CN1150237C - 热塑性聚氨酯(基于聚丁二烯软链段的tpu)组合物及其制法 - Google Patents
热塑性聚氨酯(基于聚丁二烯软链段的tpu)组合物及其制法 Download PDFInfo
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Abstract
制造热塑性聚氨酯材料的方法,包括下列步骤:将NCO封端的预聚物与1,4-丁二醇铸塑成形为铸塑组合物;将铸塑组合物挤塑成形为至少1根聚氨酯弹性体的线料;将至少一根所述聚氨酯弹性体切粒,成形为至少1种粒料;以及将至少1种粒料加工成形为热塑性制品。
Description
发明背景
基于官能度为2.0的聚丁二烯软链段的聚氨酯公开在Yokelson等人的专利(美国专利5,589,543)中。然而,Yokelson等人却没有公开聚氨酯作为热塑性塑料的应用。市售的羟基封端聚丁二烯被用来配制各种铸塑用聚氨酯树脂和粘合剂。然而,由于这些聚丁二烯具有大于2.0的官能度,它们形成的是热固性聚氨酯材料。以这种聚丁二烯为基础的聚氨酯无法按照热塑性塑料来加工(挤塑或注塑加工)。官能度为2.0的羟基封端聚丁二烯公开在Chung等人的美国专利5,247,023、Grubbs等人的美国专利5,750,815以及Nubel等人的美国专利5,512,635、5,559,190、5,519,101及5,403,904专利中。然而,这种聚丁二烯没有被用来制造热塑性聚氨酯材料。
由官能度等于2的聚丁二烯二醇制造的聚氨酯弹性体,据公开,可按照如下过程制造:制备聚丁二烯二醇的甲苯二异氰酸酯(TDI)预聚物,掺混在methylene bis-ortho chloroaridine(MbOCA)中,然后在高温和压力下对其压制,从而使混合物固化。另外,此种弹性体,据公开,还可按照一步流程制造,即,将1,4-丁二醇与聚丁二烯二醇掺混,加入熔融二苯基-甲基的二异氰酸酯(MDI),然后,在高温和压力下对反应混合物压制,参见Frisch等人,《Cell Polym》(1996),15(6),第395页。然而,已发现,按照预聚物方法由MDI、聚丁二烯二醇及1,4丁二醇的混合物铸塑而成的聚氨酯具有非常差的初始机械性能。即使在经过长时间高温后固化(18h,110℃)之后,这种聚合物仍旧不足以坚韧到能够切断并接受机械性能测试。然而,我们却令人惊奇地发现,用铸塑材料进行挤塑,可显著改善其机械性能。
发明概述
本发明涉及制造热塑性聚氨酯材料的方法,包括下列步骤:将NCO封端的预聚物与1,4-丁二醇一起铸塑成形为铸塑组合物;将铸塑组合物挤塑成形为聚氨酯弹性体线料;将聚氨酯弹性体线料切粒,成形为粒料;然后,将粒料加工成形为聚氨酯制品。本发明还涉及用上述方法制造的热塑性聚氨酯材料。
发明详述
本发明涉及包含NCO封端预聚物的聚氨酯,该预聚物包含多异氰酸酯与没有支化侧链基团的、链端官能化的线型非交联聚烯烃的反应体系,其中制造该聚氨酯的方法包括将NCO封端预聚物与1,4-丁二醇铸塑成形为铸塑组合物的步骤。该预聚物还可与1,3-丙二醇、1,3-丁二醇、1,6-己二醇或其他二醇一起铸塑。铸塑是在大气压下在50~120℃的模具中进行的。
该铸塑组合物,随后经挤塑,成形为至少1根聚氨酯弹性体线料。优选的是,挤塑加工在挤塑如单螺杆或双螺杆挤塑机中进行。最优选的是双螺杆挤塑机,例如,Werner & Pfleiderer ZSK-V 53mm挤塑机。
聚氨酯弹性体线料,随后在切粒机中切成粒料,例如,在任何旋转刀片切粒机或Cumberland 6英寸切粒机中。最后,粒料再通过Newbury 7吨,或任何类似的模塑机器中接受注塑加工。粒料还可接受挤塑、吹塑、吹胀为薄膜,等等。
本发明的聚烯烃的制备包括,使链转移剂与环状烯烃在催化剂存在下起反应,从而制成要求的聚烯烃。
特别是,该聚烯烃是羟基官能化的聚丁二烯(HFPB),它是通过“开环易位聚合”(“ROMP”)法(Grubbs等人,美国专利5,750,815)制备的。
HFPB的合成需要链转移剂(CTA),它起着在聚合物链端加上官能性(羟基基团)的作用。CTA的使用要根据所使用的ROMP催化剂种类而定。在本发明中,最优选的链转移剂是1,4-双乙酸基-2-丁烯。相应地,此种链转移剂只有在与钌基易位催化剂配合使用时才起作用,而且对聚丁二烯二醇的粘度有显著影响。
在本发明中,优选的环状烯烃是环丁烯和环辛二烯,而最优选的环状烯烃是1,5-环辛二烯,它最优选与1,4-双乙酸基-2-丁烯,在催化剂存在下起反应,生成本发明的HFPB。按该方法生成的HFPB具有如下结构:
HO[CH2-CH=CH(CH2)2-CH=CH-CH2]nCH2-CH=CH-CH2OH,
其中n是1~1000的数均值。
可用于本发明的催化剂及其制法描述在转让给加州理工学院的、Grubbs等人的专利(美国专利5,342,909)中。在优选的实施方案中,本发明要求的催化剂是以钌金属碳烯配合物为基础的化合物。在最优选的实施方案中,催化剂是双(三环己基膦)亚苄基二氯化钌。
本发明的聚烯烃,由于是线型、不饱和、官能度为2.0、不存在交联、粘度低、多分散性低,因而具有独特的物理性能,并能够将这些性能赋予其他的聚合物。
本发明的HFPB聚烯烃的粘度为500~40,000mPa.s,最优选为800~16,000mPa.s。此种聚烯烃的官能度在1.8~2.0的范围,最优选是2.0。官能度是通过滴定和气相渗透压法测定的。HFPB的数均分子量在196~200,000g/mol,最优选在1,500~6,500g/mol的范围。
低粘度预聚物也可采用此种聚烯烃制备。这类预聚物,即,可用作本发明中的二异氰酸酯组分者,是由单体二异氰酸酯与本发明的聚烯烃HFPB来制备的。
本发明预聚物的平均官能度为1.8~2.0,最优选2.0。另外,该预聚物优选具有的NCO含量在3~20%,最优选在4~15%的范围。最后,预聚物优选具有的25℃下的粘度在500~20,000mPa.s,最优选在1000~10,000mPa.s的范围。
合适的单体二异氰酸酯可用下式表示:
R(NCO)2
其中R代表有机基团。这类二异氰酸酯的分子量为约112~1,000,优选约140~400,最优选174~300。本发明方法优选使用的二异氰酸酯是那些所包含的R代表4~40,优选4~18个碳原子的二价脂族烃基的、5~15个碳原子的二价环脂族烃基的、7~15个碳原子的二价芳脂族烃基或者6~15个碳原子的二价芳基的。
合适的有机二异氰酸酯的例子包括:1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯、2,2,4-三亚甲基-1,6-六亚甲基二异氰酸酯、1,12-十二亚甲基二异氰酸酯、环己烷-1,3-及-1,4-二异氰酸酯、1-异氰酸根合-2-异氰酸根合甲基环戊烷、1-异氰酸根合-3-异氰酸根合甲基-3,5,5-三甲基-环己烷(异佛尔酮二异氰酸酯或IPDI)、双(4-异氰酸根合环己基)-甲烷、2,4’-二环己基-甲烷二异氰酸酯、1,3-及1,4-(异氰酸根合甲基)-环己烷、双-(4-异氰酸根合-3-甲基-环己基)-甲烷、α,α,α‘,α‘-四甲基-1,3-和/或-1,4-亚二甲苯基二异氰酸酯、1-异氰酸根合-1-甲基-4(3)-异氰酸根合甲基环己烷、2,4-和/或2,6-六氢甲代亚苯基二异氰酸酯、1,3-和/或1,4-亚苯基二异氰酸酯、2,4-二异氰酸根合甲苯(及其与优选最多35wt%2,6-二异氰酸根合-甲苯的混合物,以混合物为基准计)、4,4’二苯基甲烷二异氰酸酯(及其与2,4’-二苯基-甲烷二异氰酸酯和/或2,2’-二苯基-甲烷二异氰酸酯的混合物)、1,5-二异氰酸根合萘,以及其混合物。
优选的有机二异氰酸酯包括1,6-六亚甲基二异氰酸酯、1-异氰酸根合-3-异氰酸根合甲基-3,5,5-三甲基环己烷(异佛尔酮二异氰酸酯或IPDI)、双(4-异氰酸根合环己基)-甲烷、1-异氰酸根合-1-甲基-4(3)-异氰酸根合甲基环己烷、2,4-和/或2,6-甲代亚苯基二异氰酸酯以及2,4-二苯基甲烷二异氰酸酯。最优选使用4,4’-二苯基甲烷二异氰酸酯及4,4’-二环己基甲烷二异氰酸酯。
当然,本发明的预聚物可包含催化剂、增塑剂、光稳定剂、热稳定剂、润滑剂、抗氧剂及其他添加剂。
本发明热塑性聚氨酯可用于制造聚氨酯或聚氨酯制品,例如用于弹性体、密封剂、涂料、封铸剂、吹胀薄膜、粘合剂及片材。
本发明将通过下面的实施例得到进一步的说明,然而,本发明并不受这些实施例的限制,其中所有的份数和百分数,除非另行指明,一律指重量而言。
实施例
实例1
7.0%NCO预聚物的制备:以市售材料PolyBD R45M(2501g)与MDI(997.2)为原料,在87℃下搅拌过夜。随后,该预聚物与1,4-丁二醇(252.5g)在90℃下反应使分子链得到增长,倒入模具,并在90℃下固化过夜。所生成的以R45HT为基础的聚氨酯被置于熔体指数测定仅中,在205℃,圆筒上加载10kg质量重物的条件下进行测定。该聚氨酯不流动,而发生结焦,这是由于聚氨酯中存在交联的缘故。
实例2
