CN114591710A - 一种双组分pu结构胶及其制备方法 - Google Patents
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 21
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000005070 sampling Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003381 stabilizer Substances 0.000 claims description 22
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 18
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 235000011037 adipic acid Nutrition 0.000 claims description 13
- 239000001361 adipic acid Substances 0.000 claims description 13
- 150000002009 diols Chemical class 0.000 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 13
- 229920000728 polyester Polymers 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 description 14
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
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Abstract
本发明公开了一种双组分PU结构胶,包含A组分与B组分;其步骤包括:S1、异氰酸酯与1,4‑丁二醇按照质量比加入反应釜,控制釜内温度为60±2℃,搅拌混合反应至少3h,取样分析,NCO质量分数为20.0%‑20.2%,出料得A组分;S2、将所述的B组分物质,按照质量比加入反应釜,于60±2℃搅拌混合均匀,2h后取样分析,羟值为146~155mgKOH/g,得B组分。在压缩强度和压缩模量上面有了非常大的提升,现有的产品几乎没有加强作用,通过碳纳米管的加入,减轻整体重量的同时,大大提升了使用的部位的支撑性能和抗冲击性能,在汽车碰撞过程中减少使用部位的变形量,大大提升了安全性能。
Description
技术领域
本发明涉及一种双组分PU结构胶及其制备方法。
背景技术
针对汽车的空腔部位,在设计时一般采用加强钣金或者塑料进行增强,同时使用普通PU泡沫或发泡橡胶进行填充,但是这类材料几乎没有增强的功能,导致车辆在受到撞击时很容易发生变形,进而威胁乘客的生命安全,原因是这些普通PU泡沫均为软质材料,固化后模量较低,且材质较脆不能很好地提升钣金的耐冲击性。如何解决上述技术问题,是本领域技术人员致力于解决的事情。
发明内容
本发明所要解决的技术问题是:提供一种粘结性好,发泡后产品强度高,具有一定的支撑性的双组分PU结构胶。
为解决上述技术问题,本发明所采用的技术方案为:一种双组分PU结构胶,包含A组分与B组分;所述的A组分NCO质量分数为20.0%-20.2%;所述的 B组分羟值为146~155mgKOH/g;
所述的A组分为异氰酸酯与1,4-丁二醇按照质量比为8~9:1形成的预聚物;所述的异氰酸酯为MDI、TDI、HMDI中的一种或多种;
