CN114478998B - 一种用于板簧的复合材料及其制备方法 - Google Patents

一种用于板簧的复合材料及其制备方法 Download PDF

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CN114478998B
CN114478998B CN202210191232.4A CN202210191232A CN114478998B CN 114478998 B CN114478998 B CN 114478998B CN 202210191232 A CN202210191232 A CN 202210191232A CN 114478998 B CN114478998 B CN 114478998B
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杨金猛
齐立志
王喆
董玉康
陆浩宇
张云磊
吴红辰
郑欣雨
李一宁
李雯
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Shandong Jiaotong University
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Abstract

本发明公开了一种用于板簧的复合材料及其制备方法,S1:将部分聚醚多元醇、部分聚酯多元醇在100‑120℃的温度下混合均匀,抽真空下脱水0.5‑1h,降温到50‑60℃加入液态异氰酸酯,升温至60‑80℃然后保温反应2‑3小时得到组分A;S2:将剩余聚醚多元醇、剩余聚酯多元醇、扩链剂、催化剂、防老化剂,在100‑120℃的温度下混合均匀,抽真空下脱水0.5‑1h,冷却至65‑70℃得到组分B;S3:在60℃下将组分A、组分B和玻璃纤维,采用长玻纤增强反应注射成型工艺将玻璃纤维与聚氨酯基体溶液混合固化后得到复合材料。本发明的复合材料含气泡少,性能更稳定,另外通过软段和硬段的合适配比‚得到的复合材料硬度高,具有优良的抗蠕变、抗冲击、抗撕裂和抗疲劳性能。

