CN106866924A - 隔震聚氨酯弹性体材料组合物及其制备方法 - Google Patents
隔震聚氨酯弹性体材料组合物及其制备方法 Download PDFInfo
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- CN106866924A CN106866924A CN201710087956.3A CN201710087956A CN106866924A CN 106866924 A CN106866924 A CN 106866924A CN 201710087956 A CN201710087956 A CN 201710087956A CN 106866924 A CN106866924 A CN 106866924A
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- Prior art keywords
- polyurethane elastomer
- shock insulation
- component
- elastomer material
- temperature
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及一种隔震聚氨酯弹性体材料组合物及其制备方法。采用双组分体系常温常压混合浇注固化成型,得到隔震聚氨酯弹性体材料静刚度可控制在12~18kN/mm,密度0.95~1.0g/cm3,电阻值108~1010Ω。该方法原料易得,工艺简单,成本低廉,可连续大规模生产,现场施工,主要用于建筑、轨道交通隔震及其它工程隔震。
Description
技术领域
本发明属于聚氨酯弹性体的制造方法,具体涉及一种用于生产隔震材料的双组分室温固化型聚氨酯弹性体的组合物及其制备方法。
背景技术
聚氨酯材料是以多元醇为软段、异氰酸酯及扩链剂等为硬段组成的含有大量氨基甲酸酯基团且具有软硬段交替排列嵌段结构的线性或交联聚合物,具有较好的力学性能、耐磨耗性能、耐油、耐低温、减震等性能,而且可以在室温下现场混合、浇注施工,常温固化形成低硬度隔震弹性体材料。通过合理配方设计可以得到力学性能、动态性能、电性能等满足隔震要求的弹性体材料。
现有的技术如专利CN200510111548公开了一种NDI基聚氨酯微孔弹性体的制备方法,旨在解决现有技术中聚氨酯微孔弹性体耐候性,尤指水解稳定性差的技术问题。本发明的制备方法包括如下步骤:(1)预聚体的制备:过量的多异氰酸酯与多元醇在120-140℃条件下反应,形成端-NCO基的预聚体;(2)浇注:将预聚体与扩链剂组分按比例混合,反应料液注入温度为80-95℃的模具中,预熟化后脱模;(3)后熟化:脱模后的制品于110℃后熟化13-16小时。通过本发明方法制备的产品用作承受动态疲劳的高强度阻尼元件如汽车等交通工具的缓冲减震元件和桥梁减震块 等。
CN200510111549公开了一种MDI基聚氨酯微孔弹性体的制备方法,旨在解决现有技术中聚氨酯微孔弹性体动态疲劳形变率大的技术缺陷。本发明的制备方法包括如下步骤:(1)预聚体的制备:过量的多异氰酸酯与多羟基化合物在70-90℃条件下反应,形成端-NCO基的预聚体;(2)浇注:将预聚体与扩链剂组分按比例混合,反应料液注入温度为80-95℃的模具内,预熟化后脱模;(3)后熟化:脱模后的制品于110℃后熟化13-16小时。通过本发明方法制备获得的产品用作汽车等交通工具的缓冲减震元件。
