CN117430786B - 用于充电桩线缆的高强度tpu材料及其制备方法 - Google Patents
用于充电桩线缆的高强度tpu材料及其制备方法 Download PDFInfo
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- CN117430786B CN117430786B CN202311777673.3A CN202311777673A CN117430786B CN 117430786 B CN117430786 B CN 117430786B CN 202311777673 A CN202311777673 A CN 202311777673A CN 117430786 B CN117430786 B CN 117430786B
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- charging pile
- tpu material
- pile cable
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003063 flame retardant Substances 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 24
- 229920005862 polyol Polymers 0.000 claims abstract description 23
- 150000003077 polyols Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
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- 239000012948 isocyanate Substances 0.000 claims abstract description 21
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 19
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 19
- 230000002195 synergetic effect Effects 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 6
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 10
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 6
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- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 4
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- ZQBAKBUEJOMQEX-UHFFFAOYSA-N salicylic acid phenyl ester Natural products OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 3
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- LTGPEBRDBMFYBR-UHFFFAOYSA-N ethyl 4-[(n-ethylanilino)methylideneamino]benzoate Chemical compound C1=CC(C(=O)OCC)=CC=C1N=CN(CC)C1=CC=CC=C1 LTGPEBRDBMFYBR-UHFFFAOYSA-N 0.000 claims description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
