CN106459348A - 热塑性聚氨酯、其制备和用途 - Google Patents
热塑性聚氨酯、其制备和用途 Download PDFInfo
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- CN106459348A CN106459348A CN201580017110.1A CN201580017110A CN106459348A CN 106459348 A CN106459348 A CN 106459348A CN 201580017110 A CN201580017110 A CN 201580017110A CN 106459348 A CN106459348 A CN 106459348A
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- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
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- 229960004756 ethanol Drugs 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
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- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
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- 239000013110 organic ligand Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
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- 230000035939 shock Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及热塑性聚氨酯、其制备方法及其用途。
Description
本发明涉及热塑性聚氨酯、其制备方法及其用途。
热塑性聚氨酯(TPU)由于其良好的弹性体性能和可热塑性加工性具有极大的工业重要性。关于TPU的制备、性能和应用的概述记载在例如Kunststoff Handbuch, 第7卷 "Polyurethane" , Carl Hanser Verlag, München, Wien, 1983中。TPU的其它综述可见于Kunststoffe 68 (1978), 第819-825页和Kautschuk, Gummi, Kunststoffe 35 (1982),第568-584页。
TPU大多由线性多元醇(大分子二醇)例如聚酯二醇、聚醚二醇或聚碳酸酯二醇、有机二异氰酸酯和短链的大多二官能的醇(扩链剂)形成。它们可以连续或不连续地制备。最为人所知的制备方法是带式法(Bandverfahren)(GB-A 1 057 018)和挤出机法(DE-A 1964 834)。
可热塑性加工的聚氨酯弹性体可以分步(预聚体计量加入法)或通过所有组分在一步中同时反应(一步法)形成。
TPU的加工技术是非常多样的,例如注塑、挤出、压延、粉末搪塑(powder slush)。因此可以产生用于各种不同应用的模制品、型材、薄膜、箔、外皮等,其中每种用途对聚合物材料提出特定要求。因此市场始终需要用于不同应用的具有新型或改进性能的TPU。
因此本发明的目的是提供具有改进性能的热塑性聚氨酯。
令人惊讶地,所述目的通过基于聚甲醛嵌段共聚物,特别是低聚甲醛基多元醇的热塑性聚氨酯得以实现。
本发明提供由组分a)、b)和c)在d)、e)、f)存在下的反应可得到的热塑性聚氨酯:
a) 至少一种有机二异氰酸酯,
b) 在每种情况下具有500-10000 g/mol数均分子量的对于异氰酸酯反应性的化合物,其中b)下的全部组分的数均官能度为1.8-2.5,
c) 在每种情况下具有60-490 g/mol数均分子量的扩链剂,其中c)下的全部扩链剂的数均官能度为1.8-2.5,
d) 任选的催化剂,
e) 任选的单官能链终止剂,
f) 任选的助剂和/或添加剂,
其中组分(b)包含至少一种基于低聚甲醛的多元醇(b1)。
本发明进一步提供通过a)与b)和c)在d)、e)和f)存在下的反应制备本发明的热塑性聚氨酯的方法:
a) 至少一种有机二异氰酸酯,
b) 在每种情况下具有500-10000 g/mol数均分子量的对于异氰酸酯反应性的化合物,其中b)下的全部组分的数均官能度为1.8-2.5,
c) 具有对于异氰酸酯反应性的基团和在每种情况下具有60-490 g/mol数均分子量的扩链剂,其中c)下的全部扩链剂的数均官能度为1.8-2.5,优选1.8-2.2,
d) 任选的催化剂,
e) 任选的单官能链终止剂,
f) 任选的助剂和/或添加剂,
其中组分b)包含至少一种基于低聚甲醛的多元醇(b1)。
本发明的TPU的硬度可通过结构组分(Aufbaukomponent) a)-c)相对广泛变化的摩尔比进行调节。
组分b)和c)中对于异氰酸酯反应性的基团与组分a)中的异氰酸酯基团的摩尔比优选为0.8:1.0-1.2:1.0,特别优选为0.9:1.0-1.1:1.0。
本发明的热塑性聚氨酯通过已知的方法制备,通常以一步法或预聚体法在带式设备上或在反应挤出机中进行。在此,反应中涉及的组分a)-c)在任选的d)、e)和f)存在下一起或以预定的顺序合并并进行反应。在反应挤出机法的情况下,所述结构组分a)-c)在d)和任选e)和f)存在下单独地相继或一起以混合物的形式引入到挤出机中,例如在100℃-250℃,优选150℃-230℃的温度下,并进行反应。所得TPU由挤出机中排放,冷却和造粒。
例如,可以使用已知的方法,如注塑、挤出、压延或烧结将通常以粒料或粉末的形式使用的本发明的TPU加工成为塑料部件,如薄膜、外皮、涂层和箔。
TPU的注塑和挤出是众所周知和广泛描述的。在本申请中的注塑或挤出的塑料部件是可通过注塑或挤出制备的所有形状的部件、物件和成型体(Formen)。所述注塑加工或挤出加工可以在本领域技术人员已知的常规设备上进行。用于制备所述塑料部件的加工温度通常为140℃-240℃,其中在TPU的制备过程中通过组分b)和c)中对于异氰酸酯反应性的基团与组分a)中的异氰酸酯基团之比和/或通过使用单官能链终止剂e)进行有针对性的分子量调节,可以调节有针对性的加工温度窗口。
可由本发明的TPU制备的术语“塑料部件”例如是箔、门把手和门密封件、旋转按钮和开关按钮、滑轮、车门储物盒、扶手、工具手柄、冲击吸收器、软管、电缆护套、气囊盖、仪表盘、保险杠、汽车天线、百叶窗和饮料架。
本发明的TPU的制备中通常使用的组分a)-f)例如如下进行描述:
使用的有机二异氰酸酯a)是常规的芳族、脂族和/或环脂族二异氰酸酯。可以提及的具体实例是:
芳族二异氰酸酯,例如甲苯2,4-二异氰酸酯、甲苯2,4-二异氰酸酯与甲苯2,6-二异氰酸酯的混合物、二苯基甲烷 4,4'-二异氰酸酯、二苯基甲烷2,4'-二异氰酸酯和二苯基甲烷2,2'-二异氰酸酯、二苯基甲烷2,4'-二异氰酸酯与二苯基甲烷4,4'-二异氰酸酯的混合物、氨基甲酸酯改性的液体二苯基甲烷4,4'-二异氰酸酯和二苯基甲烷2,4'-二异氰酸酯、4,4'-二异氰酸根合-1,2-二苯基乙烷、萘1,5-二异氰酸酯。优选使用具有>96重量%的二苯基甲烷4,4'-二异氰酸酯含量的二苯基甲烷二异氰酸酯异构体混合物,特别是二苯基甲烷4,4'-二异氰酸酯和萘1,5-二异氰酸酯作为芳族有机二异氰酸酯。所提及的二异氰酸酯可以单独地或以彼此的混合物的形式使用。它们也可与最多15重量%(基于二异氰酸酯的总量计)的多异氰酸酯,例如三苯基甲烷4,4',4''-三异氰酸酯或多苯基多亚甲基多异氰酸酯一起使用。
