CN116254088A - 一种双组分聚氨酯灌封胶及其制备方法和应用 - Google Patents
一种双组分聚氨酯灌封胶及其制备方法和应用 Download PDFInfo
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- CN116254088A CN116254088A CN202310123031.5A CN202310123031A CN116254088A CN 116254088 A CN116254088 A CN 116254088A CN 202310123031 A CN202310123031 A CN 202310123031A CN 116254088 A CN116254088 A CN 116254088A
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
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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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- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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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Abstract
本发明提供一种双组分聚氨酯灌封胶及其制备方法和应用,所述双组分聚氨酯灌封胶包括A组分和B组分,所述A组分包括特定份数的多亚甲基多苯基多异氰酸酯、稀释剂和异氰酸酯封端聚合物的组合,所述B组分包括油脂多元醇、聚醚多元醇、导热填料、促粘接剂和催化剂的组合;所述双组分聚氨酯灌封胶具有粘度低、无沉降以及阻燃效果好的优势,且具有可操作时间长的优势,同时固化后对裸铝、PET膜等基材均具有优异粘接性能,能够用于新能源动力电池的灌封粘接。
Description
技术领域
本发明属于粘结剂技术领域,具体涉及一种双组分聚氨酯灌封胶及其制备方法和应用。
背景技术
随着人们环保意识的不断加强,对于新能源汽车的关注度在逐步升高。新能源汽车的整体性能在很大程度上取决于其电机、电池和电控的性能,其中热管理是重中之重。目前,新能源汽车动力电池大多数是锂离子电池,汽车电池包中的锂离子电池在充放电过程中会产生热量。为了将电池产生的热量传递至电池包的降温系统中,需要用导热材料。电池包中电池组装结构紧凑,电池之间的空隙小,需要导热材料在固化前具有优异的流动性,从而填满电池的空隙。另外,在汽车行驶过程中,电池包难免会受到震动,因此导热材料需要具有优异的粘接性能和减震性。
导热灌封胶是目前新能源电动汽车应用较为广泛的一种热管理材料。导热灌封胶主要可以分为环氧导热灌封胶、聚氨酯导热灌封胶和有机硅导热灌封胶三大类;其中,环氧导热灌封胶韧性差、易开裂、不耐冷热冲击,有机硅导热灌封胶硬度低、粘接强度低,而聚氨酯灌封胶具有软硬度可调、粘接强度适中、高弹性、高抗冲击性、高耐磨性和优异的耐低温性能等特点,因此聚氨酯导热灌封胶在新能源电池中的使用越来越广泛。
传统灌封胶应用领域对灌封胶与基材的粘接性能普遍无强制性要求。对于新能源电池用导热灌封胶,通常要求灌封胶对电池包基材有较好的粘接性,新能源电池涉及的灌封基材包括3系铝、6系铝及PET膜等;另一方面,由于部分灌封件缝隙小,灌封胶需要长期保持低粘度才能完全灌满粘接零部件。
CN102627937A公开了一种双组分导热聚氨酯灌封胶及其制备方法,其中组分I是为聚合物多元醇、扩链剂、催化剂、消泡剂和改性导热填料混合均匀得到,组分II为异氰酸酯。该聚氨酯灌封胶具有绝缘性好、柔韧性好、导热系数高。然而该双组分导热聚氨酯灌封胶的粘度上升快,并且对铝等基材的粘接性比较差,因而难以用做新能源电池导热灌封胶。
因此,开发一种粘度低、粘接性高、断裂伸长率高且可操作时间长的双组分聚氨酯灌封胶,成为本领域迫切需要解决的技术问题。
发明内容
针对现有技术的不足,本发明的目的在于提供一种双组分聚氨酯灌封胶及其制备方法和应用,所述双组分聚氨酯灌封胶具有粘度低、无沉降、阻燃效果好以及可操作时间长的优势,同时对裸铝、PET膜等基材均具有优异的粘接性能,能够在新能源动力电池的灌封粘接中使用。
为达此目的,本发明采用以下技术方案:
第一方面,本发明提供一种双组分聚氨酯灌封胶,所述双组分聚氨酯灌封胶包括A组分和B组分;
所述A组分按照重量份包括如下组分:
多亚甲基多苯基多异氰酸酯 50~80重量份
稀释剂 5~20重量份
异氰酸酯封端聚合物 10~40重量份;
所述B组分按照重量份包括如下组分:
其中,所述多亚甲基多苯基多异氰酸酯可以为55重量份、60重量份、65重量份、70重量份或75重量份等。