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- 239000000806 elastomer Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及聚氨酯技术领域,具体涉及用于充电桩线缆的高强度TPU材料及其制备方法。所述用于充电桩线缆的高强度TPU材料的原料包括:混合多元醇、异氰酸酯、复合扩链剂、抗氧剂、耐水解剂、催化剂、分散剂、协效阻燃剂、紫外吸收剂;混合多元醇为聚己内酯二醇、聚四亚甲基醚二醇中的至少一种与端羟丁基封端的聚二甲基硅氧烷混合;复合扩链剂为1,4‑丁二醇和三羟甲基丙烷复合;协效阻燃剂为硅烷偶联剂改性纳米Sb2O3粉体。本发明解决了阻燃剂与基体之间相容性差的问题,提升了TPU材料的阻燃效果、耐热性和力学性能。
Description
技术领域
本发明涉及聚氨酯技术领域,具体涉及用于充电桩线缆的高强度TPU材料及其制备方法。
背景技术
充电桩线缆作为新能源汽车的重要配套设施,与传统的线缆材料相比,其使用环境和安全性要求更高,因此对充电桩线缆的包覆材料也提出了更高的要求。
目前充电桩线缆的包覆材料主要有两种:一种是聚氯乙烯(PVC)为基材的弹性体材料,例如:专利CN104194220A中公开的一种电动汽车充电桩用PVC弹性体材料,虽然该弹性体材料具有较好的性能,能基本满足充电桩线缆的使用要求且价格较为低廉;但是PVC弹性体燃烧时生烟量大,不符合环保的趋势,使PVC基弹性体材料的使用大大受限。
另一种是以热塑性聚氨酯弹性体(TPU)为基材的弹性材料,该材料易加工,硬度范围宽,性能较优异,符合环保的要求;但是TPU本身属于易燃材料,为了达到充分的阻燃效果,需要加入大量的无卤阻燃剂,该类阻燃剂能够抑制燃烧或减缓火焰蔓延速度,但是大量添加会对材料的力学等性能产生很大的影响,并且填料与聚合物之间的相容性一般较差,液体阻燃剂易析出。此外,TPU材料的耐热性和力学性能也需要进一步提升。
发明内容
本发明的目的是提供一种用于充电桩线缆的高强度TPU材料,通过反应将阻燃基团接枝到聚氨酯分子链上,从根本上解决了阻燃剂与基体之间相容性差的问题,提升了TPU材料的阻燃效果,并通过端羟丁基封端的聚二甲基硅氧烷的加入、交联反应和两段螺杆连接挤出工艺提升了TPU材料的耐热性和力学性能;本发明还提供其制备方法。
本发明所述的用于充电桩线缆的高强度TPU材料,包括以下质量份数的原料:
混合多元醇50-70份,
异氰酸酯25-40份,
复合扩链剂5-10份,
抗氧剂0.1-0.3份,
耐水解剂0.05-0.2份,
催化剂0.02-0.1份,
分散剂0.01-0.03份,
协效阻燃剂0.005-0.01份,
紫外吸收剂0.05-0.3份;
所述混合多元醇为聚己内酯二醇(PCL)、聚四亚甲基醚二醇(PTMG)中的至少一种与端羟丁基封端的聚二甲基硅氧烷(PDMS)混合;
所述复合扩链剂为85-99wt.%的1,4-丁二醇(BDO)和1-15wt.%的三羟甲基丙烷(TMP)复合;
所述异氰酸酯为90-95wt.%的二苯基甲烷二异氰酸酯(MDI)和5-10wt.%的二环己基甲烷二异氰酸酯(HMDI)的混合物;
所述协效阻燃剂为硅烷偶联剂改性纳米Sb2O3粉体。
优选的,所述聚己内酯二醇和聚四亚甲基醚二醇的数均分子量为500-2000。
优选的,所述端羟丁基封端的聚二甲基硅氧烷的数均分子量为1500-2000,结构式如下:
。
优选的,所述混合多元醇中,端羟丁基封端的聚二甲基硅氧烷的质量百分比为5-15%。