所述的B组分,按照质量份数,聚四氢呋喃多元醇10-45份,己二酸系聚酯二元醇10-15份,聚己内酯多元醇5-10份,改性聚醚多元醇35-40份,三氧化二锑3-5份,有机硅匀泡剂2-6份,碳纳米管5-10份,叔胺类催化剂0.5-1 份,三乙烯二胺0.5-1份,去离子水1-3份,发泡剂2-3份,稳定剂0.3-0.6份,抗氧剂0.3-0.6份;
所述的己二酸系聚酯二元醇的制备步骤,包括:反应釜内用N2置换后升温至 60~80℃时,投入15.6Wt.%的EG、26.1%的DEG和58.2%的AA;再升温至9O℃时,N2改从上部通入;100℃时蒸馏塔送蒸汽;继续升温至140℃,稳定在140℃反应1h;逐渐升温至220℃,当无水馏出之后,在220-225℃保温反应1h,投入催化剂钛酸四异丙酯,混合反应0.5h,,减压真空反应170min,调整N2流速为8~ 12m3/h,取样分析,当酸值≤0.6mgKOH/g,黏度在75℃时为350~380mPa·s,羟值80~85mgKOH/g。
所述的A组分为异氰酸酯与1,4-丁二醇按照质量比为8:1形成的预聚物;
所述的异氰酸酯为MDI、TDI、HMDI中的一种或多种;
所述的B组分,按照质量份数,聚四氢呋喃多元醇35-40份,己二酸系聚酯二元醇12-15份,聚己内酯多元醇8-10份,改性聚醚多元醇35-38份,三氧化二锑3-4份,有机硅匀泡剂3-5份,碳纳米管8-10份,叔胺类催化剂0.5-0.8 份,三乙烯二胺0.5-0.8份,去离子水2-3份,发泡剂2-2.5份,稳定剂0.3-0.5 份,抗氧剂0.5-0.6份。
所述的B组分,按照质量份数,聚四氢呋喃多元醇38份,己二酸系聚酯二元醇15份,聚己内酯多元醇10份,改性聚醚多元醇36份,三氧化二锑4 份,有机硅匀泡剂3份,碳纳米管10份,叔胺类催化剂0.6份,三乙烯二胺0.8 份,去离子水2份,发泡剂2.5份,稳定剂0.4份,抗氧剂0.6份。
所述改性聚醚多元醇的官能度为3,羟值为210±10mgKOH/g。
所述的稳定剂为无重金属离子的液态稳定剂。
所述的碳纳米管,直径为5~15nm。
所述的发泡剂为无机发泡剂。
本申请所要解决的第二个技术方案是:提供一种双组分PU结构胶的制备方法。
为解决第二个技术问题,采用的技术方案是:一种双组分PU结构胶的制备方法,其步骤包括:
S1、异氰酸酯与1,4-丁二醇按照质量比加入反应釜,控制釜内温度为60± 2℃,搅拌混合反应至少3h,取样分析,NCO质量分数为20.0%-20.2%,出料得 A组分;
S2、将所述的B组分物质,按照质量比加入反应釜,于60±2℃搅拌混合均匀,2h后取样分析,羟值为146~155mgKOH/g,得B组分。
本发明技术效果:在压缩强度和压缩模量上面有了非常大的提升,现有的产品几乎没有加强作用,通过碳纳米管的加入,减轻整体重量的同时,大大提升了使用的部位的支撑性能和抗冲击性能,在汽车碰撞过程中减少使用部位的变形量,大大提升了安全性能。
所述的改性聚醚多元醇的官能度为3,与异氰酸酯反应后,形成立体网状结构,增强了聚氨酯的支撑性,同时也增加了PU的粘结性能和填充性。
具体实施方式
下面结合实施例,对本发明技术方案进行进一步描述:
实施例1
一种双组分PU结构胶,包含A组分与B组分;所述的A组分NCO质量分数为20.0%-20.2%;所述的B组分羟值为146~155mgKOH/g;
所述的A组分为异氰酸酯与1,4-丁二醇按照质量比为9:1形成的预聚物;所述的异氰酸酯为MDI;
所述的B组分,按照质量份数,聚四氢呋喃多元醇45份,己二酸系聚酯二元醇12份,聚己内酯多元醇10份,改性聚醚多元醇38份,三氧化二锑4 份,有机硅匀泡剂5份,碳纳米管9份,叔胺类催化剂0.5份,三乙烯二胺1 份,去离子水3份,发泡剂2份,稳定剂0.5份,抗氧剂0.6份;
