CN107915990B - 一种轻量化发泡浇铸尼龙材料及其制备方法和应用 - Google Patents
一种轻量化发泡浇铸尼龙材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开轻量化发泡浇铸尼龙材料,由以下重量份数的组分反应制备得到︰酰胺单体40~99.6份,催化剂0.1~5份,助催化剂0.1~15份,发泡剂0.1~20份,增韧剂0.1~20份。本轻量化发泡浇铸尼龙材料针对现有发泡浇铸生产过程中,发泡难以控制和机械性能差的缺点,本发明利用发泡剂复配增韧剂,再结合MCPA6配方工艺的调整,使发泡剂在MCPA6单体熔体中发泡,进而聚合成型。不仅解决了MCPA6成型收缩的问题,还提供一种轻量化发泡浇铸尼龙材料的制备工艺,该材料的发泡工艺稳定,得到的材料机械性能好。本发明的轻量化发泡浇铸尼龙能拓展其应用领域,可用于汽车的轻量化和减震降噪领域。
Description
技术领域
本发明涉及浇铸尼龙材料及其制备和应用,更具体地,涉及一种轻量化发泡浇铸尼龙材料及其制备方法和应用。
背景技术
尼龙材料以其强度高、硬度大、韧性好,低蠕变耐磨耗及化学稳定性好而著称,浇铸尼龙制品作为工程塑料之一,除具有普通尼龙材料的特点外,由于其分子量大、结晶度高,机械强度比一般尼龙高1.5倍,能直接铸造成型几十公斤乃至上百公斤大型机件,在冶金、化工,特别是当代机械装备制造产业,应用前景十分广阔。浇铸尼龙在机械方面作为减振耐磨材料代替有色金属及合金钢,其润滑性使其不损坏磨件,减少磨耗,从而延长零件使用寿命,降低成本,并且降低了机械振动,磨擦噪音。
浇铸尼龙简称MC尼龙,是一种广泛应用于石油化工、机械和纺织等工业领域的工程塑料。随着业内应用范围的扩大和对材料各项指标要求的提高,浇铸尼龙在力学强度和精度等方面需要得到进一步改善。
随着浇铸尼龙的大量使用和机械设备的轻量化要求,对浇铸尼龙自身的减重轻量也有了新的要求,20世纪60年代,国外有研究制备了发泡MCPA6,为了达到浇铸尼龙的轻量化,但因发泡难以控制和机械性能差,而未得到推广应用。
发明内容
本发明主要针对现有发泡浇铸生产过程中,发泡难以控制和机械性能差的缺点,本发明利用发泡剂复配增韧剂,再结合MCPA6配方工艺的调整,使发泡剂在MCPA6单体熔体中发泡,进而聚合成型轻量化发泡浇铸尼龙材料。不仅解决了MCPA6成型收缩的问题,还提供一种轻量化发泡浇铸尼龙材料的制备工艺,该材料的发泡工艺稳定,得到的材料机械性能好。
本发明的另一目的在于提供一种轻量化发泡浇铸尼龙材料的应用。
本发明通过以下技术方案予以实现:
公开一种轻量化发泡浇铸尼龙材料,由以下重量份数的组分反应制备得到︰酰胺单体40~99.6份,催化剂0.1~5份,助催化剂0.1~15份,发泡剂0.1~20份,增韧剂0.1~20份。
其中,所述酰胺单体为己内酰胺或十二内酰胺的至少一种,所述发泡剂为无机发泡剂、有机发泡剂的一种或几种复配。
本发明的轻量化发泡浇铸尼龙材料将原料中创造性地引入了发泡剂,发泡剂能使浇铸尼龙形成微孔结构,再结合增韧剂,能使浇铸尼龙轻量化的同时保持强度和韧性。铸型尼龙单体熔体粘度低,发泡过程中容易形成串孔,而加入增韧剂能提高熔体粘度,使泡孔为闭孔,另外增韧剂本身使铸型尼龙韧性提高。
本发明的轻量化发泡浇铸尼龙材料利用催化剂引发己内酰胺的开环合聚,通过添加发泡剂和增韧剂成功地由己内酰胺单体制备得到发泡浇铸尼龙材料。
进一步地,所述催化剂为氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、碳酸钠、钠代己内酰胺盐、己内酰胺溴化镁、格氏试剂中的任意一种或几种复配。
进一步地,所述助催化剂为异氰酸酯、磺酸酯、羧酸酯、乙酰基己内酰胺的任意一种或几种复配。
更进一步地,所述异氰酸酯为MDI、TDI、HDI、NDI、PAPI、HTDI、HMDI、TMXDI、IPDI、JQ胶。