优选的,所述硅烷偶联剂改性纳米Sb2O3粉体中,纳米Sb2O3粉体的平均粒径在30-50nm之间。
硅烷偶联剂改性的目的是改善纳米Sb2O3粉体的分散性和相容性。其中,硅烷偶联剂采用市售硅烷偶联剂型号均可,例如硅烷偶联剂KH-550、硅烷偶联剂KH-560等,其型号的改变对改性效果无明显影响;硅烷偶联剂的使用量为纳米Sb2O3粉体质量的0.05-0.2%,在该用量范围内均能起到较好的改性效果。
在一种实施方式中,所述硅烷偶联剂改性纳米Sb2O3粉体的制备方法如下:
将平均粒径在30-50nm之间的纳米Sb2O3粉体、硅烷偶联剂KH-550、无水乙醇按照质量比1:0.05:2共同置于球磨罐中,在转速500r/min条件下球磨10h,然后真空干燥,得到硅烷偶联剂改性纳米Sb2O3粉体。
优选的,所述抗氧剂为亚磷酸酯类抗氧剂;进一步优选为亚磷酸三(2,4-二叔丁基苯基)酯。
优选的,所述耐水解剂为碳化二亚胺。
优选的,所述催化剂为有机锡催化剂;进一步优选为辛酸亚锡。
优选的,所述分散剂为硬脂酸单甘油酯、三硬脂酸甘油酯、硬脂酸钡、硬脂酸钙中的至少一种;进一步优选为质量比1:1.5的硬脂酸单甘油酯和三硬脂酸甘油酯的混合物。
优选的,所述紫外吸收剂为N-(乙氧基羰基苯基)-N'-甲基-N'-苯基脒(UV-1)、N-(乙氧基羰基苯基)-N'-乙基-N'-苯基甲脒(UV-2)、邻羟基苯甲酸苯酯、2-(2'-羟基-5'-甲基苯基)苯并三氮唑(UV-P)、2,4-二羟基二苯甲酮(UV-O)、2-羟基-4-甲氧基二苯甲酮(UV-9)、2-羟基-4-正辛氧基二苯甲酮(UV-531)中的至少一种;进一步优选为N-(乙氧基羰基苯基)-N'-甲基-N'-苯基脒(UV-1)。
本发明所述的用于充电桩线缆的高强度TPU材料的制备方法,包括以下步骤:
采用中双轴双螺杆和长双轴双螺杆连接的两段式双螺杆挤出机进行连续聚合反应,先将抗氧剂、耐水解剂、分散剂、协效阻燃剂、紫外吸收剂加到混合多元醇中,与部分异氰酸酯和催化剂在中双轴双螺杆内进行预聚反应,得到预聚物;再将预聚物输送至长双轴双螺杆内,与剩余异氰酸酯和复合扩链剂进行聚合反应,经水下切造粒得到用于充电桩线缆的高强度TPU材料。
优选的,中双轴双螺杆分四个温区,从第一区到第四区的温度依次为180℃、185℃、185℃、190℃;主机转速为180r/min。
优选的,长双轴双螺杆分十四个温区,从第一区到第十四区的温度依次为190℃、195℃、200℃、205℃、200℃、195℃、185℃、180℃、165℃、165℃、165℃、165℃、180℃、190℃;模头出口温度为215℃;主机转速为210r/min。
在一种实施方式中,所述用于充电桩线缆的高强度TPU材料的制备方法,具体包括以下步骤:
(1)将抗氧剂、耐水解剂、分散剂、协效阻燃剂、紫外吸收剂加到混合多元醇里,通过搅拌头混合,经混合器灌注到中双轴双螺杆第一区,催化剂由另一台设备连续灌注注入中双轴双螺杆的混合器,1/2量的异氰酸酯灌注到中双轴双螺杆第一区,在中双轴双螺杆内进行预聚反应,得到预聚物;中双轴双螺杆共四个主机筒加热温区,各区分段加热控温,从第一区到第四区的温度依次为180℃、185℃、185℃、190℃,主机转速180r/min;
(2)预聚物经中双轴双螺杆输送至长双轴双螺杆主机筒第一区,扩链剂灌注到长双轴双螺杆主机筒第一区,剩余1/2量的异氰酸酯灌注到长双轴双螺杆主机筒第二区,在长双轴双螺杆内进行聚合反应,经水下切造粒、干燥,得到用于充电桩线缆的高强度TPU材料;长双轴双螺杆共十四个主机筒加热温区,各区分段加热控温,从第一区到第十四区的温度依次为190℃、195℃、200℃、205℃、200℃、195℃、185℃、180℃、165℃、165℃、165℃、165℃、180℃、190℃,模头出口温度为215℃,主机转速为210r/min。
与现有技术相比,本发明的有益效果如下:
