CN115433452B - 高硬度热塑性聚氨酯弹性体及其制备方法 - Google Patents
高硬度热塑性聚氨酯弹性体及其制备方法 Download PDFInfo
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 13
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- DNNXXFFLRWCPBC-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C1=CC=CC=C1 DNNXXFFLRWCPBC-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及热塑性聚氨酯弹性体领域,具体为一种高硬度热塑性聚氨酯弹性体及其制备方法。本发明通过强酸对碳纳米管和炭黑进行处理,将表面不稳定的碳原子氧化成羧基;采用含多个端基为‑NH2的树枝状聚合物PAMAM接枝碳纳米管和炭黑,制得复合材料碳纳米管/PAMAM/炭黑;再经过碳酸二甲酯进行改性,将PAMAM的端基‑NH2与甲酸酯的羰基反应得到氨基甲酸酯基,改性后的复合材料碳纳米管/PAMAM/炭黑作为加工助剂能更均匀地分散在聚氨酯中,充分发挥炭黑和碳纳米管的作用,综合提高热塑性聚氨酯弹性体的性能。
Description
技术领域
本发明涉及热塑性聚氨酯弹性体技术领域,具体为一种高硬度热塑性聚氨酯弹性体及其制备方法。
背景技术
热塑性聚氨酯弹性体又称热塑性聚氨酯橡胶,是一种性能介于塑料和橡胶之间的高分子合成材料,受热可塑化,能被溶剂溶解,具有高强度、高韧性、耐磨、耐油等优异的综合性能。热塑性聚氨酯弹性体分子主要由软段和硬段组成,受热力学控制,软段和硬段会自发分离,形成软段相和硬段相,分别赋予热塑性聚氨酯弹性和强度。
热塑性聚氨酯弹性体的硬度范围宽泛且可调控,从邵氏硬度65A至邵氏硬度85D之间,随着硬度的不断提高,其加工难度加大且往往表现出一定刚性。不同硬度的聚氨酯弹性体具有不同的应用场景,浇注型高硬度聚氨酯弹性体可以通过模具浇注替代不同形状的金属作为工程材料,可减轻物体的重量,节能降噪;聚醚型弹性体的韧性极佳且耐低温性能强,可以替代ABS等塑料在低温下使用。
热塑性聚氨酯弹性体的制备主要涉及多异氰酸酯、低聚物多元醇(氨)和扩链剂三种原料,每种原料都有非常多的选择,因此在合成热塑性聚氨酯弹性体时,可根据实际应用需要选择原料。随着汽车工业、机械制造、医疗产业、交通运输的迅速发展,人们对高硬度热塑性聚氨酯弹性体的需求越来越大,对性能要求也越来越高,因此亟需对现有工艺进行改性,制备耐老化、高强度、高硬度的热塑性聚氨酯弹性体。
发明内容
本发明的目的在于提供一种高硬度热塑性聚氨酯弹性体及其制备方法,以解决上述背景技术中提出的问题。
为了解决上述技术问题,本发明提供如下技术方案:一种高硬度热塑性聚氨酯弹性体的制备方法,包括以下重量组分:100~110份A组分,25~36份B组分,15~25份加工助剂;包括以下制备步骤:
步骤(1):制备A组分:
向反应釜中加入多元醇,高温脱水后降温至室温,再加入混合异氰酸酯,通入氮气保护,加热反应后降温至室温,加入小分子醇和混合异氰酸酯,再次加热反应,经过真空脱泡,降温出料;
步骤(2):选择扩链剂作为B组分:液体扩链剂可直接使用,固态扩链剂需加热熔化后备用;
步骤(3):制备加工助剂:
S1:炭黑粉末和碳纳米管的预处理:
将炭黑粉末和碳纳米管粉末加入强酸溶液中,超声水浴,再经过洗涤、过滤、干燥得到酸化炭黑和酸化碳纳米管;
S2:制备碳纳米管/PAMAM复合材料C:
将PAMAM溶于甲醇中,加入酸化碳纳米管,超声分散后加热反应,再经过洗涤、过滤、干燥得到碳纳米管/PAMAM复合材料C;
S3:酸化炭黑和复合材料C的复合与改性:
将碳纳米管/PAMAM复合材料C溶于丙酮,加入酸化炭黑,超声分散后加热复合得到碳纳米管/PAMAM/炭黑复合材料;随后加入催化剂、促进剂、碳酸二甲酯改性,清洗、过滤、干燥后得到加工助剂;
步骤(4):将A组分、B组分和加工助剂混合,搅拌均匀后真空脱泡浇注入模具内固化,得到高硬度聚氨酯弹性体。
步骤(1)中,所述A组分包括以下重量组分:
多元醇: 100~110份;
小分子醇: 10~20份;
混合异氰酸酯:60~120份
进一步的,多元醇脱水温度为100~130℃;两次加热反应条件为:温度80~90℃,时间2h;所述多元醇为聚碳酸酯多元醇、聚己内脂多元醇、聚四氢呋喃多元醇、聚环氧丙烯多元醇中的任一种,数均分子量为1200~2500;所述小分子醇为1,4-丁二醇、1,4-环己烷二甲醇、二乙二醇、1,2-丙二醇中的任一种;混合异氰酸酯为对苯二异氰酸酯、异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、三甲硅烷基异氰酸酯等中的两种混合,质量比为1:1~1:1.5;
步骤(2)中,所述扩链剂为二羟甲基丙酸、二邻氯苯胺甲烷、甲基丙二醇、乙二胺、2,4-二氨基-3甲硫基-5丙基氯苯、N,N-二羟基(二异丙基)苯胺中的任一种;
步骤S1中,所述强酸为质量浓度65%的浓硝酸或70%的浓硫酸;水浴温度:60~90℃;酸氧化时间:3h;干燥条件:温度70~100℃,真空度-0.1~-0.05MPa;按重量计,2.5~5份炭黑;2.5~5份碳纳米管,15份强酸溶液;
步骤S2中,所述PAMAM选择末端基团为-NH2;所述加热反应温度为85~95℃,反应时间为12h;
进一步的,所述PAMAM为C62H128N26O12、C142H288N58O28、C302H608N122O28中的任一种;按重量计,2.5~5份酸化碳纳米管,1.5~2份PAMAM,70~85份甲醇;
步骤S3中,按重量计,1~1.5份碳纳米管/PAMAM复合材料C,2.5~5份酸化炭黑,30份丙酮,20~30份碳酸二甲酯,5~8份催化剂,3~6份促进剂;所述催化剂为甲醇钠、甲醇钙、乙醇钙、乙醇钾、叔丁醇钡中的任一种;所述促进剂为甲酸甲酯、乙酸甲酯、丙烯酸甲酯中的任一种;复合温度为60~85℃,复合时间为12h;改性温度为70~80℃,改性时间为12h;
步骤(4)中,各组分混合温度为60~80℃;搅拌速度为1200rpm~1500rpm;搅拌时间为3~5min;固化温度为100~120℃,固化时间为20~24h。
前述方法制备的高硬度聚氨酯弹性体。
与现有技术相比,本发明所达到的有益效果是:将炭黑作为加工助剂合成高硬度热塑性聚氨酯弹性体,能有效增强硬度和抗老化性能,但炭黑存在会导致拉伸强度出现降低。加入碳纳米管能提高聚氨酯的拉伸强度,解决这一问题。因此可以同时用炭黑和碳纳米管对聚氨酯弹性体进行改性,但是使用研磨法将炭黑和碳纳米管物理混合后,会面临混合物在聚氨酯中分散不均匀的问题,甚至会有负面影响。而经强酸处理的碳纳米管和炭黑表面不稳定的碳原子被氧化成羧基,能与端基为-NH2的树枝状聚合物PAMAM(聚酰胺-胺型树枝状高分子)复合。复合后的碳纳米管/PAMAM/炭黑为大分子网状结构,提高交联作用;经过碳酸二甲酯改性后,PAMAM端基-NH2与甲酸酯基反应得到氨基甲酸酯基,改性后的复合材料碳纳米管/PAMAM/炭黑作为加工助剂,能更好地分散在聚氨酯中,有效提高聚氨酯弹性体的硬度、拉伸强度和抗老化能力。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
以下实施例中,材料来源如下:
异氟尔酮二异氰酸酯(CAS号:4098-71-9,南京国晨化工有限公司);苯二异氰酸酯(CAS号:104-49-4,湖北世能化工科技有限公司);聚碳酸酯多元醇(CAS号:32472-85-8,青岛瑞诺化工有限公司);乙二胺(CAS号:107-15-3;南京华曦化工有限公司);浓硝酸(CAS号:7697-37-2;扬州市江都区龙业化工厂);炭黑(天津宝驰化工科技有限公司);碳纳米管(天津宝驰化工科技有限公司);C62H128N26O12(威海晨源,牌号CYD-110A);丙酮(CAS号:67-64-1,浙江润东新材料有限公司);甲醇(CAS号:67-56-1,南通市耀鑫化工有限公司);甲酸甲酯(CAS号:107-31-3,上海波以尔化工有限公司);碳酸二甲酯(CAS号:616-38-6,无锡友为化工有限公司)。
实施例1
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1混合制备混合异氰酸酯;向反应釜中加入100份聚碳酸酯多元醇(数均分子量为1200),在100℃下脱水后,降温至室温;加入50份混合异氰酸酯,通入氮气保护,80℃下反应2h,降温至室温;加入10份二乙二醇和10份混合异氰酸酯,80℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):制备加工助剂:
S1:炭黑粉末预处理:
将2.5份炭黑粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至60℃,酸氧化3h,再经过洗涤、过滤,在70℃、-0.1MPa环境下干燥得到酸化炭黑;将2.5份碳纳米管粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至60℃,酸氧化3h,再经过洗涤、过滤,在70℃、-0.1MPa环境下干燥得到酸化碳纳米管;
S2:制备碳纳米管/PAMAM复合材料C:
将1.5份C62H128N26O12溶于70份甲醇中,加入2.5份酸化碳纳米管,超声分散后加热至85℃反应12h,再经过洗涤、过滤、干燥得到碳纳米管/PAMAM复合材料C;
S3:酸化炭黑和复合材料C的复合与改性:
将1份碳纳米管/PAMAM复合材料C溶于30份丙酮,加入2.5份酸化炭黑,超声分散后加热至60℃反应12h得到碳纳米管/PAMAM/炭黑复合材料,随后分别加入5份甲醇钠、3份甲酸甲酯、20份碳酸二甲酯进行改性,70℃下搅拌反应12h,清洗、过滤、干燥后得到加工助剂;
步骤(4):将100份A组分、25份B组分和15份加工助剂在60℃下混合,搅拌速度为1200rpm,搅拌时间为3min,真空脱泡浇注入模具内固化,固化温度为100℃,固化时间为24h,得到高硬度聚氨酯弹性体。
实施例2
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1.5混合制备混合异氰酸酯;向反应釜中加入107份聚碳酸酯多元醇(数均分子量为1800),在120℃下脱水后,降温至室温;加入70份混合异氰酸酯,通入氮气保护,85℃下反应2h,降温至室温;加入15份二乙二醇和25份混合异氰酸酯,85℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):制备加工助剂:
S1:炭黑粉末和碳纳米管粉末预处理:
将分别将3份炭黑粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至80℃,酸氧化3h,再经过洗涤、过滤,在85℃、-0.06MPa环境下干燥得到酸化炭黑;将4份碳纳米管粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至80℃,酸氧化3h,再经过洗涤、过滤,在85℃、-0.06MPa环境下干燥得到酸化碳纳米管;
S2:制备碳纳米管/PAMAM复合材料C:
将1.8份C62H128N26O12溶于80份甲醇中,加入3份酸化碳纳米管,超声分散后加热至90℃反应12h,再经过洗涤、过滤、干燥得到碳纳米管/PAMAM复合材料C;
S3:酸化炭黑和复合材料C的复合与改性:
