CN1185501A - 铁路混凝土用聚氨酯弹性体轨枕垫板 - Google Patents
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Abstract
一种填充聚氨酯弹性体所制造的铁路混凝土用弹性体轨枕垫板,它是由一定量的低聚多元醇、多异氰酸酯、扩链剂、助剂及矿物土填充剂组成而制得的填充聚氨酯弹性体,经注射或热压制造的弹性体轨枕垫板。该种矿物土填充聚氨酯弹性体的弹性体轨枕垫板物性好于普通橡胶轨枕垫板性能,同时大大降低其成本。填充的矿物土无需进一步加工或再处理,该填充聚氨酯弹性轨枕垫板制备工艺简单。
Description
本发明属于高分子类聚合物实用技术领域,具体地说是一种矿物土填充聚氨酯弹性体轨枕垫板及制法。
聚氨酯树脂(PU)是合成材料之一,其中,聚氨酯弹性体生产量约占其总生产量的10%左右。
聚氨酯弹性体按其加工方法可分为:浇注、热塑、混炼和反应注射几种类型。若从原料多元醇来分,可分为聚醚型和聚酯型。
聚氨酯弹性体具有可发泡性、弹性、耐低温性、耐溶浏性、耐生物老化性、耐臭氧、耐辐射、隔热、绝缘及优异的耐磨性、抗撕裂性、粘接性等,是一种发展较快的高性能高分子材料。
正是由于这些优异的性能,其广泛应有于机电、船舶、航空、车辆土木建造、轻工、纺织等各行各业,且其产量及品种逐年增加,在材料工业中占有相当的地位。
聚氨酯弹性体的性能优异,但价格较高,使其应用受到一定限制,因而人们注意到了以降低聚氨酯弹性体的价格为目的的研究及应用开发工作。
在本发明曾有填充聚氨酯弹性体的报导,即在热塑性聚氨酯弹性体中加入各种填料,如:碳黑、白碳黑、高岭土、碳酸钙及铝粉等。但其或多或少均对聚氨酯弹性体的性能有不良影响,而使聚氨酯弹性体的价格下降幅度不大。
本发明的目的是提供一种采用矿物土作为填充剂制备填充聚氨酯弹性体轨枕垫板制造的方法。该种填充聚氨酯弹性体的性能与未填充的对应的聚氨酯弹性体的性能相同,但价格降低50-70%。这样大大降低了材料的使用成本,扩大了其材料的应用范围。
本发明的目的是采用如下技术方案来实现的:
填充聚氨酯弹性体的组成:
填充剂、低聚多元醇、多异氰酸酯、扩链剂及助剂
填充剂为一种粘矿物土。化学组成:Al2O3·nSiO2·nH2O。外观为白色粉末,SiO2含量≥60%,相对密度为2.54-2.60,熔点≥1800℃,200目筛余物≤2%。该矿矿床分布十分广泛,几乎在我国各省均有蕴藏。其填充量为0-100份数(对100份聚氨酯)。
低聚多元醇为聚酯、聚醚及其他低聚物多元醇。聚酯包括一般聚酯。即二元酸和二元醇或有时加少量的多元醇如甘油、三羟甲基丙烷等原料而制备的,二元酸包括己二酸、癸二酸及芳香族二酸等;二元醇包括乙二醇、丙二醇、丁二醇及二乙二醇等;聚内酯,一般为聚ε-乙内酯。聚醚包括聚氧化丙烯醚二醇、聚四氢呋喃醚二醇及氨基聚醚等。其他低聚物多元醇包括端羟基烃类化合物、含羟基接枝化合物、聚碳酸酯二醇、蓖麻油、聚酯酰胺等。分子量1000-3000,一般使用其中一种或一种以上复合使用。
多异氰酸酯为各种脂肪族及芳香族二异氰酸酯。如甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六次甲基二异氰酸酯、碳化二亚胺化二异氰酸酯及大分子二异氰酸酯等。一般使用其中一种或一种以上复合使用。
扩链剂为二元胺或二元醇。二元胺为芳香族二胺如3,3-二氯-4,4-二苯基甲烷二胺等,二元醇包括丁二醇、乙二醇及对苯二酚二羟乙基醚等,也包括甘油、三羟甲基丙烷及季戊四醇等多元醇。一般使用基中一种或一种以上复合使用,也可不用。
助剂包括:催化剂如吗啡啉、三乙基四胺等叔胺类及辛酸亚锡、二月桂酸二丁基锡等有机锡类;增塑剂如苯二甲酸二甲氧基乙二醇酯等苯二甲酸酯类、磷酸三甲酯等磷酸酯类及脂肪酸酯类和其他树脂;减磨剂如硅油、二硫化钼、石墨及聚四氟乙烯等;润滑剂如硬脂酸及其盐类、石蜡类以及硬脂酸酯和哽脂酰胺类等;着色剂如汉撒红R、日光坚牢橙等有机染料及氧化铬绿、氧化铁红及钛白粉等无机颜料。以及硫化体系助剂及光稳定剂、抗氧剂、抗静电剂、热稳定剂、水稳定剂、防霉剂和阻燃剂等。可根据要求适当选用。
本发明的填充聚氨酯弹性体适合普通聚氨酯弹性体的任何加工方法,如浇注、热塑、混炼和反应注射等方法。
制备方法按填充聚氨酯弹性体的加工方法不同而略有不同。填料矿物土随低聚多元醇一起加入。
矿物土在搅拌的剪切力下很好地分散在高聚物中,且因聚氨酯聚合物链中的脲基、氨基甲酸酯基及酰胺基等极性基团与矿物土的铝氧基及硅氧基通过次价键力而很好的集聚在一起。