进一步地,所述增韧剂为聚醚多元醇、聚异戊二烯、环氧树脂、多元胺的任意一种或几种复配。
进一步地,所述无机发泡剂为碳酸氢钠、碳酸钠、亚硝酸钠、氯化铵的任意一种或几种复配。
进一步地,所述有机发泡剂为偶氮化合物、磺酰肼类化合物、亚硝基化合物、阴离子表面改性剂、非离子型表面改性剂、脲基化合物的任意一种或几种复配。
无机发泡剂一般通过热解产生发泡气体,分解逸出二氧化碳、氮气等惰性气体,逸出气体对空气和环境无污染,且发泡效果好,泡孔均匀,数量较大。
本发明的另一目的在于,公开轻量化发泡浇铸尼龙材料的制备方法,所述制备方法包括以下步骤:
S1.将上述重量份的酰胺单体,按重量份1﹕1分别加入到A、B反应釜内,抽真空至0.1Mpa,加热熔融,在120~150℃下,脱水5~30min;
S2.将反应釜A,加入上述重量份的催化剂,将釜内熔体温度恒定在120~140℃下,抽真空10~30min;得到活性料A;同时,反应釜B,依次加入助催化剂、增韧剂,维持釜内熔体温度120~140℃下,抽真空10~30min,得到活性料B;
S3.将所述活性料A与活性料B喷射混合,喷射混合过程中加入发泡剂,喷射浇铸到已经预热到140~180℃的模具中,对模具内的熔体进行磁力搅拌或超声波处理,同时进行抽真空0~30min,使熔体发泡,保持模具温度5~30min,制得发泡浇铸尼龙材料。
本发明的另一目的在于公开上述轻量化发泡浇铸尼龙材料汽车的轻量化和减震降噪领域。
与现有技术相比,本发明具有如下有益效果:
本发明提供的轻量化发泡浇铸尼龙材料采用常见的原料,创造性的将发泡材料用于浇铸尼龙材料体系中进行改性和分散,再加入催化剂和助催化剂相互作用,引发浇铸尼龙材料反应成型,制备得到的轻量化发泡浇铸尼龙材料质量轻,综合性能良好,使过程安全可靠。
本发明提供的轻量化发泡浇铸尼龙材料泡孔均匀,不仅能抵消浇铸尼龙成型收缩,还能使其体积膨胀。
本发明的轻量化发泡浇铸尼龙材料选用发泡剂和增韧剂复配,不仅能更好的控制泡孔还是解决发泡制品的脆性,提高发泡制品的韧性。
本发明的轻量化发泡浇铸尼龙能拓展其应用领域,可用于汽车的轻量化和减震降噪领域。
具体实施方式
下面结合具体实施例进一步详细说明本发明。除非特别说明,本发明实施例使用的各种原料均可以通过常规市购得到,或根据本领域的常规方法制备得到,所用设备为实验常用设备。除非另有定义或说明,本文中所使用的所有专业与科学用语与本领域技术熟练人员所熟悉的意义相同。
本发明公开的轻量化发泡浇铸尼龙材料,由以下重量份数的组分反应制备得到︰酰胺单体40~99.6份,催化剂0.1~5份,助催化剂0.1~15份,发泡剂0.1~20份,增韧剂0.1~20份。
其中,酰胺单体为己内酰胺或十二内酰胺的至少一种,发泡剂为无机发泡剂、有机发泡剂的一种或几种复配;无机发泡剂为碳酸氢钠、碳酸钠、亚硝酸钠、氯化铵的任意一种或几种复配。有机发泡剂为偶氮化合物、磺酰肼类化合物、亚硝基化合物、阴离子表面改性剂、非离子型表面改性剂、脲基化合物的任意一种或几种复配。
催化剂为氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、碳酸钠、钠代己内酰胺盐、己内酰胺溴化镁、格氏试剂中的任意一种。浇铸尼龙是阴离子本体聚合反应,通常阴离子是强碱夺取己内酰胺中氮上的氢而产生的活性离子,催化剂可以从己内酰胺单体上提取酰胺基上的氢,使之成为阴离子。
助催化剂为异氰酸酯、磺酸酯、羧酸酯、乙酰基己内酰胺的任意一种或几种复配。异氰酸酯为MDI、TDI、HDI、NDI、PAPI、HTDI、HMDI、TMXDI、IPDI、JQ胶。
增韧剂为聚醚多元醇、聚异戊二烯、环氧树脂、多元胺的任意一种或几种复配。
本发明的轻量化发泡浇铸尼龙材料的制备方法,它包括下列步骤︰
S1.将上述重量份的酰胺单体,按重量份1﹕1分别加入到浇铸尼龙材料设备的A、B反应釜内,抽真空至0.1Mpa,加热熔融,在120~150℃下,脱水5~30min;