所述稀释剂包括7重量份、9重量份、11重量份、13重量份、15重量份、17重量份或19重量份等。
所述异氰酸酯封端聚合物可以为15重量份、20重量份、25重量份、30重量份或35重量份等。
所述油脂多元醇可以为42重量份、44重量份、46重量份、48重量份、50重量份、52重量份、54重量份、56重量份或58重量份等。
所述聚醚多元醇可以为4重量份、6重量份、8重量份、10重量份、12重量份或14重量份等。
所述导热填料可以为55重量份、60重量份、65重量份、70重量份或75重量份等。
所述促粘接剂可以为1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份或4.5重量份等。
所述催化剂可以为0.005重量份、0.01重量份、0.03重量份、0.05重量份、0.07重量份或0.09重量份等。
本发明提供的双组分聚氨酯灌封胶包括A组分和B组分,所述A组分包括特定份数的多亚甲基多苯基多异氰酸酯、稀释剂和异氰酸酯封端聚合物的组合;所述B组分包括特定份数的油脂多元醇、聚醚多元醇、导热填料、促粘接剂和催化剂的组合;采用上述A组分和B组分进行搭配,通过添加特定的异氰酸酯封端聚合物在A组分以及添加特定的促粘接剂在B组分,使得到的双组分聚氨酯灌封胶具有粘度低、无沉降和阻燃效果好的优势,且A组分和B组分接触后粘度上升的比较慢,进而具有较长的可操作时间;且固化后对裸铝、PET膜等基材均具有优异粘接性能,能够用于新能源动力电池的灌封粘接。
优选地,所述稀释剂包括磷酸三甲苯酯和/或磷酸甲酚二苯酯。
优选地,所述异氰酸酯封端聚合物的制备原料包括异氰酸酯和聚酯多元醇。
优选地,所述聚酯多元醇包括聚碳酸酯二元醇和/或聚己内酯二元醇。
优选地,所述聚碳酸酯二元醇具体可以选择旭化成T4672、T4671、T5652或T5651中的任意一种或至少两种的组合。
优选地,所述聚己内酯二元醇具体可以选择大赛璐PLACCEL L212AL、PLACCELL220AL、PLACCEL L320AL、PLACCEL E220EB或PLACCEL E220EC中的任意一种或至少两种的组合。
优选地,所述聚酯多元醇的羟值为30~120mgKOH/g,例如40mgKOH/g、50mgKOH/g、60mgKOH/g、70mgKOH/g、80mgKOH/g、90mgKOH/g、100mgKOH/g或110mgKOH/g等。
优选地,所述异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯或二苯基甲烷二异氰酸酯中的任意一种或至少两种的组合。
优选地,所述异氰酸酯封端聚合物的R值大于2.5,例如3、4、5、6、7、8或9等。
优选地,所述异氰酸酯封端聚合物通过如下方法制备得到,所述方法包括:将聚酯多元醇和异氰酸酯进行反应,得到所述异氰酸酯封端聚合物。
优选地,所述反应的温度为60~80℃,例如62℃、64℃、66℃、68℃、70℃、72℃、74℃、76℃或78℃等。
优选地,所述反应的时间为1~3h,例如1.2h、1.4h、1.6h、1.8h、2h、2.2h、2.4h、2.6h或2.8h等。
优选地,所述反应在真空条件下进行。
作为本发明的优选技术方案,所述方法包括:将聚酯多元醇加入反应器,在100~140℃下真空脱水1~3h,然后降温到70℃以下,加入异氰酸酯在60~80℃真空搅拌反应1~3h,降温出料,得到异氰酸酯封端聚合物。
优选地,所述油脂多元醇包括菜籽油改性多元醇、蓖麻油改性多元醇、大豆油改性多元醇或棕榈油改性多元醇中的任意一种或至少两种的组合。
优选地,所述油脂多元醇选具体可以选择凡特鲁斯DB oil、D120、D140、D265、D290,巴斯夫Sovermol818、Sovermol819、Sovermol830、Sovermol860、Sovermol908、Sovermol1092、Sovermol1102或Sovermol1140中的任意一种或至少两种的组合。
优选地,所述油脂多元醇的官能度为2~3。
优选地,所述油脂多元醇的羟值为100~300mgKOH/g,例如120mgKOH/g、140mgKOH/g、160mgKOH/g、180mgKOH/g、200mgKOH/g、220mgKOH/g、240mgKOH/g、260mgKOH/g或280mgKOH/g等。
优选地,所述聚醚多元醇包括聚环氧丙烷醚二元醇和/或聚环氧丙烷醚三元醇。
优选地,所述聚环氧化丙烯二醇具体可以选择东大化学的DL2000、DL1000、DL4000,万华化学的C2010D、/>C2020、/>C2030、C2040D,陶氏化学的VORANOL2110TB、VORANOL2120、VORANOL3000LM、VORANOL4240或VORANOL222-056中的任意一种或至少两种的组合。
优选地,所述聚环氧化丙烯三醇具体可以选择万华化学的F3135,陶氏化学的VORANOL 3003N、2471、WT5000、230-042N、4701、CP6001或CP6005中的任意一种或至少两种的组合。