(1)本发明采用聚己内酯二醇、聚四亚甲基醚二醇中的至少一种与端羟丁基封端的聚二甲基硅氧烷混合作为软段,合成含硅嵌段TPU,促进聚氨酯的微相分离,提升聚氨酯材料的耐水性和力学性能;
(2)本发明通过加入硅烷偶联剂改性纳米Sb2O3粉体作为协效阻燃剂,有效提高了聚氨酯材料的阻燃性,且硅烷偶联剂改性纳米Sb2O3粉体与聚氨酯可以通过反应接枝到聚氨酯分子链上,从根本上解决了阻燃剂与基体之间相容性差的问题,同时提高了聚氨酯材料的耐热性和阻燃效果;
(3)本发明采用小分子二醇与三羟甲基丙烷混合作为扩链剂,通过交联反应进一步提升聚氨酯材料的力学性能;
(4)本发明采用少量的HMDI和MDI混合,在确保TPU材料力学性能的基础上,可以提高TPU材料的透明性和耐黄变性;
(5)本发明采用中双轴双螺杆和长双轴双螺杆连接的生产工艺,通过中双轴双螺杆预聚反应输送,长双轴双螺杆输送混炼聚合反应,连续生产,大大提高了材料的稳定性和加工性能,生产效率高,安全环保,同时两段螺杆挤出工艺使聚氨酯的分子链段分布更加均匀,得到的聚氨酯分子链更长,提高了材料的力学性能。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例中所使用的原料,如无特别说明,均为市售常规原料;实施例中所使用的工艺方法,如无特别说明,均为本领域常规方法。
实施例中所采用的硅烷偶联剂改性纳米Sb2O3粉体的制备方法如下:
将平均粒径在30-50nm之间的纳米Sb2O3粉体、硅烷偶联剂KH-550、无水乙醇按照质量比1:0.05:2共同置于球磨罐中,在转速500r/min条件下球磨10h,然后真空干燥,得到硅烷偶联剂改性纳米Sb2O3粉体。
实施例中所采用的PTMG-1500、PTMG-2000数均分子量依次为1500、2000,由晓星化工(嘉兴)有限公司生产;
实施例中所采用的PCL-1500、PCL-500数均分子量依次为1500、500,由湖南聚仁新材料股份公司生产;
实施例中所采用的PDMS数均分子量在1500-2000之间,结构式如下:
。
实施例1
一种用于充电桩线缆的高强度TPU材料,包括以下质量份数的原料:
混合多元醇(质量比90:10的PTMG-1500和PDMS)60份,
异氰酸酯(质量比95:5的MDI和HMDI)30份,
复合扩链剂(质量比96:4的BDO和TMP)10份,
抗氧剂(亚磷酸三(2,4-二叔丁基苯基)酯)0.2份,
耐水解剂(碳化二亚胺)0.15份,
催化剂(辛酸亚锡)0.07份,
分散剂(质量比1:1.5的硬脂酸单甘油酯和三硬脂酸甘油酯)0.02份,
协效阻燃剂(硅烷偶联剂改性纳米Sb2O3粉体)0.01份,
紫外吸收剂(UV-1)0.15份。
制备方法如下:
(1)将抗氧剂、耐水解剂、分散剂、协效阻燃剂、紫外吸收剂加到混合多元醇里,通过搅拌头混合,经混合器灌注到中双轴双螺杆第一区,催化剂由另一台设备连续灌注注入中双轴双螺杆的混合器,1/2量的异氰酸酯灌注到中双轴双螺杆第一区,在中双轴双螺杆内进行预聚反应,得到预聚物;中双轴双螺杆共四个主机筒加热温区,各区分段加热控温,从第一区到第四区的温度依次为180℃、185℃、185℃、190℃,主机转速180r/min;
(2)预聚物经中双轴双螺杆输送至长双轴双螺杆主机筒第一区,复合扩链剂灌注到长双轴双螺杆主机筒第一区,剩余1/2量的异氰酸酯灌注到长双轴双螺杆主机筒第二区,在长双轴双螺杆内进行聚合反应,经水下切造粒、干燥,得到用于充电桩线缆的高强度TPU材料;长双轴双螺杆共十四个主机筒加热温区,各区分段加热控温,从第一区到第十四区的温度依次为190℃、195℃、200℃、205℃、200℃、195℃、185℃、180℃、165℃、165℃、165℃、165℃、180℃、190℃,模头出口温度为215℃,主机转速为210r/min。
实施例2
本实施例与实施例1的不同点仅在于,混合多元醇中PTMG-1500和PDMS的质量比为95:5。