CN201010284073公开了一种高速铁路用微孔聚氨酯弹性体减震元件,其特征是由23-40份聚醚多元醇A、5-10份扩链剂、0.1-0.5份水、0.2-0.55份硅油匀泡剂和0.15-0.3份催化剂构成的混合物I和由2.5-8份改性纳米高岭土、24-30份聚醚多元醇B和30-40份多异氰酸酯反应制备的半预聚物II于35-55℃下搅拌混合2-5分钟后浇注于预热至45-70℃并涂覆有脱模剂的模具中成型,成型脱模后于80-100℃下熟化10-20小时得到减震元件。
CN201510409642公开了一种低压缩永久变形的PPDI基聚氨酯弹性体及其制备方法。本发明通过有机多元醇与PPDI反应得到NCO含量为2%-9%的异氰酸酯基封端的预聚物,然后该预聚物与质量分数为10%-60%小分子二醇扩链剂和40%-90%的小分子三醇交联剂混合物反应,生产一种力学性能较好且压缩永久变形较 低的浇注型PPDI基聚氨酯弹性体。
然而上述技术难以满足更高强度的建筑、轨道交通隔震及其它工程隔震要求。
空心微球中的有机空心微球外壳为热塑性丙烯酸聚合物,内核为烷烃气体组成的球状塑料颗粒,粒径一般在10-30微米,壳体有良好的弹性并可承受较压力,加热膨胀之后形成轻质空心微球,同时保持自身的良好性能。将空心微球与其他材料结合形成复合材料以提高材料的隔震性能,如CN201310032320一种轻质复合材料,更具体的是涉及空心微球和纤维体复合材料。由均匀分布的基材、纤维体和空心微球组成。纤维体和空心微球体积总和与基材的比例为1:5~1:1;基材为热塑性或热固性树脂;纤维体为麻纤维、碳纤维、玻璃纤维、丙纶、芳纶、玄武岩纤维的至少一种;空心微球为空心玻璃微球、空心陶瓷微球中的至少一种;纤维体和空心微球的体积比为1:5~1:1;纤维体和空心微球通过基材粘结在一起。解决现有复合材料内部多为实心结构,其在隔热、隔音、减震等方面效果并不理想的问题。
然而现有技术中并未报道将聚氨酯弹性体与空心微球复合在一起提高其隔震性能,且还可以提高聚氨酯弹性体的动态性能,保持较强的机械性能,达到良好的减震效果。
本发明采用MDI体系的二苯基甲烷二异氰酸酯、多苯基甲烷多异氰酸酯的混合物或由聚环氧丙烷醚多元醇与二苯基甲烷二异氰酸酯反应得到的预聚物为一个组分;聚醚多元醇和胺类扩链剂、醇类扩 链剂、催化剂、空心微球及其它助剂组成聚合物多元醇组分。两组分室温下混合、浇注固化得到一种具有隔震功能的复合材料,和常用的聚氨酯弹性体产品相比可以现场、常温施工,隔震效果更好,且还可以提高聚氨酯弹性体的动态性能,保持较强的机械性能。
发明内容
本发明目的是提供一种室温固化双组分聚氨酯弹性体组合物,该材料生产过程简单,且具有适当的粘度、良好的流动性及合理的固化时间,所得材料既具有一定的物理机械性能还具有良好的动态性能的特点。可以用于现场灌注隔震施工,这一应用具有很大的经济意义。
本发明隔震聚氨酯弹性体材料组合物及其制备方法采用双组分聚氨酯弹性体体系,由两种组分组成:
A组分:以重量百分数计,将聚环氧丙烷醚多元醇和接枝聚合物多元醇68~70%、芳香族二元胺扩链剂1.4~1.8%,脂肪族二元醇扩链剂0.3~0.7%,无机填料15~20%,催化剂0.01~0.05%,抗老化剂、消泡剂各0.2~0.7%,液体增塑剂5~10%,在100~110℃混合均匀脱气至水分含量小于0.05%,降温至25~35℃,加入空心微球0.3~1%,并混合均匀。
所述的聚合物多元醇官能度为3,数均分子量在4000~7000范围内的聚环氧丙烷醚多元醇和接枝聚合物多元醇。
B组份:异氰酸酯组分,所用异氰酸酯由二苯基甲烷二异氰酸酯及多苯基甲烷多异氰酸酯按照质量比10/90~90/10混合而成,或由2官能度聚环氧丙烷醚多元醇在70℃~90℃与二苯基甲烷二异氰酸酯反应得到异氰酸根含量为8~15%的预聚物。
A组份与B组份以100/5~100/15重量比混合,混合温度为常温,然后浇注成型,常温固化24小时,室温下熟化168小时。得到静刚度在12~18kN/mm,密度在0.9~1.0g/cm3,电阻108~1010Ω,动静刚度比1.5~2的材料。