Description

一种用于板簧的复合材料及其制备方法
技术领域
本发明属于板簧生产技术领域,特别涉及一种用于板簧的复合材料及其制备方法。
背景技术
当今,能源需求与环境污染压力日趋严峻,2020年9月,习近平主席在第七十五届联合国大会提出我国2030年前碳达峰、2060年前碳中和目标。汽车工业作为国民经济的重要支柱产业,我国汽车保有量从2010年的1.3亿辆急增至2020年的2.8亿辆,其中商用车保有量约0.33亿辆、占比11.8%,但商用车耗油总量却与乘用车耗油总量基本持平。商用车轻量化技术的应用能大幅降低能耗水平、环境污染,在保障国家能源战略安全,助力汽车工业达成“双碳”目标中发挥至关重要的作用。
随着《机动车安全技术检验项目和方法》2021年1月1日正式实施,该法规强制要求商用车新车整备误差±100kg、用车误差±200kg,而目前占轻卡数量60%左右的蓝牌轻卡整备质量普遍超过限值200kg以上,造成新车上牌、在用车年检困难,蓝牌轻卡亟需轻量化。在商用车轻量化技术开发方面,高强钢、铝材等已经普遍应用,进一步轻量化的空间非常有限。复合材料由于密度小、强度大等优点,复合材料在商用车行业的应用迎来新的发展机遇。
虽在复合材料在非承重结构件已有应用,但在重量占比较大的车体承重结构件方面的研发还处于试探性阶段,板簧是商用车主要的承重结构件,相对于其他承重结构件,复合材料板簧在减重方面具有明显的减重效果。特别是轻卡复合材料板簧在国内刚起步,鲜有批量产品应用到量产车上,主要原因是成本较高、生产节拍长、缺乏精准设计能力。。
发明内容
为解决上述问题,本发明提供了一种用于板簧的复合材料及其制备方法。
本发明为实现上述目的,提供了一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,复合材料通过反应注射成型工艺将所述玻璃纤维骨架与聚氨酯基体溶液混合固化后得到,所述聚氨酯基体包括以下组分:聚醚多元醇15-20份、聚酯多元醇40-50份、异氰酸酯30-40份、扩链剂0.5-1份、催化剂0.3-0.7份、防老化剂2-4份;所述聚醚多元醇包括分子量为1000-3000的聚醚二元醇和聚醚三元醇、分子量为1000的聚氧四亚甲基二醇5或8份,所述聚酯多元醇为分子量为500-2000的聚酯二元醇,所述异氰酸酯为4,4'-二环己基甲烷二异氰酸酯与甲苯二异氰酸酯的混合物
优选的,所述扩链剂为胺类和醇类扩链剂,所述催化剂为锡类催化剂,所述防老化剂为胺类防老化剂。
优选的,所述玻璃纤维骨架为E玻璃纤维。
另外,本发明还提供了种用于板簧的复合材料的制备方法,包括以下步骤:
S1:将部分聚醚多元醇、部分聚酯多元醇在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态异氰酸酯,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将剩余聚醚多元醇、剩余聚酯多元醇、扩链剂、催化剂、防老化剂,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
S3:在60℃下采用长玻纤增强反应注射成型工艺将组分A、组分B和玻璃纤维混合固化后得到复合材料。
优选的,所述组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.0-1.1。
优选的,所述组分A和组分B混合物和玻璃纤维的质量比为1:。
本发明的聚氨酯基体组分A和组分B粘度低、流动性好、容易混合均匀,脱泡容易,使反应固化后的复合材料含气泡少,性能更稳定,另外通过软段和硬段的合适配比‚得到的复合材料硬度高,具有优良的抗蠕变、抗冲击、抗撕裂和抗疲劳性能,采用长玻纤增强反应注射成型工艺在高压浇注机混合头附近将长玻璃纤维切割成可变长度的纤维,聚氨酯物料注入模腔之前,在混合头内与直接添入的切碎纤维浸润、混合,经化学反应固化成型制得玻璃纤维增强的聚氨酯复合材料,使纤维在聚氨酯基体中分布非常均匀,大大提高原料的充模性能,同时显著提高复合材料的机械性能,复合材料强度高,重量轻,使复合材料板簧具有明显的减重效果。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但是本发明不局限于这些实施例。
实施例和对比例中涉及到简称代表的物质如下:
PPG-1000:分子量为1000的聚氧化丙烯二醇,上海高桥石油化工公司;
PPG-2000:分子量为2000的聚氧化丙烯二醇,上海高桥石油化工公司;
PTMG-1000 :分子量为1000的聚氧四亚甲基二醇,日本三菱化学株式会社;
N-330:分子量为3000的聚醚三元醇,江苏钟山化工有限公司;
PEA-1000:分子量为1000的聚己二酸乙二醇酯,济宁棠邑化工有限公司
PBA-1000:分子量为2000的聚己二酸丁二醇酯多元醇,济宁棠邑化工有限公司;
POL-3195:分子量为600的聚酯二元醇,青岛新宇田化工有限公司;
POL-256:分子量为2000的聚酯二元醇,青岛新宇田化工有限公司;
TDI:甲苯二异氰酸酯酯,烟台万华聚氨酯有限公司;
H12MDI:4,4'-二环己基甲烷二异氰酸酯,烟台万华聚氨酯有限公司;
MOCA:3,3’-二氯-4,4’-二苯基甲烷二胺,张家港雅瑞化工有限公司;
DEAE:二乙氨基乙醇,张家港雅瑞化工有限公司;
T-9:辛酸亚锡,美国空气化工产品有限公司
防老剂4020:烟台市裕盛化工有限公司。
实施例1
本实施例提供了一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,所述聚氨酯基体包括以下组分:PPG-1000 6份、PPG-2000 5份、PTMG-1000 5份、PEA-1000 15份、POL-3195 22份、POL-256 8份、H12MDI 35份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份;玻璃纤维骨架为E玻璃纤维。
复合材料以下步骤:
S1:将PPG-1000 6份、PEA-1000 8份、PTMG-1000 5份、在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态H12MDI 35份,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将PPG-2000 5份、PEA-1000 7份POL-3195 22份、POL-256 8份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.1
S3:在60℃下采用长玻纤增强反应注射成型工艺将组分A、组分B和玻璃纤维混合固化后得到复合材料。
组分A和组分B混合物和玻璃纤维的质量比为1:0.2。
实施例2
本实施例提供了一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,聚氨酯基体包括以下组分:PPG-1000 6份、PPG-2000 5份、PTMG-1000 8份、PEA-1000 15份、POL-3195 22份、POL-256 8份、TDI18份、H12MDI 17份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份;玻璃纤维骨架为E玻璃纤维。
复合材料以下步骤:
S1:将PPG-1000 6份、PEA-1000 8份、PTMG-1000 8份、在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态H12MDI 35份,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将PPG-2000 5份、PEA-1000 7份POL-3195 22份、POL-256 8份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.0
S3:在60℃下采用长玻纤增强反应注射成型工艺将组分A、组分B和玻璃纤维混合固化后得到复合材料。
组分A和组分B混合物和玻璃纤维的质量比为1:0.2。
实施例3
本实施例提供了一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,聚氨酯基体包括以下组分:PPG-1000 12份、PPG-2000 3份、PTMG-1000 5份、PEA-1000 20份、POL-3195 18份、POL-256 10份、H12MDI 35份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份;玻璃纤维骨架为E玻璃纤维。