S2.将反应釜A,加入上述重量份的催化剂,将釜内熔体温度恒定在120~140℃下,抽真空10~30min;,得到活性料A;同时,反应釜B,依次加入助催化剂、增韧剂,维持釜内熔体温度120~140℃下,抽真空10~30min,得到活性料B;
S3.将活性料A与活性料B喷射混合,喷射混合过程中加入发泡剂,喷射浇铸到已经预热到140~180℃的模具中,对模具内的熔体进行磁力搅拌或超声波处理后抽真空,使熔体发泡,保持模具温度、抽真空和磁力搅拌或超声波处理5~30min,制得发泡浇铸尼龙材料。
具体实施如下。
实施例1
(1)轻量化发泡浇铸尼龙材料
本实施例的轻量化发泡浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为己内酰胺,催化剂为氢氧化钠,助催化剂为异氰酸酯MDI,发泡剂为碳酸钠,增韧剂为聚醚多元醇。
(2)轻量化发泡浇铸尼龙材料的制备方法
本实施例的轻量化发泡浇铸尼龙材料的制备方法,包括下列步骤︰
S1.将81.7重量份己内酰胺按重量份1︰1,分别加入到浇铸尼龙设备的A、B反应釜内,抽真空至0.1MPa,加热熔融,在120℃下脱水30min,停止抽真空,通入氮气保护;
S2.将反应釜A,加入0.3重量份氢氧化钠,维持反应釜内熔体温度在120℃下,抽真空30min,得到活性料A;同时,在反应釜B中,依次加入3重量份MDI、10重量份的聚醚多元醇,维持釜内熔体温度120℃下,抽真空10min后,维持反应釜内熔体温度120℃,并保持20min;得到活性料B;
S3.将上述活性料A和活性料B通过混合喷射抢打入密闭模具中,模具的温度已经预热到160℃,对模具内的熔体进行磁力搅拌,磁力搅拌的转数为0~2000rpm,喷射过程中,在喷射头混入5重量份发泡剂碳酸钠,抽真空,保持密闭模具温度25min,制得发泡浇铸尼龙。
实施例2
(1)轻量化发泡浇铸尼龙材料
本实施例的轻量化发泡浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为己内酰胺,催化剂为氢氧化钠,助催化剂为TDI,发泡剂为AC发泡剂,增韧剂为异戊二烯。
(2)轻量化发泡浇铸尼龙材料的制备方法
本实施例的轻量化发泡浇铸尼龙材料的制备方法,包括下列步骤︰
S1.将66.5重量份己内酰胺按重量份1︰1,分别加入到浇铸尼龙设备的A、B反应釜内,抽真空至0.1MPa,加热熔融,在140℃下脱水5min,停止抽真空,通入氮气保护;
S2.将反应釜A,加入0.5重量份氢氧化钠,维持反应釜内熔体温度在140℃下10min;同时反应釜B中加入3重量份TDI、20重量份的聚异戊二烯,维持釜内熔体温度140℃下,抽真空30min,并保持5min;得到活性料B;
S3.将上述活性料A和活性料B通过混合喷射抢打入密闭模具中,模具的温度已经预热到140℃,对模具内的熔体进行超声波处理,其超声频率为50KHz,喷射过程中,在喷射头混入10重量份AC发泡剂,抽真空,保持模具温度25min,制得发泡浇铸尼龙。
实施例3
(1)轻量化发泡浇铸尼龙材料
本实施例的轻量化发泡浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为己内酰胺和十二内酰胺复配,催化剂为乙醇钠,助催化剂为JQ胶,发泡剂为甲苯磺酰肼发泡剂,增韧剂为异戊二烯。
(2)轻量化发泡浇铸尼龙材料的制备方法
本实施例的轻量化发泡浇铸尼龙材料的制备方法,包括下列步骤︰
S1.将54.6重量份己内酰胺和20重量份十二内酰胺按重量份1︰1分别加入到浇铸尼龙设备的A、B反应釜内,抽真空至0.1MPa,加热熔融,在120℃下脱水15min,停止抽真空,通入氮气保护;
S2.将反应釜A,加入0.4重量份乙醇钠,维持反应釜内熔体温度在120℃下20min;同时反应釜B中加入5重量份JQ胶、5重量份聚异戊二烯,维持反应釜内熔体温度120℃,抽真空10min,并保持10min;