实施例3
本实施例与实施例1的不同点仅在于,混合多元醇中PTMG-1500和PDMS的质量比为85:15。
实施例4
一种用于充电桩线缆的高强度TPU材料,包括以下质量份数的原料:
混合多元醇(质量比45:45:10的PCL-500、PTMG-2000、PDMS)70份,
异氰酸酯(质量比92:8的MDI和HMDI)25份,
复合扩链剂(质量比90:10的BDO和TMP)5份,
抗氧剂(亚磷酸三(2,4-二叔丁基苯基)酯)0.3份,
耐水解剂(碳化二亚胺)0.1份,
催化剂(辛酸亚锡)0.05份,
分散剂(三硬脂酸甘油酯)0.03份,
协效阻燃剂(硅烷偶联剂改性纳米Sb2O3粉体)0.005份,
紫外吸收剂(UV-P)0.1份。
制备方法同实施例1。
实施例5
一种用于充电桩线缆的高强度TPU材料,包括以下质量份数的原料:
混合多元醇(质量比90:10的PCL-1500和PDMS)65份,
异氰酸酯(质量比95:5的MDI和HMDI)28份,
复合扩链剂(质量比99:1的BDO和TMP)7份,
抗氧剂(亚磷酸三(2,4-二叔丁基苯基)酯)0.2份,
耐水解剂(碳化二亚胺)0.2份,
催化剂(辛酸亚锡)0.1份,
分散剂(硬脂酸镁)0.01份,
协效阻燃剂(硅烷偶联剂改性纳米Sb2O3粉体)0.01份,
紫外吸收剂(UV-O)0.3份。
制备方法同实施例1。
实施例6
一种用于充电桩线缆的高强度TPU材料,包括以下质量份数的原料:
混合多元醇(质量比90:10的PCL-1500和PDMS)50份,
异氰酸酯(质量比90:10的MDI和HMDI)40份,
复合扩链剂(质量比85:15的BDO和TMP)10份,
抗氧剂(亚磷酸三(2,4-二叔丁基苯基)酯)0.1份,
耐水解剂(碳化二亚胺)0.05份,
催化剂(辛酸亚锡)0.02份,
分散剂(硬脂酸单甘油酯)0.03份,
协效阻燃剂(硅烷偶联剂改性纳米Sb2O3粉体)0.01份,
紫外吸收剂(UV-2)0.05份。
制备方法同实施例1。
对比例1
本对比例与实施例1的不同点仅在于,将混合多元醇替换为等质量份数的PTMG-1500。
对比例2
本对比例与实施例1的不同点仅在于,不添加协效阻燃剂(硅烷偶联剂改性纳米Sb2O3粉体)。
对比例3
本对比例与实施例1的不同点仅在于,复合扩链剂中BDO和TMP的质量比为80:20。
对比例4
本对比例与实施例1的不同点仅在于,将复合扩链剂替换为等质量份数的BDO。
对比例5
本对比例与实施例1的不同点仅在于,异氰酸酯采用质量比80:20的MDI和HMDI。
对比例6
本对比例与实施例1采用相同的原料组成,不同点仅在于制备方法只使用长双轴双螺杆,具体如下:
将抗氧剂、耐水解剂、分散剂、协效阻燃剂、紫外吸收剂加到混合多元醇里,通过搅拌头混合,经混合器灌注到长双轴双螺杆主机筒第一区,复合扩链剂灌注到长双轴双螺杆主机筒第一区,催化剂由另一台设备连续灌注注入长双轴双螺杆的混合器,异氰酸酯灌注到长双轴双螺杆主机筒第一区,在长双轴双螺杆内进行聚合反应,经水下切造粒、干燥,得到用于充电桩线缆的高强度TPU材料。
将各实施例和对比例制备的TPU材料进行性能测试,其中:
拉伸强度、断裂伸长率、100%定伸应力参照标准ASTM-D412进行测试;
撕裂强度参照标准ASTM-D624进行测试;
透光率测试方法为:将TPU材料注塑成2mm厚的试片,采用彩谱分光测色仪CS-820测试试片透光率;
阻燃等级按照UL94垂直燃烧试验方法进行测试,阻燃等级由高到低依次为V-0、V-1、V-2;
析出情况测试条件为:将试样在60℃下放置120h,取出后室温下静置3h,观察并记录试样表面析出情况,并按照析出量多少分为无析出、轻微析出、明显析出三个级别;
耐高温老化性测试条件为:将试样在100℃下放置168h,取出后室温下静置2h,测试拉伸强度、断裂伸长率;