所述的己二酸系聚酯二元醇的制备步骤,包括:反应釜内用N2置换后升温至 60~80℃时,投入15.6Wt.%的EG、26.1%的DEG和58.2%的AA;再升温至9O℃时,N2改从上部通入;100℃时蒸馏塔送蒸汽;继续升温至140℃,稳定在140℃反应1h;逐渐升温至220℃,当无水馏出之后,在220-225℃保温反应1h,投入催化剂钛酸四异丙酯,混合反应0.5h,,减压真空反应170min,调整N2流速为8~ 12m3/h,取样分析,当酸值≤0.6mgKOH/g,黏度在75℃时为350~380mPa·s,羟值80~85mgKOH/g。
双组分PU结构胶的制备方法,其步骤包括:
S1、异氰酸酯与1,4-丁二醇按照质量比加入反应釜,控制釜内温度为60± 2℃,搅拌混合反应至少3h,取样分析,NCO质量分数为20.0%-20.2%,出料得 A组分;
S2、将所述的B组分物质,按照质量比加入反应釜,于60±2℃搅拌混合均匀,2h后取样分析,羟值为146~155mgKOH/g,得B组分。
实施例2
一种双组分PU结构胶,包含A组分与B组分;所述的A组分NCO质量分数为20.0%-20.2%;所述的B组分羟值为146~155mgKOH/g;
所述的A组分为异氰酸酯与1,4-丁二醇按照质量比为8:1形成的预聚物;
所述的异氰酸酯为TDI;
所述的B组分,按照质量份数,聚四氢呋喃多元醇38份,己二酸系聚酯二元醇15份,聚己内酯多元醇10份,改性聚醚多元醇36份,三氧化二锑4 份,有机硅匀泡剂3份,碳纳米管10份,叔胺类催化剂0.6份,三乙烯二胺0.8 份,去离子水2份,发泡剂2.5份,稳定剂0.4份,抗氧剂0.6份。
所述改性聚醚多元醇的官能度为3,羟值为210±10mgKOH/g。
双组分PU结构胶的制备方法,其步骤包括:
S1、异氰酸酯与1,4-丁二醇按照质量比加入反应釜,控制釜内温度为60± 2℃,搅拌混合反应至少3h,取样分析,NCO质量分数为20.0%-20.2%,出料得 A组分;
S2、将所述的B组分物质,按照质量比加入反应釜,于60±2℃搅拌混合均匀,2h后取样分析,羟值为146~155mgKOH/g,得B组分。
实施例3
一种双组分PU结构胶,包含A组分与B组分;所述的A组分NCO质量分数为20.0%-20.2%;所述的B组分羟值为146~155mgKOH/g;
所述的A组分为异氰酸酯与1,4-丁二醇按照质量比为8.5:1形成的预聚物;所述的异氰酸酯为HMDI;
所述的B组分,按照质量份数,聚四氢呋喃多元醇25份,己二酸系聚酯二元醇12份,聚己内酯多元醇10份,改性聚醚多元醇36份,三氧化二锑4 份,有机硅匀泡剂3份,碳纳米管10份,叔胺类催化剂1份,三乙烯二胺0.8 份,去离子水1份,发泡剂3份,稳定剂0.5份,抗氧剂0.4份;
所述的己二酸系聚酯二元醇的制备步骤,包括:反应釜内用N2置换后升温至 60~80℃时,投入15.6Wt.%的EG、26.1%的DEG和58.2%的AA;再升温至9O℃时,N2改从上部通入;100℃时蒸馏塔送蒸汽;继续升温至140℃,稳定在140℃反应1h;逐渐升温至220℃,当无水馏出之后,在220-225℃保温反应1h,投入催化剂钛酸四异丙酯,混合反应0.5h,,减压真空反应170min,调整N2流速为8~ 12m3/h,取样分析,当酸值≤0.6mgKOH/g,黏度在75℃时为350~380mPa·s,羟值80~85mgKOH/g。
一种双组分PU结构胶的制备方法,其步骤包括:
S1、异氰酸酯与1,4-丁二醇按照质量比加入反应釜,控制釜内温度为60± 2℃,搅拌混合反应至少3h,取样分析,NCO质量分数为20.0%-20.2%,出料得 A组分;
S2、将所述的B组分物质,按照质量比加入反应釜,于60±2℃搅拌混合均匀,2h后取样分析,羟值为146~155mgKOH/g,得B组分。
实施例的性能指标测试:
性能 | 实施例1 | 实施例2 | 实施例3 |
闪点℃ | 195 | 203 | 198 |