7.0%NCO预聚物的制备:以HFPB(317.25g)与MDI(130.50g)为原料,在87℃下搅拌过夜。随后,该预聚物(326.6g)与1,4-丁二醇(23.4g)在90℃下反应使分子链得到增长,倒入模具,并在90℃下固化过夜。所生成的试样盘柔软并象干酪似的。无法测定该材料的机械性能。该聚氨酯被置于熔体指数测定仪中,在205℃,圆筒上加载10kg质量重物的条件下进行测定。该聚氨酯在所述条件下易于流动(MFI=8g/10min)。
实例3
实例2中制备的聚氨酯在干冰中冷却,然后,在机械研磨机中磨碎。与作为加工助剂的Acrawaxc掺混之后,材料在1.5英寸单螺杆挤塑机中在如下条件下进行挤塑:
表1挤塑条件
段1,温度,℃ | 182 |
段2,温度,℃ | 182 |
段3,温度,℃ | 182 |
段4,温度,℃ | 193 |
螺杆速度,rpm | 30 |
冷却后,从挤塑机出来的线料被切成粒料。粒料在如下条件下注塑为试样盘:
表2注塑条件
段1,温度,℃ | 235 |
段2,温度,℃ | 235 |
段3,温度,℃ | 240 |
注塑时间,s | 10 |
完整周期时间,s | 45 |
注塑压力,psi | 130 |
与周围温度达到平衡之后,测定了注塑试样盘的下列性能。
表3试样的机械性能
拉伸强度,psi | 911 |
伸长,% | 196 |
伸长形变,% | 8 |
100%伸长时的模量,psi | 740 |
撕裂强度,口型C,pli(磅/延英寸) | 212 |
硬度,肖尔A | 79 |
熔体流动指数,g/10min,荷重10kg,205℃ | 8 |
以HFPB为基础的铸塑聚氨酯的低下物理性能,经过挤塑得到显著改善。这种改善,对PolyBD R45 M材料则不可能实现,因为,这种材料的官能度大于2.0,因此它们形成了交联聚氨酯,在热和压力作用下不流动。
虽然在上面为举例说明已对本发明做了详细描述,但是,应当理解,给出这些细节的目的仅限于此,且本领域技术人员能够从中联想出各种变换方案,均不偏离本发明的精神和范围,后者则唯一地由权利要求界定。
Claims (17)
1.一种制造热塑性聚氨酯材料的方法,包括下列步骤:
a)将NCO封端的预聚物与1,4-丁二醇铸塑成形为铸塑组合物;其中所述NCO封端的预聚物包含多异氰酸酯与没有支化侧链基团的、链端官能化线型非交联聚烯烃的反应体系,该聚烯烃是通过1,4-双乙酸基-2-丁烯与1,5-环辛二烯在包含钌金属碳烯配合物的催化剂存在下起反应,然后加工生成羟基而制成的,特征在于,所述聚烯烃的官能度数值,按滴定和气相渗透压法测定,为2.0或更低,且所述聚烯烃的粘度,在25℃时为800~16,000mPa.s,其中所述聚烯烃具有如下的分子结构:
HO[CH2-CH=CH(CH2)2-CH=CH-CH2]nCH2-CH=CH-CH2OH,
其中n是13~60的数均值;
b)将所述铸塑组合物挤塑成形为至少1根聚氨酯弹性体的线料;
c)对所述至少1根所述聚氨酯弹性体线料进行切粒,成形为至少1种粒料;以及
d)将所述至少1种粒料加工成形为所述热塑性聚氨酯材料。
2.按照权利要求1的方法,其中所述催化剂是双(三环己基膦)亚苄基-二氯化钌。
3.按照权利要求1的方法,其中所述预聚物的官能度为2.0或更低,NCO含量在4~15重量%的范围,且25℃的粘度为500~20,000mPa.s。
4.按照权利要求1的方法,其中是用挤塑机将所述铸塑组合物挤塑成形为至少1根聚氨酯弹性体线料的。
5.按照权利要求4的方法,其中所述挤塑机是单螺杆挤塑机。
6.按照权利要求4的方法,其中所述挤塑机是双螺杆挤塑机。
7.按照权利要求1的方法,其中所述加工是对所述粒料进行注塑。
8.按照权利要求1的方法,其中所述加工是对所述粒料进行挤塑。
9.按照权利要求1的方法,其中所述加工是对所述粒料进行薄膜吹塑。
10.一种热塑性聚氨酯材料,它是采用包括下列步骤的方法制备的:
a)将NCO封端的预聚物与二醇铸塑成形为铸塑组合物;其中所述NCO封端的预聚物包含多异氰酸酯与没有支化侧链基团的、链端官能化线型非交联聚烯烃的反应体系,该聚烯烃是通过1,4-双乙酸基-2-丁烯与1,5-环辛二烯在包含钌金属碳烯配合物的催化剂存在下起反应,然后加工生成羟基而制成的,特征在于,所述聚烯烃的官能度数值,按滴定和气相渗透压法测定,为2.0或更低,且所述聚烯烃的粘度,在25℃时为800~16,000mPa.s,其中所述聚烯烃具有如下的分子结构:
HO[CH2-CH=CH(CH2)2-CH=CH-CH2]nCH2-CH=CH-CH2OH,
其中n是13~60的数均值;
b)将所述铸塑组合物挤塑成形为至少1根聚氨酯弹性体的线料;
c)对所述至少1根所述聚氨酯弹性体线料进行切粒,成形为至少1种粒料;以及