本发明A组份和B组份独立包装,在现场施工生产时,A与B组份常温混合、浇注成型、固化而成。
所述的聚环氧丙烷醚多元醇数均分子量为4800和6000。聚环氧丙烷醚多元醇优选GEP-330N,GEP-3600(市售,上海高桥石化公司)。
所述的接枝聚合物多元醇(乙烯基聚合物接枝聚醚多元醇,Polyether Polyol)数均分子量为6000。接枝聚合物多元醇优选GPOP-36/28(市售,上海高桥石化公司)。
所述的异氰酸酯优选多苯基多次甲基多异氰酸酯如PM200(市售,万华化学集团股份有限公司)和二苯基甲烷二异氰酸酯如MDI-100,MDI-50(市售,万华化学集团股份有限公司)。
所述芳香二元胺扩链剂优选3,5-二甲硫基甲苯(E-300)(市售,美国雅宝公司)
所述脂肪族二元醇优选用1,4-丁二醇。
催化剂选有基锡和叔胺类,优选二月桂酸二丁基锡和三亚乙基二胺(A33)(市售,美国气体化学公司)。
无机填料优选硫酸钡。
所述抗老化剂优选抗氧剂1010、紫外线吸收剂UV-P(市售,德国朗盛公司)。
所述消泡剂优选BYK-066N(市售,德国BYK化学公司)
空心微球选用空心玻璃微球和具有核壳结构的有机微球,优选有机发泡微球WU-150W(市售,西能化工科技(上海)有限公司)。
所述2官能度、分子量400-2000的聚环氧丙烷醚多元醇,优选Tdiol-1000数均分子量1000,不饱和度≤0.01mmol/g和Tdiol-2000数均分子量2000,不饱和度≤0.01mmol/g聚环氧丙烷醚二元醇(市售,天津石化三厂)。
隔震聚氨酯弹性体的制备方法,将A组分、B组分以扩链系数为0.85~1.0的范围进行混合反应,混合温度为常温;然后进行现场常温浇注、常温固化成型,得到隔震聚氨酯弹性体。
固化温度为常温,最低适用温度为-20℃。
固化成型为常温固化24小时,168小时达到最佳性能。
扩链系数为NH2/NCO(0H/NCO)的当量数比,即多元醇组分(包括多元醇组分中扩链剂)中氨基、羟基的量与异氰酸酯或预聚体中NCO的量的比值。
与现有技术相比,本发明具有以下有益效果:
本发明隔震聚氨酯弹性体材料组合物及其制备方法,使隔震材料可以现场常温浇注施工,本发明工艺性能良好,制品的隔震性能得到了较大提高,且还可以提高聚氨酯弹性体的动态性能,保持较强的机械性能,这一应用有很大的经济意义。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的保护范围。此外应理解,在阅读本发明讲授的内容之后,本领域技术人员可以对本发明做各种改动或修改,这些等价形式同样属于本申请所附权利要求书所限定的范围。
以下实施例所用材料如下:未作特别说明,各百分数均指的是质量百分数。
Tdiol-1000数均分子量1000,不饱和度≤0.01mmol/g聚环氧丙烷醚二元醇
Tdiol-2000数均分子量2000,不饱和度≤0.01mmol/g聚环氧丙烷醚二元醇
GEP-3600数均分子量6000,不饱和度≤0.01mmol/g聚环氧丙烷醚三元醇
GEP-36/28数均分子量6000,接枝聚合物三元醇
GEP-330N数均分子量4800,不饱和度≤0.01mmol/g聚环氧丙烷醚三元醇
PM200多苯基多次甲基多异氰酸酯(PAPI)
MDI-100 4,4′-二苯基甲烷二异氰酸酯
MDI-50 4,4′-二苯基甲烷二异氰酸酯50%与2,4′-二苯基甲烷二异氰酸酯50%混合物
1,4-BDO 1,4-丁二醇
E-300 3,5-二甲硫基甲苯二胺
催化剂二月桂酸二丁基锡,A33三亚乙基二胺
BYK-066N有机硅类消泡剂
WU-150W有机发泡微球
抗氧剂1010四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯
UV-P紫外线吸收剂2-(2ˊ-羟基-5ˊ-甲基苯基)苯并三氮唑
实施例1:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量6000的聚环氧丙烷醚多元醇(GEP-3600)60,分子量为6000的接枝聚醚多元醇(GPOP-36/28)40,扩链剂E-300,14.5,扩链剂1,4-BDO6.4,紫外线吸收剂UV-P 0.5、催化剂二月桂酸二丁基锡0.05,催化剂A33 0.1,硫酸钡15,有机空心微球WU-150W 0.5,抗氧剂1010,0.5,消泡剂BYK-066N0.6,在100±10℃,真空度-0.1MPa下混合搅拌、抽真空。
B组分:异氰酸酯组分:按照如下制备方法得到:以重量百分数计,PM-200与MDI-50按照质量比1:1混合
异氰酸酯组分与多元醇组分以0.90的扩链系数进行混合反应,混合温度、固化温度为常温,40min凝胶,试样尺寸250mm×180mm×30mm,室温停放24小时后脱模,室温放置168小时后得到聚氨酯 弹性体制品。
电阻率测定按照国家标准GB/T2439-2001进行;
刚度测试条件为:试验环境温度为(23±2)℃。位移速度0.01mm/s,位移控制:位移大小0~-1mm,再从-1mm~0,不停留,反复试验3次,将第3次加载时在-0.2mm、-0.8mm位移测得的加载力分别记为F1和F2,即为在ΔA(-0.2mm)和ΔB(-0.8mm)时隔离式试样的加载力F1和F2。
静刚度按下式计算:
S0=F1-F2/(ΔA-ΔB)
动刚度测试条件为:试验环境温度23±2℃。加载频率(4±1)Hz,周期荷载0.072kN~0.36kN,循环1000次。在最后的100次荷载循环中,记录10个循环的实际施加荷载F1ai、F2ai和加载平台的位移D1i、D2i。计算F1ai、F2ai、D1i、D2i的平均值,记为F1a、F2a、D1、D2。用下公式计算动刚度:
动刚度与静刚度之比即为动静刚度比。(以下测试条件同实施例1)
实施例2:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量6000的聚环氧丙烷醚多元醇(GEP-3600)70,分子量为6000的接枝聚醚多元醇(GPOP-36/28)30,扩链剂E-30014.5,扩链剂1,4-BDO 6.4,紫外线吸收剂UV-P 0.5、催化剂二月桂酸二丁基锡0.05,催化剂A33 0.1,硫酸钡15,有机空心微球WU-150W 0.8,抗氧剂1010 0.5,消泡剂BYK-066N 0.6,在100±10℃,真空度-0.1MPa下混合搅拌、抽真空。
B组分:异氰酸酯组分:按照如下制备方法得到:以重量百分数计,PM-200与MDI-50按照质量比60:40混合
异氰酸酯组分与多元醇组分以0.90的扩链系数比进行混合反应,混合温度、固化温度为常温,40min凝胶,室温停放24小时后脱模,室温放置168小时后得到聚氨酯弹性体制品。
实施例3:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量6000的聚环氧丙烷醚多元醇(GEP-3600)60,分子量为6000的接枝聚醚多元醇(GPOP-36/28)40,扩链剂E-30014.5,扩链剂1,4-BDO6.4,紫外线吸收剂UV-P 0.5、催化剂二月桂酸二丁基锡0.05,催化剂A33 0.1,硫酸钡15,有机空心微球WU-150W 0.5,抗氧剂1010 0.5,消泡剂BYK-066N 0.6,在100±10℃,真空度-0.1MPa下混合搅拌、抽真空。