举热塑性聚氨酯弹性体轨枕垫板制备流程如下:
先将低聚二元醇、矿物土、填料及二异氰酸酯按比例计量混合,然后一同加到双螺杆挤出机中挤出,挤出后造粒。在模具中注射成型,即得产品。包装。
本发明的独到之处在于首次得用价格十分低廉、存在广泛的矿物土填充聚氨酯弹性体,制得了填充聚氨酯弹性体轨枕垫板。其保持相应聚氨酯弹性体的优异性能,并大大降低了聚氨酯弹性体的价格,使聚氨酯弹性体轨枕垫板与普通橡胶轨枕垫板价格相近,且性能远优于普通橡胶轨枕垫板。
本发明具有极高的工业生产及应用的可行性,具有较大的经济意义及理论研究意义。其优点如下:
1、采用该种矿物土填充聚氨酯弹性体可得到价格低廉的聚氨酯弹性体。
2、填充后的聚氨酯弹性体的应用性能得以保持,并有些性能得以提高,其制得轨枕垫板的性能好于普通橡胶轨枕垫板。
3、填充用的矿物土无需进一步加工或处理,即可直接使用。
4、填充工艺简单,弹性体轨枕垫板制备简单。
下面通过实施例对本发明作进一步说明:
实施例
将脱水的低聚物二元醇和小分子二元醇(对二异氰酸酯的当量比为0.97-1.03)、矿物土(对100重量份聚合物加0-100份)和二异氰酸酯从储槽中计量后,送入高速搅拌的混合头中,均匀混合和浇注在熟化炉内120℃热的传送带上。连续浇注的混合物在传送带上边移动,边熟化。固化后的胶块自动进入粉碎机,大块胶料粉碎成小块粒,再连续进入挤出造粒机造粒,再用注射机注射成形制得聚氨酯弹性体轨枕垫板。
实例1:
将脱水的分子量1000的聚己二元酸乙二醇酯与1,4丁二醇(当量比为1∶2、20%矿物土(对聚合物重量)熔融后和熔融的MDI(对二元醇的当量比为3∶3)计量打入高速搅拌的混合头中,120℃反应3分钟,均匀混合和浇注在熟化炉内120℃热的传送带上热化2小时。固化后胶块粉碎、挤出造粒。注射成形制聚氨酯弹性体轨枕垫板。
实例2:
同实例1,仅改变填充的矿物土的用量占总重量的30%,制备聚氨酯弹性轨枕垫板。
实例3:
同实例1,仅改变填充的矿物土的用量占总重量的40%,制备聚氨酯弹性体轨枕垫板。
实例4:
同实例1,仅改变填充的矿物土的用量占总重量的50%,制备聚氨酯弹性体轨枕垫板。
实例5:
同实例2,仅用部分一缩乙二醇代替部分丁二醇(与丁二醇的重比为1∶1),制备聚氨酯弹性体轨枕垫板。
实例6:
将胶水的分子量1000的聚四氢呋喃醚二醇与1,4丁二醇(当量比为1∶2、30%的矿物土(对聚合物重量)熔融后和熔融的MDI(对二元醇的当量比为3∶3)计量打入高速搅拌的混合头中,100℃反应2分钟,均匀混合,浇注在熟化炉内120℃热的传送带上熟化1小时。固化后胶块粉碎、挤出造粒。注射成形制聚氨酯弹性体轨枕垫板。
实例7:
同实例6,仅改变填充的矿物土的用量占总重量的50%,制备聚氨酯弹性体轨枕垫板。
实例8:
同实例6 ,仅用部分一缩乙二醇代替部分丁二醇(与丁二醇重量比为1∶1),制备聚氨酯弹性体轨枕垫板。
比较例1:
同实例1,但不填充矿物土,制得聚氨酯弹性体轨枕垫板。
比较例2:
同实例6,但不填充矿物土,制得聚氨酯弹性体轨枕垫板。
水发明实施例及比较例的试样的聚合物组成、反应条件及物性如表1和表2:
表1 试样的聚合物组成、反应条件
注:低聚二元醇与二异氰酸酯的当量比为1.00;二异氰酸酯为MDI表2 试样的物性实施例 拉伸强度 伸长率 200%模量 永久变形 硬度 体积电阻 空气热老化(100℃×72h
低聚二元醇 混合温度/时间 熟化温度/时间 矿物填充量℃/min ℃/hr % | |
实施例比较例 | 1己二酸乙二醇 120/3 120/2 202 303 404 505 /丁二醇/一缩乙二醇 306四氢呋喃醚醇 100/2 120/1 307 508 /丁二醇/一缩乙二醇 301己二酸乙二醇 120/3 120/2 02四氢呋喃醚醇 100/2 120/1 0 |
Mpa % Mpa % 邵A ×10-10Ω.cm 拉伸强度MPa 伸长率%1 49.9 680 19.0 10.5 90 200.0 30.7 4102 43.0 650 22.0 10.5 94 17.0 26.3 3903 39.8 400 23.0 62 95 11.0 19.9 2304 36.5 180 25.0 7.5 93 9.0 17.8 1605 38.9 660 19.0 23 68 10000 19.5 4006 28.9 450 6.8 60 92 5700 18.9 2907 32.0 200 6.0 36 96 1700 18.1 1708 31.0 380 7.0 39 65 22100 16.9 210比较例1 36.2 674 25.6 60 85 8800 17.9 4202 31.0 550 8.0 63 83 19000 11.0 290阿克隆磨耗(Cm3/1.61Km)均≤0.06