凝胶时间s | 38 | 40 | 36 |
体积膨胀率% | 280 | 290 | 270 |
压缩强度kPa | 9700 | 9900 | 9600 |
压缩模量kPa | 383000 | 395000 | 386000 |
Claims (9)
1.一种双组分PU结构胶,包含A组分与B组分;所述的A组分NCO质量分数为20.0%-20.2%;所述的B组分羟值为146~155mgKOH/g;
所述的A组分为异氰酸酯与1,4-丁二醇按照质量比为8~9:1形成的预聚物;所述的异氰酸酯为MDI、TDI、HMDI中的一种或多种;
所述的B组分,按照质量份数,聚四氢呋喃多元醇10-45份,己二酸系聚酯二元醇10-15份,聚己内酯多元醇5-10份,改性聚醚多元醇35-40份,三氧化二锑3-5份,有机硅匀泡剂2-6份,碳纳米管5-10份,叔胺类催化剂0.5-1份,三乙烯二胺0.5-1份,去离子水1-3份,发泡剂2-3份,稳定剂0.3-0.6份,抗氧剂0.3-0.6份;
所述的己二酸系聚酯二元醇的制备步骤,包括:反应釜内用N2置换后升温至60~80℃时,投入15.6Wt.%的EG、26.1%的DEG和58.2%的AA;再升温至9O℃时,N2改从上部通入;100℃时蒸馏塔送蒸汽;继续升温至140℃,稳定在140℃反应1h;逐渐升温至220℃,当无水馏出之后,在220-225℃保温反应1h,投入催化剂钛酸四异丙酯,混合反应0.5h,,减压真空反应170min,调整N2流速为8~12m3/h,取样分析,当酸值≤0.6mgKOH/g,黏度在75℃时为350~380mPa·s,羟值80~85mgKOH/g。
2.根据权利要求1所述的双组分PU结构胶,其特征在于:所述的A组分为异氰酸酯与1,4-丁二醇按照质量比为8:1形成的预聚物;
所述的异氰酸酯为MDI、TDI、HMDI中的一种或多种。
3.根据权利要求1所述的双组分PU结构胶,其特征在于:所述的B组分,按照质量份数,聚四氢呋喃多元醇35-40份,己二酸系聚酯二元醇12-15份,聚己内酯多元醇8-10份,改性聚醚多元醇35-38份,三氧化二锑3-4份,有机硅匀泡剂3-5份,碳纳米管8-10份,叔胺类催化剂0.5-0.8份,三乙烯二胺0.5-0.8份,去离子水2-3份,发泡剂2-2.5份,稳定剂0.3-0.5份,抗氧剂0.5-0.6份。
4.根据权利要求3所述的双组分PU结构胶,其特征在于:所述的B组分,按照质量份数,聚四氢呋喃多元醇38份,己二酸系聚酯二元醇15份,聚己内酯多元醇10份,改性聚醚多元醇36份,三氧化二锑4份,有机硅匀泡剂3份,碳纳米管10份,叔胺类催化剂0.6份,三乙烯二胺0.8份,去离子水2份,发泡剂2.5份,稳定剂0.4份,抗氧剂0.6份。
5.根据权利要求1~4任一项所述的双组分PU结构胶,其特征在于:所述改性聚醚多元醇的官能度为3,羟值为210±10mgKOH/g。
6.根据权利要求1~4任一项所述的双组分PU结构胶,其特征在于:所述的稳定剂为无重金属离子的液态稳定剂。
7.根据权利要求1~4任一项所述的双组分PU结构胶,其特征在于:所述的碳纳米管,直径为5~15nm。
8.根据权利要求1~4任一项所述的双组分PU结构胶,其特征在于:所述的发泡剂为无机发泡剂。
9.权利要求1~8所述的一种双组分PU结构胶的制备方法,其步骤包括:
S1、异氰酸酯与1,4-丁二醇按照质量比加入反应釜,控制釜内温度为60±2℃,搅拌混合反应至少3h,取样分析,NCO质量分数为20.0%-20.2%,出料得A组分;
S2、将所述的B组分物质,按照质量比加入反应釜,于60±2℃搅拌混合均匀,2h后取样分析,羟值为146~155mgKOH/g,得B组分。
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