B组分:异氰酸酯组分:按照如下制备方法得到:以重量百分数计,2官能度、分子量1000-2000的聚环氧丙烷醚多元醇(Tdiol-1000和Tdiol-2000)57%,二苯基甲烷二异氰酸酯(MDI-100)43%,在80℃反应2~3小时得到异氰酸根含量为13%的预聚物。
异氰酸酯组分与多元醇组分以0.90的扩链系数比、质量比10:100进行混合反应,混合温度、固化温度为常温,40min凝胶,室温停放24小时后脱模,室温放置168小时后得到聚氨酯弹性体制品。
实施例4:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量6000的聚环氧丙烷醚多元醇(GEP-3600)40,分子量4800的聚环氧丙烷醚多元醇(GEP-330N)20,分子量为6000的接枝聚醚多元醇(GPOP-36/28)40,扩链剂E-300,14.5,扩链剂1,4-BDO 6.4,紫外线吸收剂UV-P 0.5、催化剂二月桂酸二丁基锡0.05,催化剂A33 0.1,硫酸钡15,有机空心微球WU-150W 0.5,抗氧剂1010,0.5,消泡剂BYK-066N 0.6,在100±10℃,真空度-0.1MPa下混合搅拌、抽真空。
B组分:异氰酸酯组分:按照如下制备方法得到:以重量百分数计,PM-200与MDI-50按照质量比1:1混合
异氰酸酯组分与多元醇组分以0.90的扩链系数比进行混合反应,混合温度、固化温度为常温,40min凝胶,室温停放24小时后脱模,室温放置168小时后得到聚氨酯弹性体制品。
实施例5:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量6000的聚环氧丙烷醚多元醇(GEP-3600)30,分子量4800的聚环氧丙烷醚多元醇(GEP-330N)30,分子量为6000的接枝聚醚多元醇(GPOP-36/28)40,扩链剂E-300 14.5,扩链剂1,4-BDO 6.4,紫外线吸收剂UV-P 0.5、催化剂二月桂酸二丁基锡0.05,催化剂A33 0.1,硫酸钡15,有机空心微球WU-150W 0.5,抗氧剂1010 0.5,消泡剂BYK-066N0.6,在100±10℃,真空度-0.1MPa下混合搅拌、抽真空。
B组分:异氰酸酯组分:按照如下制备方法得到:以重量百分数计,分子量1000的聚环氧丙烷醚多元醇(Tdiol-1000)37%,分子量2000的聚环氧丙烷醚多元醇(Tdiol-2000)20%,二苯基甲烷二异氰酸酯(MDI-100)43%,在80℃反应2~3小时得到异氰酸根含量为13%的预聚物。
异氰酸酯组分与多元醇组分以0.90的扩链系数比、质量比10:100进行混合反应,混合温度、固化温度为常温,40min凝胶,室温停放24小时后脱模,室温放置168小时后得到聚氨酯弹性体制品。
对比例1:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量1000的聚四氢呋喃多元醇(PTMG-1000)74%,甲苯二异氰酸酯(T-100)26%,在70℃反应2~3小时得到异氰酸根含量为6.2%的预聚物。
B组分:固化剂选自3,3ˊ-二氯-4,4ˊ-二氨基二苯基甲烷(MOCA)。
预聚物和MOCA以0.9的扩链系数进行混合反应,混合温度为80℃,制品硫化温度为100℃,硫化40分钟脱模,在110℃后硫化10小时, 得到聚氨酯弹性体制品。
对比例2:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量6000的聚环氧丙烷醚多元醇(GEP-3600)60,分子量为6000的接枝聚醚多元醇(GPOP-36/28)40,扩链剂E-300,14.5,扩链剂1,4-BDO6.4,紫外线吸收剂UV-P 0.5、催化剂二月桂酸二丁基锡0.05,催化剂A33 0.1,硫酸钡15,抗氧剂1010,0.5,消泡剂BYK-066N 0.6,在100±10℃,真空度-0.1MPa下混合搅拌、抽真空。