耐水性测试条件为:将试样在80℃水中放置168h,取出后室温下静置1h,测试拉伸强度、断裂伸长率。
测试结果如表1所示。
表1
从表1可以看出,本发明的实施例1-6使用PDMS合成嵌段TPU,通过反应阻燃和协效阻燃、扩链剂交联、中双轴双螺杆和长双轴双螺杆连接的连续生产工艺,制备的TPU材料阻燃等级高,力学性能好,透明度高,耐热性和耐水性好,无析出。与实施例1相比,对比例1的多元醇中不添加PDMS,TPU材料的力学性能提高,但耐热性、耐水性和阻燃等级降低;对比例2不添加协效阻燃剂,力学性能略高,但阻燃等级降低;对比例3的扩链剂中TMP含量超过临界值,TPU材料的力学性能有所下降;对比例4的扩链剂中不添加TMP,TPU材料的力学性能变差;对比例5的异氰酸酯增加HMDI的含量,TPU材料的力学性能降低,TPU材料的透光率变高;对比例6的异氰酸酯使用单一组分MDI,TPU材料的透光率降低;对比例7仅使用长双轴双螺杆生产工艺,TPU材料的力学性能变差。
Claims (8)
1.一种用于充电桩线缆的高强度TPU材料,其特征在于:包括以下质量份数的原料:
混合多元醇50-70份,
异氰酸酯25-40份,
复合扩链剂5-10份,
抗氧剂0.1-0.3份,
耐水解剂0.05-0.2份,
催化剂0.02-0.1份,
分散剂0.01-0.03份,
协效阻燃剂0.005-0.01份,
紫外吸收剂0.05-0.3份;
所述混合多元醇为聚己内酯二醇、聚四亚甲基醚二醇中的至少一种与端羟丁基封端的聚二甲基硅氧烷混合;混合多元醇中,端羟丁基封端的聚二甲基硅氧烷的质量百分比为5-15%;
所述复合扩链剂为85-99wt.%的1,4-丁二醇和1-15wt.%的三羟甲基丙烷复合;
所述异氰酸酯为90-95wt.%的二苯基甲烷二异氰酸酯和5-10wt.%的二环己基甲烷二异氰酸酯的混合物;
所述协效阻燃剂为硅烷偶联剂改性纳米Sb2O3粉体;
所述用于充电桩线缆的高强度TPU材料的制备方法,包括以下步骤:
采用中双轴双螺杆和长双轴双螺杆连接的两段式双螺杆挤出机进行连续聚合反应,先将抗氧剂、耐水解剂、分散剂、协效阻燃剂、紫外吸收剂加到混合多元醇中,与部分异氰酸酯和催化剂在中双轴双螺杆内进行预聚反应,得到预聚物;再将预聚物输送至长双轴双螺杆内,与剩余异氰酸酯和复合扩链剂进行聚合反应,经水下切造粒,得到用于充电桩线缆的高强度TPU材料。
2.根据权利要求1所述的用于充电桩线缆的高强度TPU材料,其特征在于:所述聚己内酯二醇和聚四亚甲基醚二醇的数均分子量为500-2000;所述端羟丁基封端的聚二甲基硅氧烷的数均分子量为1500-2000。
3.根据权利要求1所述的用于充电桩线缆的高强度TPU材料,其特征在于:所述硅烷偶联剂改性纳米Sb2O3粉体中,纳米Sb2O3粉体的平均粒径在30-50nm之间。
4.根据权利要求1所述的用于充电桩线缆的高强度TPU材料,其特征在于:所述抗氧剂为亚磷酸酯类抗氧剂。
5.根据权利要求1所述的用于充电桩线缆的高强度TPU材料,其特征在于:所述耐水解剂为碳化二亚胺。
6.根据权利要求1所述的用于充电桩线缆的高强度TPU材料,其特征在于:所述催化剂为有机锡催化剂。
7.根据权利要求1所述的用于充电桩线缆的高强度TPU材料,其特征在于:所述分散剂为硬脂酸单甘油酯、三硬脂酸甘油酯、硬脂酸钡、硬脂酸钙中的至少一种。
8.根据权利要求1所述的用于充电桩线缆的高强度TPU材料,其特征在于:所述紫外吸收剂为N-(乙氧基羰基苯基)-N'-甲基-N'-苯基脒、N-(乙氧基羰基苯基)-N'-乙基-N'-苯基甲脒、邻羟基苯甲酸苯酯、2-(2'-羟基-5'-甲基苯基)苯并三氮唑、2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮中的至少一种。
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