可以使用的其它二异氰酸酯a)是脂族和环脂族二异氰酸酯。例如可以提及的是六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、环己烷1,4-二异氰酸酯、1-甲基环己烷2,4-二异氰酸酯和1-甲基环己烷2,6-二异氰酸酯以及相应的异构体混合物、和二环己基甲烷4,4'-、2,4'-和2,2'-二异氰酸酯以及相应的异构体混合物。优选使用的脂族有机二异氰酸酯由至少50重量%,优选75重量%和特别优选100重量%的六亚甲基1,6-二异氰酸酯构成。
可以使用的对于异氰酸酯反应性的化合物b),除了根据本发明使用的基于低聚甲醛的多元醇之外,还有公众熟知的多羟基化合物,其数均分子量Mn为500-10000 g/mol,优选600-7500 g/mol和特别优选800-5000 g/mol,优选的数均官能度为1.8-2.5,特别优选1.8-2.2和非常特别优选1.9-2.1,其中b)中全部组分的数均官能度为1.8-2.5,实例为聚酯多元醇、聚醚酯多元醇、聚醚多元醇、聚醚碳酸酯多元醇、己内酯多元醇和聚碳酸酯多元醇。
合适的聚酯多元醇可以例如由具有2-12个碳原子,优选4-6个碳原子的二羧酸和多元醇制备。例如下面的化合物可以用作二羧酸:脂族二羧酸,例如琥珀酸、马来酸、戊二酸、己二酸、辛二酸、壬二酸和癸二酸,和芳族二羧酸,例如邻苯二甲酸、间苯二甲酸和对苯二甲酸,和所提及的二羧酸的可能的环状酸酐。所述二羧酸可以单独地或以混合物的形式,例如以琥珀酸、戊二酸和己二酸混合物的形式使用。任选地可以有利地使用相应的二羧酸衍生物,例如在醇基团中具有1-4个碳原子的羧酸二酯、羧酸酐或羧酰氯代替所述二羧酸用于制备所述聚酯二醇。多元醇的实例是具有2-10个,优选2-6个碳原子的二醇,例如乙二醇、二乙二醇、1,2-和1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、2,2-二甲基-1,3-丙二醇、3-甲基-1,5-戊二醇和二丙二醇。制备所述聚酯多元醇也可任选地一起使用基于使用的二醇计0-30摩尔%含量的具有多于2个OH基团的醇。此类多元醇的实例是三羟甲基丙烷或甘油。可以按照所希望的性能,单独地或任选以彼此的混合物的形式使用所述多元醇。其它合适的是碳酸与所提及的二醇,特别是与具有4-6个碳原子的那些,例如1,4-丁二醇或1,6-己二醇的酯,羟基羧酸例如羟基己酸的缩合产物,和内酯例如任选取代的己内酯的聚合产物。优选使用的聚酯二醇是乙二醇聚己二酸酯、1,4-丁二醇聚己二酸酯、乙二醇-1,4-丁二醇聚己二酸酯、1,6-己二醇-新戊二醇聚己二酸酯、1,6-己二醇-1,4-丁二醇聚己二酸酯和聚己内酯。所述聚酯二醇的平均分子量Mn为500-5000,优选为700-4200 g/mol,且它们可以单独地或以彼此的混合物的形式使用。
合适的聚醚多元醇可以通过一种或多种在亚烷基基团中具有2-4个碳原子的氧化烯与优选含有两个键合的活性氢原子的起始剂分子的反应来制备。氧化烯的实例可以提及:环氧乙烷、1,2-环氧丙烷、表氯醇、1,2-环氧丁烷和2,3-环氧丁烷。优选使用环氧乙烷、1,2-环氧丙烷和1,2-环氧丙烷与环氧乙烷的混合物。所述氧化烯可单独、交替相继或以混合物的形式使用。可以使用的起始剂分子的实例是:水,氨基醇,例如N-烷基二乙醇胺,例如N-甲基二乙醇胺,和二醇,例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇和1,6-己二醇。也可以任选使用起始剂分子的混合物。其它合适的聚醚二醇是四氢呋喃的含羟基的聚合产物。也可以使用基于所述二官能聚醚计0-30重量%含量的三官能聚醚,但最多以得到可热塑性加工的产物的这样的量。所述基本上线性的聚醚二醇的数均分子量Mn为500-10000g/mol,优选700-4200 g/mol。它们既可以单独地使用,也可以以彼此的混合物的形式或与所述其它多元醇的混合物的形式使用。