复合材料以下步骤:
S1:将PPG-1000 12份、PEA-1000 10份、PTMG-1000 5份、在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态H12MDI 28份,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将PPG-2000 3份、PEA-1000 10份POL-3195 18份、POL-256 10份、MOCA 0.5份、DEAE 0.3份、T-9 0.5份、防老剂4020 3份,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.0
S3:在60℃下采用长玻纤增强反应注射成型工艺将组分A、组分B和玻璃纤维混合固化后得到复合材料。
组分A和组分B混合物和玻璃纤维的质量比为1:0.3。
对比例1
一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,聚氨酯基体包括以下组分:PPG-1000 6份、PPG-2000 5份、PTMG-1000 8份、PEA-1000 15份、POL-3195 22份、POL-256 8份、TDI35份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份;玻璃纤维骨架为E玻璃纤维。
复合材料以下步骤:
S1:将PPG-1000 6份、PEA-1000 8份、PTMG-1000 8份、在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态H12MDI 35份,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将PPG-2000 5份、PEA-1000 7份POL-3195 22份、POL-256 8份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.0
S3:在60℃下将组分A、组分B和玻璃纤维,采用长玻纤增强反应注射成型工艺将玻璃纤维与聚氨酯基体溶液混合固化后得到复合材料。
组分A和组分B混合物和玻璃纤维的质量比为1:0.2。
对比例2
一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,所述聚氨酯基体包括以下组分:PPG-1000 6份、PPG-2000 5份、PTMG-1000 8份、PEA-1000 15份、POL-3195 22份、POL-256 8份、MDI 35份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份;玻璃纤维骨架为E玻璃纤维。
复合材料以下步骤:
S1:将PPG-1000 6份、PEA-1000 8份、PTMG-1000 8份、在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态H12MDI 35份,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将PPG-2000 5份、PEA-1000 7份POL-3195 22份、POL-256 8份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.0
S3:在60℃下将组分A、组分B和玻璃纤维,采用长玻纤增强反应注射成型工艺将玻璃纤维与聚氨酯基体溶液混合固化后得到复合材料。
组分A和组分B混合物和玻璃纤维的质量比为1:0.2。。
对比例3
一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,所述聚氨酯基体包括以下组分:PPG-1000 14份、PPG-2000 5份、PEA-1000 15份、POL-3195 22份、POL-256 8份、TDI18份、H12MDI 17份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份;玻璃纤维骨架为E玻璃纤维。
复合材料以下步骤:
S1:将PPG-1000 6份、PEA-1000 8份、PTMG-1000 8份、在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态H12MDI 35份,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将PPG-2000 5份、PEA-1000 7份POL-3195 22份、POL-256 8份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.0
S3:在60℃下将组分A、组分B和玻璃纤维,采用长玻纤增强反应注射成型工艺将玻璃纤维与聚氨酯基体溶液混合固化后得到复合材料。
组分A和组分B混合物和玻璃纤维的质量比为1:0.2。
对比例4
使用环氧树脂为基体,E玻璃纤维为骨架,环氧树脂为基体包括以下组分双酚A型环氧树 脂100份、TMA 30份、聚硫增韧剂10份、稀释剂XY6695份、KH560 0.5 份环氧树脂与E玻璃纤维质量比为1:0.2,采用长玻纤增强反应注射成型工艺将玻璃纤维与环氧树脂基体溶液混合固化后得到复合材料。
对比例5
使用环氧树脂为基体,E玻璃纤维为骨架,环氧树脂为基体包括以下组分双酚A型环氧树 脂100份、TMA 30份、聚硫增韧剂10份、稀释剂XY6695份、KH560 0.5 份;
取玻璃纤维布和玻璃纤维丝充分浸渍在环氧树脂组合物中,将经环氧树脂浸渍的玻璃纤维布在双拼芯模的上下芯模表面敷设一层,然后开始同时一层接一层地缠绕经环氧树脂浸渍的玻璃纤维布和并列地18根玻璃纤维丝。
在敷设前,对玻璃纤维丝施加每单根纱50N的张力,随缠绕层数递增,对玻璃纤维丝施加的张力以5N/层递减,总缠绕层数为8层。
8层结束后,在玻璃纤维丝外部继续缠绕一层玻璃纤维布,使最外层 的玻璃纤维丝上敷设有一层经过浸渍的玻璃纤维布。
在1MPa的压力下,对上下芯模进行合模,得到板簧雏形,然后在4MPa 压力下常温固化2小时,得到玻璃纤维增强树脂复合材料板簧。
对比例6
本实施例提供了一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,所述聚氨酯基体包括以下组分:PPG-1000 6份、PPG-2000 5份、PTMG-1000 5份、PEA-1000 15份、POL-3195 22份、POL-256 8份、H12MDI 35份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份;玻璃纤维骨架为E玻璃纤维。
复合材料以下步骤:
S1:将PPG-1000 6份、PEA-1000 8份、PTMG-1000 5份、在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态H12MDI 35份,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将PPG-2000 5份、PEA-1000 7份POL-3195 22份、POL-256 8份、MOCA 0.5份、DEAE 0.2份、T-9 0.3份、防老剂4020 3份,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.1
取玻璃纤维布和玻璃纤维丝充分浸渍在环氧树脂组合物中,将经环氧树脂浸渍的玻璃纤维布在双拼芯模的上下芯模表面敷设一层,然后开始同时一层接一层地缠绕经环氧树脂浸渍的玻璃纤维布和并列地18根玻璃纤维丝。
在敷设前,对玻璃纤维丝施加每单根纱50N的张力,随缠绕层数递增,对玻璃纤维丝施加的张力以5N/层递减,总缠绕层数为8层。
8层结束后,在玻璃纤维丝外部继续缠绕一层玻璃纤维布,使最外层 的玻璃纤维丝上敷设有一层经过浸渍的玻璃纤维布。
在1MPa的压力下,对上下芯模进行合模,得到板簧雏形,然后在4MPa 压力下常温固化2小时,得到玻璃纤维增强树脂复合材料板簧。
对实施例1-3、对比例1-5相关性能测试的结果如表1。
表1 实施例1-3、对比例1-6相关性能测试的结果
Figure SMS_1
从表1可以看出本发明制复合材料板簧材料力学强度较好,具有优良的抗蠕变、抗冲击、抗撕裂和抗疲劳性能。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围。