将1.2份碳纳米管/PAMAM复合材料C溶于30份丙酮,加入3.5份酸化炭黑,超声分散后加热至75℃反应12h,得到碳纳米管/PAMAM/炭黑复合材料,随后分别加入7份甲醇钠、5份甲酸甲酯、24份碳酸二甲酯,75℃下搅拌反应12h,清洗、过滤、干燥后得到加工助剂;
步骤(4):将105份A组分、30份B组分和28份加工助剂在70℃下混合,搅拌速度为1400rpm,搅拌时间为4min,真空脱泡浇注入模具内固化,固化温度为110℃,固化时间为22h,得到高硬度聚氨酯弹性体。
实施例3
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1.9混合制备混合异氰酸酯;向反应釜中加入110份聚碳酸酯多元醇(数均分子量为2500),在130℃下脱水后,降温至室温;加入80份混合异氰酸酯,通入氮气保护,95℃下反应2h,降温至室温;加入20份二乙二醇和45份混合异氰酸酯,90℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):制备加工助剂:
S1:炭黑粉末和碳纳米管粉末预处理:
将5份炭黑粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至90℃,酸氧化3h,再经过洗涤、过滤,在100℃、-0.05MPa环境下干燥得到酸化炭黑;将5份碳纳米管粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至90℃,酸氧化3h,再经过洗涤、过滤,在100℃、-0.05MPa环境下干燥得到酸化碳纳米管;
S2:制备碳纳米管/PAMAM复合材料C:
将2份C62H128N26O12溶于85份甲醇中,加入5份酸化碳纳米管,超声分散后加热至95℃反应12h,再经过洗涤、过滤、干燥得到碳纳米管/PAMAM复合材料C;
S3:酸化炭黑和复合材料C的复合与改性:
将1.5份碳纳米管/PAMAM复合材料C溶于30份丙酮,加入5份酸化炭黑,超声分散后加热至85℃反应12h,得到碳纳米管/PAMAM/炭黑复合材料,随后分别加入8份甲醇钠、6份甲酸甲酯、30份碳酸二甲酯,80℃下搅拌反应12h,清洗、过滤、干燥后得到加工助剂;
步骤(4):将110份A组分、36份B组分和25份加工助剂在80℃下混合,搅拌速度为1500rpm,搅拌时间为5min,真空脱泡浇注入模具内固化,固化温度为120℃,固化时间为24h,得到高硬度聚氨酯弹性体。
对比例1
不加入加工助剂。
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1混合制备混合异氰酸酯;向反应釜中加入100份聚碳酸酯多元醇(数均分子量为1200),在100℃下脱水后,降温至室温;加入50份混合异氰酸酯,通入氮气保护,80℃下反应2h,降温至室温;加入10份二乙二醇和10份混合异氰酸酯,80℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):将100份A组分、25份B组分在60℃下混合,搅拌速度为1200rpm,搅拌时间为3min,真空脱泡浇注入模具内固化,固化温度为100℃,固化时间为24h,得到高硬度聚氨酯弹性体。
对比例2
按质量比1:1将炭黑和碳纳米管混合研磨后作为加工助剂直接加入合成热塑性聚氨酯弹性体。
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1.5混合制备混合异氰酸酯;向反应釜中加入107份聚碳酸酯多元醇(数均分子量为1800),在120℃下脱水后,降温至室温;加入70份混合异氰酸酯,通入氮气保护,85℃下反应2h,降温至室温;加入15份二乙二醇和25份混合异氰酸酯,85℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):将105份A组分、30份B组分、28份炭黑/碳纳米管混合物在70℃下混合,搅拌速度为1400rpm,搅拌时间为4min,真空脱泡浇注入模具内固化,固化温度为110℃,固化时间为22h,得到高硬度聚氨酯弹性体。