S3.将上述活性料A和活性料B通过混合喷射抢打入密闭模具中,模具的温度已经预热到140℃,对模具内的熔体进行超声波处理,其超声频率为30KHz,喷射过程中,在喷射头混入15重量份对甲苯磺酰肼发泡剂,抽真空,保持模具温度25min,制得发泡浇铸尼龙。
实施例4
(1)轻量化发泡浇铸尼龙材料
本实施例的轻量化发泡浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为己内酰胺和十二内酰胺复配,催化剂为钠代己内酰胺盐,助催化剂为HDI,发泡剂为二亚硝基五亚甲基四胺发泡剂,增韧剂为聚醚多元醇。
(2)轻量化发泡浇铸尼龙材料的制备方法
本实施例的轻量化发泡浇铸尼龙材料的制备方法,包括下列步骤︰
S1.将60重量份己内酰胺和15重量份十二内酰胺按重量份1︰1分别加入到浇铸尼龙设备的A、B反应釜内,抽真空至0.1MPa,加热熔融,在125℃下脱水25min,停止抽真空,通入氮气保护;
S2.反应釜A,加入5重量份钠代己内酰胺盐,抽真空,维持反应釜内熔体温度在125℃下25min;同时反应釜B中加入10重量份HDI、5重量份的聚醚多元醇,抽真空,维持反应釜内熔体温度140℃,并保持10min;
S3.反应釜A、B活性料制备完成后,通过混合喷射抢打入密闭模具中,模具温度为180℃,对模具内的熔体进行磁力搅拌,磁力搅拌的转数为0~2000rpm,喷射过程中,在喷射头混入5重量份二亚硝基五亚甲基四胺发泡剂,保持模具温度25min,制得发泡浇铸尼龙。
实施例5
(1)轻量化发泡浇铸尼龙材料
本实施例的轻量化发泡浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为己内酰胺和十二内酰胺复配,催化剂为己内酰胺溴化镁,助催化剂为IPDI,发泡剂为尿素,增韧剂为三乙醇胺。
(2)轻量化发泡浇铸尼龙材料的制备方法
本实施例的轻量化发泡浇铸尼龙材料的制备方法,包括下列步骤︰
S1.将54.9重量份己内酰胺和20重量份十二内酰胺按重量份1︰1,分别加入到浇铸尼龙设备的A、B反应釜内,抽真空至0.1MPa,加热熔融,在120℃下脱水20min,停止抽真空,通入氮气保护;
S2.反应釜A,加入5重量份己内酰胺溴化镁,抽真空,维持反应釜内熔体温度在120℃下10~30min;同时反应釜B中,加入10重量份IPDI、0.1重量份的三乙醇胺,抽真空,维持反应釜内熔体温度125℃,并保持15min;
S3.反应釜A、B活性料制备完成后,通过混合喷射抢打入密闭模具中,模具温度为170℃,对模具内的熔体进行磁力搅拌,磁力搅拌的转数为0~2000rpm,喷射过程中,在喷射头混入10重量份尿素发泡剂,超声波处理,超声频率0~50KHz,保持模具温度25min,制得发泡浇铸尼龙。
实施例6
(1)轻量化发泡浇铸尼龙材料
本实施例的轻量化发泡浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为十二内酰胺,催化剂为氢氧化钾,助催化剂为磺酸酯,发泡剂为氯化铵,增韧剂为环氧树脂。
(2)轻量化发泡浇铸尼龙材料的制备方法
本实施例的轻量化发泡浇铸尼龙材料的制备方法,与实施例1相同。
实施例7
(1)轻量化发泡浇铸尼龙材料
本实施例的轻量化发泡浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为十二内酰胺,催化剂为甲醇钠,助催化剂为乙酰基己内酰胺,发泡剂为亚硝酸钠,增韧剂为聚异戊二烯。
(2)轻量化发泡浇铸尼龙材料的制备方法
本实施例的轻量化发泡浇铸尼龙材料的制备方法,与实施例1相同。
对比例1
本对比例的浇铸尼龙材料,由表1的原料及配比制得。其中,酰胺单体为己内酰胺,催化剂为氢氧化钠,助催化剂为异氰酸酯MDI,增韧剂为聚醚多元醇。
本对比例的浇铸尼龙材料的制备方法:包括下列步骤︰
