作为时间(t用天表示)函数给出干燥哑铃相对最大伸长率负载(%)。相对最大伸长率负载定义为在哑铃断裂前所述材料可获得的最大长度增加百分比。虚线代表由未改性弹性体材料制备的系列哑铃。实线代表由碳二亚胺改性材料制备的系列哑铃。图4清楚地表明用碳二亚胺改性的聚丙交酯-聚氨酯共聚物材料使得所述相对最大伸长率负载在至少30天内随时间保持稳定。然而,未改性弹性体的所述相对最大伸长率负载在至少30天内随时间降低。
聚氨酯组合物粘合剂材料已经制备如下。由聚酯多元醇A(随机的)和聚酯多元醇B(ABA结构)两者制备2组分聚氨酯粘合剂。为此目的,在杯子中混合100份多元醇和46.5份二苯甲烷二异氰酸酯(MDI,Lupranat MIP,BASF)。刚好在所述粘合剂应用之前,在强烈搅拌期间向所述混合物中加入锡催化剂(二丁基二月桂酸锡,DBTL)。如此获得的粘合剂作为薄层施用在两个相同材料基底的表面上,所述基底随后压在一起和在温度110℃下固化8小时。随后针对不同的铝和聚丙烯基底测量接合部分剪切粘合力。为了对比目的,使用了商购的聚氨酯C和D。聚氨酯C(PriplastTM 3192,Croda Ltd.)包含商购的具有半结晶结构的聚酯多元醇。聚氨酯D(PTMEG,MW 2000,Invista)包含商购的具有不定形结构的聚酯多元醇。
总之,可以看出本发明涉及适用于生产聚氨酯的聚酯多元醇,所述聚酯多元醇具有ABA结构,其中A代表丙交酯低聚物和B代表引发剂。本发明的特征是所述引发剂包括含具有18或更多碳原子的长链二羧酸组分、优选二聚酸的反应产物。这种化合物表现出疏水特性。本发明还涉及生产这种聚酯多元醇的方法。本发明进一步涉及含前述聚酯多元醇的聚氨酯以及这些聚氨酯作为具有高韧度弹性体的用途。据认为所述韧度源于所述多元醇结构中所述引发剂的疏水特性和所述丙交酯部分的亲水特性的组合。本发明的聚丙交酯-聚氨酯弹性体的所述最大负载以及相对最大伸长率负载可以通过向所述弹性体材料中加入碳二亚胺进一步改进。
本领域技术人员将认识到本发明并不局限于所述优选实施方案。在实施本发明时,从附图、公开内容和所附权利要求的研究中,本领域技术人员可以理解和实施所公开实施方案的其它变化。在权利要求中,词语“包含”不排除其它元素或步骤,和不定冠词“a”或“an”不排除复数。在互异的从属权利要求中列举某些措施的事实不表明这些措施的组合不能用来获益。在权利要求中的任何附图标记均不应该视为对所述范围的限制。
Claims (12)
1.适用于生产聚氨酯的聚酯多元醇,所述聚酯多元醇具有ABA结构,其中A代表丙交酯低聚物和B代表引发剂,特征在于引发剂包含括含具有18或更多碳原子的长链二羧酸组分的反应产物。
2.权利要求1的聚酯多元醇,特征在于长链二羧酸组分基本上由二聚酸组成。
3.权利要求2的聚酯多元醇,特征在于反应产物还包含短链二羧酸组分,优选己二酸组分。
4.前述权利要求任一项的聚酯多元醇,特征在于反应产物还包含线性烷二醇,优选1,6-己二醇。
5.前述权利要求任一项的聚酯多元醇,特征在于多元醇的丙交酯低聚物部分包含4-16个乳酰单元。
6.前述权利要求任一项的聚酯多元醇,特征在于聚酯多元醇的摩尔质量为800-4000g/mol。
7.生产聚酯多元醇的方法,特征在于一定量具有18或更多碳原子的长链二羧酸和二醇在反应混合物中组合,之后混合物的温度升至高于200℃以引发反应,和在所述酸和所述二醇之间的反应结束后向所述反应混合物中加入丙交酯和催化剂。
8.权利要求7的方法,特征在于反应混合物还包含短链二羧酸,优选己二酸。
9.权利要求7或8的方法,特征在于所述二醇是1,6-己二醇。
10.包含权利要求1-7任一项的聚酯多元醇的聚氨酯组合物。
11.权利要求10的聚氨酯组合物,特征在于所述组合物还包含碳二亚胺。
12.权利要求10或11的聚氨酯组合物作为弹性体的用途,所述弹性体具有至少50MPa的韧度,优选为至少75MPa,和更优选为至少100MPa。
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JP2015512995A (ja) | 2015-04-30 |
EP2838932B1 (en) | 2019-08-07 |
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JP6030221B2 (ja) | 2016-11-24 |
US20150031848A1 (en) | 2015-01-29 |
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