B组分:异氰酸酯组分:按照如下制备方法得到:以重量百分数计,PM-200与MDI-50按照质量比1:1混合
异氰酸酯组分与多元醇组分以0.90的扩链系数比进行混合反应,混合温度、固化温度为常温,40min凝胶,室温停放24小时后脱模,室温放置168小时后得到聚氨酯弹性体制品。
对比例3:
A组分:多元醇组分:按照如下制备方法得到:以重量份计,分子量6000的聚环氧丙烷醚多元醇(GEP-3600)60,分子量为6000的接枝聚醚多元醇(GPOP-36/28)40,扩链剂E-30014.5,扩链剂1,4-BDO6.4,紫外线吸收剂UV-P 0.5、催化剂二月桂酸二丁基锡0.05,催化剂A33 0.1,硫酸钡15,抗氧剂1010 0.5,消泡剂BYK-066N 0.6,在100±10℃,真空度-0.1MPa下混合搅拌、抽真空。
B组分:异氰酸酯组分:按照如下制备方法得到:以重量百分数计,分子量1000-2000的聚环氧丙烷醚多元醇Tdiol-1000,Tdiol-200057%,二苯基甲烷二异氰酸酯(MDI-100)43%,在80℃反应2~3小时得到异氰酸根含量为13%的预聚物。
异氰酸酯组分与多元醇组分以0.90的扩链系数、质量比10:100进行混合反应,混合温度、固化温度为常温,40min凝胶,室温停放24小时后脱模,室温放置168小时后得到聚氨酯弹性体制品。
表1为实施例1-5和对比例1-3的聚氨酯弹性体制品性能测试结果。
表1实施例1-5和对比例1-3的性能测试结果
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (10)
1.一种隔震聚氨酯弹性体材料组合物,其特征在于,采用两种组分在常温常压下混合制得:
A组分:多元醇组分,以重量百分数计,将聚环氧丙烷醚多元醇和接枝聚合物多元醇68~70%、芳香族二元胺扩链剂1.4~1.8%,脂肪族二元醇扩链剂0.3~0.7%,无机填料15~20%,催化剂0.01~0.05%,抗老化剂、消泡剂、触变剂各0.2~0.7%,液体增塑剂5~10%,在100~110℃混合均匀脱气至水分含量小于0.05%,降温至25~35℃,加入空心微球0.3~1%,并混合均匀;
B组份:异氰酸酯组分,由二苯基甲烷二异氰酸酯及多苯基甲烷多异氰酸酯按照质量比10/90~90/10混合而成,或由2官能度聚环氧丙烷醚多元醇在70℃~90℃与二苯基甲烷二异氰酸酯反应得到异氰酸根含量为8~15%的预聚物。
2.根据权利要求1所述的隔震聚氨酯弹性体材料组合物,其特征在于,所述聚环氧丙烷醚多元醇为官能度为3,数均分子量为4000~7000的聚环氧丙烷醚多元醇的一种或几种的混合物,优选数均分子量为4800-7000的一种或几种的混合物。
3.根据权利要求1所述的隔震聚氨酯弹性体材料组合物,其特征在于,芳香族二元胺扩链剂选自二乙基甲苯二胺、3,5-二甲硫基甲苯、3,3′-二氯-4,4′-二氨基二苯基甲烷中的一种或几种;脂肪族二元醇选用乙二醇、丙二醇、二甘醇、1,4-丁二醇中的一种或几种;所述催化剂选自有机锡、有机铋、有机锌、叔胺类(三亚乙基二胺A33、双二甲基氨基乙基醚A-1)中的一种或几种;所述无机填料选用碳酸钙、滑石粉、二氧化硅、硫酸钡等中的一种或几种;所述液体增塑剂选用邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二甲氧乙酯、邻苯二甲酸二辛酯中的一种或几种;所述抗老化剂选用抗氧剂1010、168,紫外线吸收剂UV-326、UV-P中的一种或几种;所述消泡剂选用有机硅类消泡剂;所述触变剂选用气相法二氧化硅或缔合型增稠剂中的一种或混合物。