S1.将81.7重量份己内酰胺按重量份1︰1,分别加入到浇铸尼龙设备的A、B反应釜内,抽真空至0.1MPa,加热熔融,在120℃下脱水30min,停止抽真空,通入氮气保护;
S2.将反应釜A,加入0.3重量份氢氧化钠,维持反应釜内熔体温度在120℃下,抽真空30min,得到活性料A;同时,在反应釜B中,依次加入3重量份MDI、10重量份的聚醚多元醇,维持釜内熔体温度120℃下,抽真空10min后,维持反应釜内熔体温度120℃,并保持20min;得到活性料B;
S3.将上述活性料A和活性料B通过混合喷射抢打入密闭模具中,模具的温度已经预热到160℃,抽真空,保持密闭模具温度25min,制得浇铸尼龙材料。
如表2所示,将实施例1~实施例7的轻量化发泡浇铸尼龙材料相对于对比例1的浇铸尼龙材料将发泡材料,不但质量轻,综合性能良好,而且过程安全可靠。
表1
表2
断裂伸长率(%) | 拉伸强度(MPa) | 弯曲强度(MPa) | |
实施例1 | 185 | 54.4 | 67.6 |
实施例2 | 184 | 51.1 | 63.2 |
实施例3 | 176 | 55.7 | 56.9 |
实施例4 | 129 | 59.6 | 71.4 |
实施例5 | 223 | 60.3 | 73.2 |
实施例6 | 146 | 53.4 | 78.4 |
实施例7 | 153 | 66.7 | 69.8 |
对比例1 | 136 | 58.2 | 70.8 |
Claims (8)
1.一种轻量化发泡浇铸尼龙材料,其特征在于,由以下重量份数的组分反应制备得到︰酰胺单体40~99.6份,催化剂0.1~5份,助催化剂0.1~15份,发泡剂0.1~20份,增韧剂0.1~20份;
包括下列步骤︰
S1.将上述重量份的酰胺单体,按重量份1﹕1分别加入到A、B反应釜内,抽真空至0.1Mpa,加热熔融,在120~150℃下,脱水5~30min;
S2.将反应釜A,加入上述重量份的催化剂,将釜内熔体温度恒定在120~140℃下,抽真空10~30min,得到活性料A;同时,在反应釜B中,依次加入助催化剂、增韧剂,维持釜内熔体温度120~140℃下,抽真空10~30min,并保持5~20mim;得到活性料B;
S3.将所述活性料A与活性料B喷射混合,在其喷射混合过程中加入发泡剂,喷射浇铸到140~180℃的模具中,对模具内的熔体进行磁力搅拌或超声波处理,同时抽真空0~30min,使熔体发泡,保持模具温度5~30min,制得发泡浇铸尼龙材料。
2.根据权利要求1所述轻量化发泡浇铸尼龙材料,其特征在于,所述酰胺单体为己内酰胺或十二内酰胺的至少一种,所述发泡剂为无机发泡剂、有机发泡剂。
3.根据权利要求1所述轻量化发泡浇铸尼龙材料,其特征在于,所述催化剂为氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、碳酸钠、钠代己内酰胺盐、己内酰胺溴化镁、格氏试剂中的一种或几种复配。
4.根据权利要求1所述轻量化发泡浇铸尼龙材料,其特征在于,所述助催化剂为异氰酸酯、磺酸酯、羧酸酯、乙酰基己内酰胺的任意一种或几种复配。
5.根据权利要求4所述轻量化发泡浇铸尼龙,其特征在于所述的异氰酸酯为MDI、TDI、HDI、NDI、PAPI、HTDI、HMDI、TMXDI、IPDI、JQ胶。
6.根据权利要求1所述轻量化发泡浇铸尼龙材料,其特征在于,所述增韧剂为聚醚多元醇、聚异戊二烯、环氧树脂、多元胺的任意一种或几种复配。
7.根据权利要求2所述轻量化发泡浇铸尼龙材料,其特征在于,所述无机发泡剂为碳酸氢钠、碳酸钠、亚硝酸钠、氯化铵的任意一种或几种复配。
8.根据权利要求2所述轻量化发泡浇铸尼龙材料,其特征在于,所述有机发泡剂为偶氮化合物、磺酰肼类化合物、亚硝基化合物、阴离子表面改性剂、非离子型表面改性剂、脲基化合物的任意一种或几种复配。
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