合适的聚碳酸酯多元醇可通过使低分子量碳酸酯,例如碳酸二甲酯、碳酸二乙酯或碳酸二苯酯与合适的多元醇,优选二醇在相应的酯交换催化剂,例如四异丙醇钛的催化下进行酯交换并消去相应的一元醇,例如甲醇、乙醇或苯酚来制备。用于低分子量碳酸酯的酯交换的合适二醇的实例是上面用于制备聚酯多元醇提及的二醇或短链聚醚二醇,例如分子量Mn为大约250 g/mol的聚四氢呋喃。特别合适的聚碳酸酯多元醇基于1,6-己二醇、1,4-丁二醇、3-甲基-1,5-戊二醇或这些二醇的混合物。所述基本上线性的聚碳酸酯多元醇的数均分子量Mn为500- 6000 g/mol,优选800-4000 g/mol。
合适的聚醚碳酸酯多元醇可优选通过氧化烯与二氧化碳在特定催化剂,例如双金属氰化物催化剂的催化下的共聚合,或如上所述通过低分子量碳酸酯与聚醚二醇的酯交换来制备。所述基本上线性的聚碳酸酯多元醇的数均分子量Mn为500-6000 g/mol,优选800-4000 g/mol。
本发明重要的聚甲醛嵌段共聚物,特别是基于低聚甲醛的多元醇b1)优选通过使氧化烯和任选的其它共聚单体(例如CO2)在双金属氰化物(DMC)催化剂存在下催化加成到至少一种具有至少一个端羟基的聚合甲醛起始剂化合物上来制备,其中
(i) 在第一步中,所述DMC催化剂在聚合甲醛起始剂化合物存在下活化,其中通过加入部分量(基于用于活化和聚合的氧化烯量的总量计)的一种或多种氧化烯活化所述DMC催化剂(“活化”),
(ii) 在第二步中,将一种或多种氧化烯以及任选的其它共聚单体加入到由步骤(i)所得的混合物中,其中步骤(ii)中使用的氧化烯可与步骤(i)中使用的氧化烯相同或不同(“聚合”),
其中在第一步(i)中DMC催化剂的活化在20℃-120℃的活化温度Tact下发生。
DMC催化剂原则上由用于环氧化物均聚的现有技术已知(参见例如US 3 404 109A、US 3 829 505 A、US 3 941 849 A和US 5 158 922 A)。例如US 5 470 813 A、EP 700949 A、EP 743 093 A、EP 761 708 A、WO 97/40086 A、WO 98/16310 A和WO 00/47649 A中描述的DMC催化剂在环氧化物均聚反应中具有非常高的活性,并且能够在非常低的催化剂浓度(25 ppm或更低)下制备聚醚多元醇。EP-A 700 949中描述的除了双金属氰化物化合物(例如六氰合钴(III)酸锌)和有机配体(例如叔丁醇)外还包含数均分子量Mn大于500 g/mol的聚醚的高活性DMC催化剂是一个典型实例。
所述DMC催化剂的用量大多为小于1重量%,优选小于0.5重量%,特别优选小于500ppm和特别是小于300 ppm,每种情况下基于所述聚醚碳酸酯多元醇的重量计。
合适的聚合甲醛起始剂化合物基本上是那些低聚和聚合形式的甲醛,其具有至少一个用于与氧化烯和与任选的其它共聚单体反应的端羟基。术语“端羟基”特别是指端部的半缩醛官能团,其是通过甲醛的聚合所产生的结构特征。例如,所述起始剂化合物可以是甲醛的线性低聚物和聚合物,其具有通式HO-(CH2O)n-H,其中n是≥ 2的整数且其中聚合甲醛典型地具有n ≥ 8且≤ 100个的重复单元。
已知甲醛在少的痕量水存在下就聚合。因此,在水溶液中取决于所述溶液的浓度和温度形成不同链长度的低聚物和聚合物的混合物,其与分子甲醛和甲醛水合物处于平衡。所谓的低聚甲醛在此作为白色的溶解性差的固体从所述溶液中沉淀并通常是具有n =8-100个甲醛重复单元的线性甲醛聚合物的混合物。优选使用这一最后提及的混合物。