4.根据权利要求1所述的隔震聚氨酯弹性体材料组合物,其特征在于,所述空心微球选用空心玻璃微球或具有核壳结构的有机微球中的一种或混合物。
5.根据权利要求1所述的隔震聚氨酯弹性体材料组合物,其特征在于,所述异氰酸酯选用二苯基甲烷二异氰酸酯、改性的二苯基甲烷二异氰酸酯、多苯基甲烷多异氰酸酯中的一种或几种。
6.根据权利要求1所述的隔震聚氨酯弹性体材料组合物,其特征在于,所述2官能度聚环氧丙烷醚多元醇选用分子量400~1000的聚环氧丙烷醚多元醇的一种或几种的混合物。
7.根据权利要求1-6所述的隔震聚氨酯弹性体材料的制备方法,其特征在于,将B组分、A组分以扩链系数0.85~1.0进行混合反应,混合温度为常温,然后进行浇注、固化成型,脱模后得到聚氨酯弹性体。
8.根据权利要求1-6所述的隔震聚氨酯弹性体材料的制备方法,其特征在于,A组份与B组份以100/5~100/15重量比混合,混合温度为常温,然后浇注成型,常温固化24小时,室温下熟化168小时。
9.根据权利要求7所述的隔震聚氨酯弹性体材料的制备方法,其特征在于,混合、固化成型温度为常温。
10.根据权利要求8或9所述的隔震聚氨酯弹性体材料的制备方法,其特征在于,固化温度最低适用温度为-20℃。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1934176A (zh) * | 2004-03-22 | 2007-03-21 | 3M创新有限公司 | 填充纤维增强的热塑性复合材料 |
CN101781454A (zh) * | 2009-12-25 | 2010-07-21 | 山东东大一诺威聚氨酯有限公司 | 一种低硬度聚氨酯弹性体组合物 |
CN102040826A (zh) * | 2010-09-10 | 2011-05-04 | 山东东大一诺威聚氨酯有限公司 | 一种汽车止滑垫用聚氨酯弹性体组合物 |
CN103087463A (zh) * | 2013-01-28 | 2013-05-08 | 奇瑞汽车股份有限公司 | 一种轻质复合材料 |
-
2017
- 2017-02-18 CN CN201710087956.3A patent/CN106866924A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1934176A (zh) * | 2004-03-22 | 2007-03-21 | 3M创新有限公司 | 填充纤维增强的热塑性复合材料 |
CN101781454A (zh) * | 2009-12-25 | 2010-07-21 | 山东东大一诺威聚氨酯有限公司 | 一种低硬度聚氨酯弹性体组合物 |
CN102040826A (zh) * | 2010-09-10 | 2011-05-04 | 山东东大一诺威聚氨酯有限公司 | 一种汽车止滑垫用聚氨酯弹性体组合物 |
CN103087463A (zh) * | 2013-01-28 | 2013-05-08 | 奇瑞汽车股份有限公司 | 一种轻质复合材料 |
Non-Patent Citations (1)
Title |
---|
林晓甜等: ""有机微球对聚氨酯弹性体性能的影响"", 《塑料工业》 * |
Cited By (16)
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CN109824847A (zh) * | 2017-11-23 | 2019-05-31 | 北京市建筑工程研究院有限责任公司 | 一种聚氨酯-脲减振缓冲柔性阻尼材料及其制备方法 |
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