d)将所述至少1种粒料加工成形为所述热塑性聚氨酯材料。
11.按照权利要求10的热塑性聚氨酯材料,其中所述多异氰酸酯是甲基二异氰酸酯。
12.按照权利要求10的热塑性聚氨酯材料,其中所述催化剂是双(三环己基膦)亚苄基二氯化钌。
13.按照权利要求10的热塑性聚氨酯材料,其中所述二醇是1,4-丁二醇。
14.按照权利要求10的热塑性聚氨酯材料,其中所述二醇是1,4-丁二醇,且所述多异氰酸酯是甲基二异氰酸酯。
15.按照权利要求10的热塑性聚氨酯材料,其中所述加工是对所述粒料进行注塑。
16.按照权利要求10的热塑性聚氨酯材料,其中所述加工是对所述粒料进行挤塑。
17.按照权利要求10的热塑性聚氨酯材料,其中所述加工是对所述粒料进行薄膜吹塑。
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US6780957B1 (en) * | 1999-12-29 | 2004-08-24 | Bayer Polymers Llc | Hydrophobic light stable polyurethane elastomer with improved mechanical properties |
US6476167B2 (en) * | 2000-12-14 | 2002-11-05 | Bayer Corporation | End-functionalized polyolefin prepared via ring opening metathesis polymerization in the presence of a novel chain transfer agent, and a process for the preparation of the end-functionalized polyolefin via ring opening metathesis polyermization |
US7226984B2 (en) | 2002-04-26 | 2007-06-05 | Sanyo Chemical Industries, Ltd | Binder for electrostatic image developing toner |
US7417094B2 (en) * | 2004-11-18 | 2008-08-26 | Pripro Polymer, Inc. | Cross-linked thermoplastic polyurethane/polyurea and method of making same |
US7540990B1 (en) * | 2004-11-18 | 2009-06-02 | Callaway Golf Company | Cross-linked thermoplastic polyurethane/polyurea and method of making same |
US20070033739A1 (en) * | 2005-08-12 | 2007-02-15 | Austen Timothy F | Inflatable support system having thermoplastic polyurethane construction |
CN100460437C (zh) * | 2006-08-11 | 2009-02-11 | 中国石油天然气集团公司 | 高性能多用途聚氨酯弹性体的合成方法 |
KR100864615B1 (ko) * | 2007-03-12 | 2008-10-22 | 주원테크 주식회사 | 열가소성 폴리우레탄과, 열가소성 고무와, 열가소성폴리우레탄 및 고무 공중합체 |
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CN101235129B (zh) * | 2008-03-05 | 2011-04-13 | 安徽大学 | 聚丁二烯基水性聚氨酯及其改性乳液的制备方法 |
US20150064382A1 (en) * | 2013-08-30 | 2015-03-05 | Sabic Innovative Plastics Ip B.V. | Composition and article comprising thermoplastic polyurethane and particulate engineering polymer |
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