适合用于本发明的TPU的聚甲醛嵌段共聚物是包含至少一个聚甲醛嵌段以及至少一个由氧化烯或氧化烯与其它共聚单体制成的额外的低聚嵌段(例如聚氧化烯嵌段或聚氧化烯碳酸酯嵌段)的聚合物,并优选不超过四位数范围内的分子量。
所述聚甲醛嵌段共聚物相对于现有聚合物提供一系列优点。例如,通过所述聚甲醛嵌段相对于其它低聚嵌段的长度,可以有针对性地控制某些物理性能,例如玻璃化转变温度、熔融范围、粘度和溶解度。所得聚甲醛嵌段共聚物的合成上可变的片段结构另外能够提供分子水平上定制的“硬-软”片段。
与相同分子量的聚甲醛均聚物相比,本发明的聚甲醛嵌段共聚物中的部分结晶度通常降低;玻璃化转变温度、熔点和粘度也更低。化学和热稳定性同样显著提高。所用的聚甲醛嵌段共聚物通常另外在不同的溶剂中具有良好的溶解度,并且大多可以容易地且没有质量损失地熔融或在低温下为液态。与聚甲醛均聚物相比,所述聚甲醛嵌段共聚物显示出显著更好的可加工性和工艺性能。
与相同分子量的聚醚多元醇相比,由相应的氧化烯制备的聚甲醛单元的含量降低对应于聚甲醛的含量,这有利于产物的有利的经济性。
可以使用的其它的对于异氰酸酯反应性的化合物c)(所谓的扩链剂)是公众熟知的多羟基化合物和/或多胺化合物,其数均分子量为60-490 g/mol,优选60-400 g/mol和特别优选62-300 g/mol,全部扩链剂c)的数均官能度优选为1.8- 2.5,优选1.8-2.2和特别优选1.9-2.1。合适的多胺化合物的实例是二胺,例如(环)脂族二胺,例如异佛尔酮二胺、乙二胺、1,2-丙二胺、1,3-丙二胺、N-甲基-1,3-丙二胺、N,N'-二甲基乙二胺,和芳族二胺,例如2,4-甲苯二胺、2,6-甲苯二胺、3,5-二乙基-2,4-甲苯二胺或3,5-二乙基-2,6-甲苯二胺或单-、二-、三-或四烷基取代的4,4'-二伯氨基二苯基甲烷。还可以使用氨基醇,例如N-2-(甲基氨基)乙醇或3-(甲基氨基)-1-丙醇作为扩链剂c)。优选使用选自以下的一种或多种化合物作为扩链剂c):具有2-14个碳原子的脂族二醇,例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,10-癸二醇、1,12-十二烷二醇、二乙二醇、二丙二醇、1,4-环己二醇、1,4-二甲醇环己烷和新戊二醇。然而,其它合适的是对苯二甲酸与具有2-4个碳原子的二醇的二酯,例如对苯二甲酸双(乙二醇)酯或对苯二甲酸双(1,4-丁二醇)酯,氢醌的羟基亚烷基醚,例如1,4-二(β-羟基乙基)氢醌,乙氧基化的双酚,例如1,4-二(β-羟基乙基)双酚A。所提及的二醇也可以与不同摩尔量的ε-己内酯以开环反应进行反应,从而得到数均分子量为最高490 g/mol的相应扩链剂。特别优选使用的扩链剂是乙二醇、1,4-丁二醇、1,6-己二醇、1,4-二甲醇环己烷、1,4-二(β-羟基乙基)氢醌和1,4-二(β-羟基乙基)双酚A和它们与ε-己内酯的反应产物。除此之外,也可以加入较少量,基于组分c)的总量计最多10重量%的三元醇,例如三羟甲基丙烷或甘油。
合适的催化剂d)可任选在本发明方法的第一和/或第二步中使用。适合用于制备TPU的催化剂是现有技术中常规和已知的叔胺,例如三乙胺、二甲基环己胺、N-甲基吗啉、N,N'-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂双环[2.2.2]辛烷,以及有机金属化合物,例如钛化合物,例如四异丙醇钛、四丁醇钛、钛螯合物,铁化合物,例如乙酰丙酮铁(III),锆化合物,例如锆螯合物,或锡化合物,例如二乙酸锡、二辛酸锡、二月桂酸锡或脂族羧酸二烷基锡盐,例如二乙酸二丁基锡或二月桂酸二丁基锡。优选的催化剂是有机金属化合物,特别是钛化合物、铁化合物、锆化合物和锡化合物。
TPU中的催化剂总量通常为大约0-5重量%,优选0.0001-1重量%并特别优选0.0002-0.5重量%。