Claims (7)
1、一种新型聚氨酯弹性体所制造的铁路混凝土用的轨枕垫板,其特征在于:
a、采用扩链剂使用多元醇和异氰酸酯合成的聚氨酯弹性体;
b、采用助剂、矿物土填充剂组成而制得的填充聚氨酯弹性体;
c、经注塑或热压制造弹性体轨枕垫板。
2,制造轨枕垫板的聚氨酯弹性性体原料,按照权利要求,其特征在于:
a、其特征在于所说的扩链剂是1,4-丁二醇是三羟甲基丙烷3,3-三氯-4,4-二苯甲烷二胺;
b、其特征在于加入按摩尔配出计算为:
多元醇二扩链剂∶异氰酸酯=1∶(1-3)∶(2-4)
c、其特征在于所使用的催化剂是有机锡类及吗啡淋。
3、该轨枕垫板的制造,按照权利的要求是弹性体与矿物土配比是1∶0.1-0.6。
4、该轨枕垫板的制造,按权利要求其特征在于所用的偶联剂是KH-550、KH-560、KH-570,所用的润滑剂是硬脂酸及其盐类、石蜡类;
5、该轨枕垫板的制造,按照权利的要求,其特征在于:所用的光稳定剂是苯酚类;
6、本发明的独到之处是按有关配比一次造粒成型,工艺简单,价格低廉,制成的垫板比普通橡胶轨枕垫板的性能优异;
7、本发明的独到之处是填充用的矿物土,无需进一步加工或处理可直接使用。
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Cited By (3)
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---|---|---|---|---|
CN100457669C (zh) * | 2006-01-17 | 2009-02-04 | 宜昌永固科技开发有限公司 | 公路常温快速铺彩混凝土 |
CN102762623A (zh) * | 2009-12-21 | 2012-10-31 | 巴斯夫欧洲公司 | 包含集料和弹性体组合物的复合材料 |
CN108929532A (zh) * | 2017-05-28 | 2018-12-04 | 毛利 | 一种铁路注塑降噪橡胶垫板及其制备工艺 |
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1996
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100457669C (zh) * | 2006-01-17 | 2009-02-04 | 宜昌永固科技开发有限公司 | 公路常温快速铺彩混凝土 |
CN102762623A (zh) * | 2009-12-21 | 2012-10-31 | 巴斯夫欧洲公司 | 包含集料和弹性体组合物的复合材料 |
US8710135B2 (en) | 2009-12-21 | 2014-04-29 | Basf Se | Composite materials comprising aggregate and an elastomeric composition |
US9631088B2 (en) | 2009-12-21 | 2017-04-25 | Basf Se | Composite pavement structures |
CN106699011A (zh) * | 2009-12-21 | 2017-05-24 | 巴斯夫欧洲公司 | 包含集料和弹性体组合物的复合材料 |
US9850625B2 (en) | 2009-12-21 | 2017-12-26 | Basf Se | Composite pavement structures |
US10480128B2 (en) | 2009-12-21 | 2019-11-19 | Basf Se | Composite pavement structures |
CN108929532A (zh) * | 2017-05-28 | 2018-12-04 | 毛利 | 一种铁路注塑降噪橡胶垫板及其制备工艺 |
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