对比例3
不用强酸处理炭黑和碳纳米管。
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1.5混合制备混合异氰酸酯;向反应釜中加入107份聚碳酸酯多元醇(数均分子量为1800),在120℃下脱水后,降温至室温;加入70份混合异氰酸酯,通入氮气保护,85℃下反应2h,降温至室温;加入15份二乙二醇和25份混合异氰酸酯,85℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):制备加工助剂:
S1:制备碳纳米管/PAMAM复合材料C:
将1.8份C62H128N26O12溶于80份甲醇中,加入3份碳纳米管,超声分散后加热至90℃反应12h,再经过洗涤、过滤、干燥得到碳纳米管/PAMAM复合材料C;
S2:酸化炭黑和复合材料C的复合与改性:
将1.2份碳纳米管/PAMAM复合材料C溶于30份丙酮,加入3.5份炭黑,超声分散后加热至75℃反应12h,随后分别加入7份甲醇钠、5份甲酸甲酯、24份碳酸二甲酯,75℃下搅拌反应12h,清洗、过滤、干燥后得到加工助剂;
步骤(4):将105份A组分、30份B组分和28份加工助剂在70℃下混合,搅拌速度为1400rpm,搅拌时间为4min,真空脱泡浇注入模具内固化,固化温度为110℃,固化时间为22h,得到高硬度聚氨酯弹性体。
对比例4
不加入碳纳米管粉末。
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1.9混合制备混合异氰酸酯;向反应釜中加入110份聚碳酸酯多元醇(数均分子量为2500),在130℃下脱水后,降温至室温;加入80份混合异氰酸酯,通入氮气保护,95℃下反应2h,降温至室温;加入20份二乙二醇和45份混合异氰酸酯,90℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):制备加工助剂:
S1:炭黑粉末预处理:
将分别将5份炭黑粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至90℃酸氧化3h,再经过洗涤、过滤,在100℃、-0.05MPa环境下干燥得到酸化炭黑;
S2:制备炭黑/PAMAM复合材料C:
将2份C62H128N26O12溶于85份甲醇中,加入5份酸化炭黑,超声分散后加热至95℃反应12h,再经过洗涤、过滤、干燥得到炭黑/PAMAM复合材料C;
S3:炭黑/PAMAM复合材料C改性:
将1.5份炭黑/PAMAM复合材料C溶于30份丙酮,超声分散后加热至85℃反应12h,得到炭黑/PAMAM/炭黑复合材料,随后分别加入8份甲醇钠、6份甲酸甲酯、30份碳酸二甲酯,80℃下搅拌反应12h,清洗、过滤、干燥后得到加工助剂;
步骤(4):将110份A组分、36份B组分和25份加工助剂在80℃下混合,搅拌速度为1500rpm,搅拌时间为5min,真空脱泡浇注入模具内固化,固化温度为120℃,固化时间为24h,得到高硬度聚氨酯弹性体。
对比例5
不加入炭黑粉末。
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1.9混合制备混合异氰酸酯;向反应釜中加入110份聚碳酸酯多元醇(数均分子量为2500),在130℃下脱水后,降温至室温;加入80份混合异氰酸酯,通入氮气保护,95℃下反应2h,降温至室温;加入20份二乙二醇和45份混合异氰酸酯,90℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):制备加工助剂:
S1:碳纳米管粉末预处理:
将分别将5份碳纳米管粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至90℃酸氧化3h,再经过洗涤、过滤,在100℃、-0.05MPa环境下干燥得到酸化碳纳米管;
S2:制备碳纳米管/PAMAM复合材料C:
将2份C62H128N26O12溶于85份甲醇中,加入5份酸化碳纳米管,超声分散后加热至95℃反应12h,再经过洗涤、过滤、干燥得到碳纳米管/PAMAM复合材料C;
S3:碳纳米管/PAMAM复合材料C改性:
将1.5份碳纳米管/PAMAM复合材料C溶于30份丙酮,超声分散后加热至85℃反应12h,得到碳纳米管/PAMAM/炭黑复合材料,随后分别加入8份甲醇钠、6份甲酸甲酯、30份碳酸二甲酯,80℃下搅拌反应12h,清洗、过滤、干燥后得到加工助剂;
步骤(4):将110份A组分、36份B组分和25份加工助剂在80℃下混合,搅拌速度为1500rpm,搅拌时间为5min,真空脱泡浇注入模具内固化,固化温度为120℃,固化时间为24h,得到高硬度聚氨酯弹性体。
对比例6
酸化炭黑和复合材料C的复合后,不使用碳酸二甲酯改性,直接将作为加工助剂加入合成热塑性聚氨酯弹性体。
步骤(1):制备A组分:
将异氟尔酮二异氰酸酯和对苯二异氰酸酯按质量比1:1.9混合制备混合异氰酸酯;向反应釜中加入110份聚碳酸酯多元醇(数均分子量为2500),在130℃下脱水后,降温至室温;加入80份混合异氰酸酯,通入氮气保护,95℃下反应2h,降温至室温;加入20份二乙二醇和45份混合异氰酸酯,90℃下反应2h,经过真空脱泡,降温出料;
步骤(2):B组分选择乙二胺作为扩链剂备用;
步骤(3):制备加工助剂:
S1:炭黑粉末和碳纳米管粉末预处理:
将5份炭黑粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至90℃酸氧化3h,再经过洗涤、过滤,在100℃、-0.05MPa环境下干燥得到酸化炭黑;将5份碳纳米管粉末加入15份质量浓度65%的浓硝酸溶液中,超声后水浴加热至90℃酸氧化3h,再经过洗涤、过滤,在100℃、-0.05MPa环境下干燥得到酸化碳纳米管;
S2:制备碳纳米管/PAMAM复合材料C:
将2份C62H128N26O12溶于85份甲醇中,加入5份酸化碳纳米管,超声分散后加热至95℃反应12h,再经过洗涤、过滤、干燥得到碳纳米管/PAMAM复合材料C;
S3:酸化炭黑和复合材料C的复合:
将1.5份碳纳米管/PAMAM复合材料C溶于30份丙酮,加入5份酸化炭黑,超声分散后加热至85℃反应12h,得到碳纳米管/PAMAM/炭黑复合材料,随后分别加入8份甲醇钠、6份甲酸甲酯、30份碳酸二甲酯,80℃下搅拌反应12h,清洗、过滤、干燥后得到加工助剂;
步骤(4):将110份A组分、36份B组分和25份加工助剂在80℃下混合,搅拌速度为1500rpm,搅拌时间为5min,真空脱泡浇注入模具内固化,固化温度为120℃,固化时间为24h,得到高硬度聚氨酯弹性体。
实验:对实施例1~3和对比例1~6制备的高硬度热塑性聚氨酯弹性体进行性能测试。根据《ASTM D2240 硬度计硬度的标准试验方法》测试热塑性聚氨酯弹性体的硬度;根据《ASTM D412 (Die C) 硫化橡胶和热塑性弹性体拉伸试验方法》测试热塑性聚氨酯弹性体的拉伸强度;根据《GB T7762-2003 硫化橡胶和热塑性橡胶耐臭氧静态拉伸试验》,在臭氧浓度25~50pphm,温度40℃,20%伸长的条件下120h,观察热塑性聚氨酯弹性体是否出现龟裂;在35±1℃环境下紫外照射300h,测试拉伸强度保有率和硬度变化率,试验结果如下表所示:
结论:实施例1~3数据表明,使用本发明提供的方法制备得到的热塑性聚氨酯弹性体具有良好的硬度、拉伸强度、抗臭氧老化和抗紫外老化的能力。以实施例1为参照组,对比例1数据表明,不加加工助剂的情况下,制备的热塑性聚氨酯弹性体各项性能均降低;对比例2数据表明,将炭黑和碳纳米管物理混合后在聚氨酯中的分散效果不佳,对产品性能的提升效果有限。以实施例2为参照组,对比例3数据表明,不对炭黑和碳纳米管进行酸处理,制备得到的加工助剂对产品性能提升不大,说明酸处理后的炭黑和碳纳米管能更好地与PAMAM结合。以实施例3为参照组,对比例4和对比例5数据表明,炭黑和碳纳米管的加入有协同作用,能够在提高硬度的同时保持较好的拉伸强度;对比例6数据表明,用碳酸二甲酯对碳纳米管/PAMAM/炭黑复合材料改性步骤非常关键,改性后的加工助剂能更好地分散在聚氨酯弹性体中,充分发挥炭黑和碳纳米管的作用。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种高硬度热塑性聚氨酯弹性体的制备方法,其特征在于:包括以下重量组分:100~110份A组分,25~36份B组分,15~25份加工助剂;包括以下制备步骤:
步骤(1):将多元醇和混合异氰酸酯加热至80~90℃,反应2h后降温至室温,再加入小分子醇和混合异氰酸酯,再次加热至80~90℃,反应2h,随后真空脱泡,降温出料得到A组分;
步骤(2):选择扩链剂作为B组分;
步骤(3):制备加工助剂;
步骤(4):将A组分、B组分和加工助剂混合,真空脱泡浇注入模具内固化,得到高硬度聚氨酯弹性体;
步骤(1)中,所述A组分包括以下重量组分:100~110份多元醇、10~20份小分子醇、60~120份混合异氰酸酯;所述多元醇为聚碳酸酯多元醇、聚己内脂多元醇、聚四氢呋喃多元醇、聚环氧丙烯多元醇中的任一种,数均分子量为1200~2500;所述小分子醇为1,4-丁二醇、1,4-环己烷二甲醇、二乙二醇、1,2-丙二醇中的任一种;混合异氰酸酯为对苯二异氰酸酯、异氟尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、三甲硅烷基异氰酸酯中的两种混合,质量比为1:1~1:1.5;
步骤(2)中,所述扩链剂为二羟甲基丙酸、二邻氯苯胺甲烷、甲基丙二醇、乙二胺、2,4-二氨基-3甲硫基-5丙基氯苯、N,N-二羟基(二异丙基)苯胺中的任一种;
制备过程中采用的加工助剂的制备方法为:
S1:强酸溶液分别处理炭黑粉末和碳纳米管,得到酸化炭黑和酸化碳纳米管;
S2:将PAMAM溶于甲醇中,加入酸化碳纳米管,加热反应得到碳纳米管和PAMAM复合材料C;
S3:将复合材料C溶于丙酮,加入酸化炭黑,加热至60~85℃,反应12h后得到碳纳米管、PAMAM和炭黑复合材料;加入催化剂、促进剂、碳酸二甲酯,在70~80℃下改性12h得到加工助剂。
2.根据权利要求1所述的一种高硬度热塑性聚氨酯弹性体的制备方法,其特征在于:步骤S1中,所述强酸为质量浓度65%的浓硝酸或70%的浓硫酸。
3.根据权利要求1所述的一种高硬度热塑性聚氨酯弹性体的制备方法,其特征在于:步骤S2中,所述PAMAM为C62H128N26O12、C142H288N58O28、C302H608N122O28中的任一种;加热反应温度为85~95℃,反应时间为12h;按重量计,2.5~5份酸化碳纳米管、1.5~2份PAMAM、70~85份甲醇。
4.根据权利要求1所述的一种高硬度热塑性聚氨酯弹性体的制备方法,其特征在于:步骤S3中,所述催化剂为甲醇钠、甲醇钙、乙醇钙、乙醇钾、叔丁醇钡中的任一种;所述促进剂为甲酸甲酯、乙酸甲酯、丙烯酸甲酯中的任一种;按重量计,1~1.5份复合材料C,2.5~5份酸化炭黑,30份丙酮,20~30份碳酸二甲酯,5~8份催化剂,3~6份促进剂。
5.根据权利要求1所述的一种高硬度热塑性聚氨酯弹性体的制备方法,其特征在于:步骤(4)中,各组分混合温度为60~80℃,搅拌速度为1200rpm~1500rpm,搅拌时间为3~5min;固化温度为100~120℃,固化时间为20~24h。
6.根据权利要求1~5中任一项所述的方法制备的高硬度聚氨酯弹性体。
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