使用的链终止剂e)可以是具有仅一个对于异氰酸酯a)反应性的基团的化合物,例如一元醇,例如乙醇、1-丙醇、2-丙醇、1-丁醇、1-己醇、1-辛醇或硬脂醇。通过此类链终止剂可以有针对性地调节分子量、熔体粘度和因此的TPU流动特性。
可以使用的其它助剂和/或添加剂f)是常规的添加剂,例如表面活性物质、阻燃剂、成核剂、润滑剂和脱模剂、染料、颜料和填料、抑制剂、针对水解、光、热、氧化或变色的稳定剂、针对微生物降解的保护剂以及增强剂和增塑剂。
本发明的TPU适合用于本身已知的塑料加工技术,例如注塑、挤出、压延、粉末搪塑等,并根据要求特征在如此制备的产物中提供改进的品质。例如在模制品的情况下,观察到与基于醚的TPU相比改进的抗张强度、刚度(模量)和更高的硬度。
应借助下面的实施例进一步解释本发明。
实施例:
使用的原料:
多元醇1:Acclaim® 2200N,基于环氧丙烷的聚醚多元醇,具有56 mg KOH/g的OH值,Bayer MaterialScience AG的商购产品。
多元醇2:聚甲醛嵌段共聚物,基于低聚甲醛(20重量%)、环氧丙烷(66重量%)和二氧化碳(14重量%),具有53 mg KOH/g的OH值。
BDO:1,4-丁二醇
MDI:二苯基甲烷4,4'-二异氰酸酯
Tyzor® AA105:钛催化剂,来自Dorf Ketal
Irganox® 1010:抗氧化剂,来自BASF AG
Licowax® C:脱模剂,来自Clariant International Ltd.。
TPU 1-3的制备
根据表1分别将多元醇、1%的Licowax® C(基于整个配制品计)和0.3%的Irganox® 1010(基于多元醇计)预先放置在反应容器中并在搅拌下加热到200°C。然后加入20 ppm的Tyzor® AA105(基于多元醇计)作为催化剂。然后在搅拌下加入全部量的加热到60℃的MDI,其中在反应容器中的温度降低至165°C。大约20秒之后,加入全部量的1,4-丁二醇。反应混合物已经达到大约215℃的温度最大值,继续剧烈搅拌(大约7-8秒)。然后将反应混合物倾倒至经涂覆的金属片上并在80℃下继续调温30分钟。冷却后得到TPU浇铸板。
表1描述了用于制备TPU的反应性组分和它们的含量。
表1:
实施例 | 多元醇1[摩尔] | 多元醇2[摩尔] | MDI[摩尔] | 1,4-丁二醇[摩尔] |
1 | 0.512 | 0.488 | 4.039 | 2.96 |
2 | 0 | 1 | 4.039 | 2.96 |
3* | 1 | 0 | 4.039 | 2.96 |
* 非根据本发明。
将所得的TPU浇铸板切割和造粒。所述粒料使用Arburg Allrounder 470S型注塑机在180-230℃的温度范围和650-750 bar压力范围内以10-35 cm3/s的注射流量加工成为棒材(模具温度:25°C;棒材尺寸:80×10×4 mm)和板材(模具温度:25°C;尺寸:125×50×2mm)。
由所制备的TPU测定熔体体积流动速率(MVR)和机械值(100%模量,300%模量,抗张强度、断裂伸长率和肖氏A硬度)。
测试条件:
1)熔体体积流动速率(MVR)
使用Göttfert的MP-D型MVR仪器根据ISO 1133在190°C和10 kg(98N)的施加重量下以5分钟预热时间测量MVR的测量值。
2)拉伸试验
拉伸试验根据DIN 53455在S1棒材上(对应于根据EN ISO 527的第5类试样,由注塑板冲压)以200 mm/min的拉伸速率进行。
3)硬度
根据DIN 53505测量硬度。
下面表2列出了测量值。
表 2:
TPU,来自 | MVR[ml/10 min.] | 100%模量[MPa] | 300%模量[MPa] | 抗张强度[MPa] | 断裂伸长率[%] | 肖氏A硬度 |
实施例1 | 8.1 | 6.7 | 9.6 | 17.0 | 680 | 86 |
实施例2 | 22.8 | 8.1 | 10.2 | 21.9 | 519 | 89 |