Claims (6)

1.一种用于板簧的复合材料,包括聚氨酯基体和玻璃纤维骨架,其特征在于,复合材料通过反应注射成型工艺将所述玻璃纤维骨架与聚氨酯基体溶液混合固化后得到,所述聚氨酯基体包括以下组分:聚醚多元醇15-20份、聚酯多元醇40-50份、异氰酸酯30-40份、扩链剂0.5-1份、催化剂0.3-0.7份、防老化剂2-4份;所述聚醚多元醇包括分子量为1000-3000的聚醚二元醇和聚醚三元醇、分子量为1000的聚氧四亚甲基二醇5或8份,所述聚酯多元醇为分子量为500-2000的聚酯二元醇,所述异氰酸酯为4,4'-二环己基甲烷二异氰酸酯与甲苯二异氰酸酯的混合物。
2.根据权利要求1所述的一种用于板簧的复合材料,其特征在于,所述扩链剂为胺类和醇类扩链剂,所述催化剂为锡类催化剂,所述防老化剂为胺类防老化剂。
3.根据权利要求1所述的一种用于板簧的复合材料,其特征在于,所述玻璃纤维骨架为E玻璃纤维。
4.一种权利要求2-3任意一项所述的用于板簧的复合材料的制备方法,其特征在于,包括以下步骤:
S1:将部分聚醚多元醇、部分聚酯多元醇在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,降温到50-60℃加入液态异氰酸酯,升温至60-80℃然后保温反应2-3小时得到组分A;
S2:将剩余聚醚多元醇、剩余聚酯多元醇、扩链剂、催化剂、防老化剂,在100-120℃的温度下混合均匀,抽真空下脱水0.5-1h,冷却至65-70℃得到组分B;
S3:在60℃下采用长玻纤增强反应注射成型工艺将组分A、组分B和玻璃纤维混合固化后得到复合材料。
5.根据权利要求4所述的一种用于板簧的复合材料的制备方法,其特征在于,所述组分A中异氰酸酯基摩尔数与组分B中活泼氢的摩尔数之比为1.0:1.0-1.1。
6.根据权利要求5所述的一种用于板簧的复合材料的制备方法,其特征在于,所述组分A和组分B混合物和玻璃纤维的质量比为1:(0.2-0.3)。
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