实施例3* | 3.0 | 5.0 | 8.4 | 16.8 | 729 | 83 |
* 非根据本发明。
在所制备的三种TPU的机械性能中发现了显著的差别。本发明的TPU1和2的100%模量、300%模量和抗张强度在每种情况下高于非根据本发明的TPU3。尽管对于全部三种TPU来说扩链剂的量是相同的,但是本发明的两种TPU的肖氏A硬度也高于对比TPU。这三种TPU的断裂伸长率值处于非常高的水平且对于所有应用而言是足够的。
Claims (3)
1.热塑性聚氨酯,其由组分a)、b)和c)在d)、e)、f)存在下的反应可得到:
a) 至少一种有机二异氰酸酯,
b) 在每种情况下具有500-10000 g/mol数均分子量的对于异氰酸酯反应性的化合物,其中b)下的全部组分的数均官能度为1.8-2.5,
c) 在每种情况下具有60-490 g/mol数均分子量的扩链剂,其中c)下的全部扩链剂的数均官能度为1.8-2.5,
d) 任选的催化剂,
e) 任选的单官能链终止剂
f) 任选的助剂和/或添加剂,
其中组分(b)包含至少一种基于低聚甲醛的多元醇(b1)。
2.通过a)与b)和c)在d)、e)和f)存在下的反应制备根据权利要求1所述的热塑性聚氨酯的方法:
a) 至少一种有机二异氰酸酯,
b) 在每种情况下具有500-10000 g/mol数均分子量的对于异氰酸酯反应性的化合物,其中b)下的全部组分的数均官能度为1.8-2.5,
c) 具有对于异氰酸酯反应性的基团和在每种情况下具有60-490 g/mol数均分子量的扩链剂,其中c)下的全部扩链剂的数均官能度为1.8-2.5,
d) 任选的催化剂,
e) 任选的单官能链终止剂,
f) 任选的助剂和/或添加剂,
其中组分(b)包含至少一种基于低聚甲醛的多元醇(b1)。
3.根据权利要求1所述的热塑性聚氨酯用于制备塑料部件的用途。
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CN108559049A (zh) * | 2018-05-11 | 2018-09-21 | 美瑞新材料股份有限公司 | 一种抗析出脂肪族热塑性聚氨酯弹性体及其制备方法 |
CN111601717A (zh) * | 2017-12-20 | 2020-08-28 | 科思创德国股份有限公司 | 基于粉末的增材制造法 |
CN111868129A (zh) * | 2018-02-28 | 2020-10-30 | 科思创知识产权两合公司 | 基于聚甲醛-聚氧化烯嵌段共聚物的聚氨酯软质泡沫材料 |
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US20180312623A1 (en) * | 2017-04-28 | 2018-11-01 | Liang Wang | Polyurethane Elastomer with High Ultimate Elongation |
EP3498746A1 (de) * | 2017-12-13 | 2019-06-19 | Covestro Deutschland AG | Verfahren zur herstellung von polyurethanpolymeren |
TW201927843A (zh) * | 2017-12-14 | 2019-07-16 | 德商巴斯夫歐洲公司 | 用於製備具有低玻璃轉變溫度的熱塑性聚胺甲酸酯的方法 |
EP3812407A1 (de) * | 2019-10-23 | 2021-04-28 | Covestro Deutschland AG | Polyurethanpolymer mit einer härte von <= 60 shore a |
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