优选地,所述聚醚多元醇的羟值为20~120mgKOH/g,例如30mgKOH/g、40mgKOH/g、50mgKOH/g、60mgKOH/g、70mgKOH/g、80mgKOH/g、90mgKOH/g、100mgKOH/g或110mgKOH/g等。
优选地,所述促粘接剂的制备原料包括氨苯基硅烷和硅烷改性剂。
优选地,所述导热填料包括氢氧化铝、氢氧化镁、氧化铝、氧化镁或氮化硅中的任意一种或至少两种的组合。
优选地,所述导热填料的D90粒径<20μm,例如18μm、16μm、14μm、12μm、10μm、8μm、6μm、4μm或2μm等。
优选地,所述催化剂包括新癸酸铋、月桂酸铋、异辛酸铋或环烷酸铋中的任意一种或至少两种的组合。
优选地,所述氨苯基硅烷包括N-苯基-γ-氨丙基三甲氧基硅烷、N-苯基-γ-氨丙基三乙氧基硅烷、N-苯氨基甲基三甲氧基硅烷或N-苯氨基甲基三乙氧基硅烷中的任意一种或至少两种的组合。
优选地,所述硅烷改性剂包括邻甲苯基缩水甘油醚、对甲苯基缩水甘油醚、苯基缩水甘油醚、三苯甲基-(S)-缩水甘油醚或间苯二酚二缩水甘油醚中的任意一种或至少两种的组合。
优选地,所述氨苯基硅烷中仲氨基与所述硅烷改性剂中缩水甘油醚基团的摩尔比为1:(0.5~1.5),例如1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.2或1:1.4等。
优选地,所述促粘接剂通过如下方法制备得到,所述方法包括:将氨苯基硅烷和硅烷改性剂进行反应,得到所述促粘接剂。
优选地,所述反应的温度为30~70℃,例如35℃、40℃、45℃、50℃、55℃、60℃或65℃等。
优选地,所述反应的时间为1~3h,例如1.2h、1.4h、1.6h、1.8h、2h、2.2h、2.4h、2.6h或2.8h等。
优选地,所述A组分和B组分的质量比为(10~30):100,例如12:100、14:100、16:100、18:100、20:100、22:100、24:100、26:100或28:100等。
优选地,所述A组分的粘度为100~500CPS,例如150CPS、200CPS、250CPS、300CPS、350CPS、400CPS或450CPS等。
优选地,所述B组分的粘度为2000~6000CPS,例如2500CPS、3000CPS、3500CPS、4000CPS、4500CPS、5000CPS或5500CPS等。
第二方面,本发明提供一种如第一方面所述双组分聚氨酯灌封胶的制备方法,所述制备方法包括如下步骤:
(1)将稀释剂、多亚甲基多苯基多异氰酸酯和异氰酸酯封端聚合物进行混合,得到A组分;
将油脂多元醇、聚醚多元醇、导热填料、促粘接剂和催化剂进行混合,得到B组分;
(2)将步骤(1)得到的A组分和B组分混合,得到所述双组分聚氨酯灌封胶。
优选地步骤(1)所述将稀释剂、多亚甲基多苯基多异氰酸酯和异氰酸酯封端聚合物进行混合的混合时间为20~70℃(例如30℃、40℃、50℃或60℃等),混合时间为1~3h(例如1.2h、1.4h、1.6h、1.8h、2h、2.2h、2.4h、2.6h或2.8h等)。
优选地,步骤(1)所述将油脂多元醇、聚醚多元醇、导热填料、促粘接剂和催化剂进行混合的具体方式包括:将将油脂多元醇、聚醚多元醇和导热填料在100~140℃(例如105℃、110℃、115℃、120℃、125℃、130℃或135℃等)搅拌脱水1~3h(例如1.2h、1.4h、1.6h、1.8h、2h、2.2h、2.4h、2.6h或2.8h等),降温到100℃以下,加入促粘接剂和催化剂混合0.5~2h(例如0.7h、0.9h、1.1h、1.3h、1.5h、1.7h或1.9h等)。
第三方面,本发明提供一种如第一方面所述的双组分聚氨酯灌封胶在新能源电池中的应用。
相对于现有技术,本发明具有以下有益效果:
本发明提供的双组分聚氨酯灌封胶包括A组分和B组分,A组分包括特定份数的多亚甲基多苯基多异氰酸酯、稀释剂和异氰酸酯封端聚合物的组合,B组分包括油脂多元醇、聚醚多元醇、导热填料、促粘接剂和催化剂的组合;所述双组分聚氨酯灌封胶具有粘度低、无沉降以及阻燃效果好的优势,且具有可操作时间长的优势,固化后对裸铝、PET膜等基材均具有优异粘接性能,能够用于新能源动力电池的灌封粘接。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
制备例1
一种异氰酸酯封端聚合物,其制备方法包括:将100g聚酯二元醇(大赛璐PLACCELE220EB)在120℃真空脱水2h,然后降温到70℃,加入50g二苯基甲烷二异氰酸酯(MDI-50),真空搅拌下反应2h,然后降温出料,得到所述异氰酸酯封端聚合物。
制备例2
一种异氰酸酯封端聚合物,其制备方法包括:将100g聚酯二元醇(旭化成T4672)在120℃真空脱水2h,然后降温到70℃,加入50g甲苯二异氰酸酯(TDI),真空搅拌下反应2h,然后降温出料,得到所述异氰酸酯封端聚合物。
制备例3
一种异氰酸酯封端聚合物,其制备方法包括:将100g聚酯二元醇(大赛璐PLACCELE220EB)在120℃真空脱水2h,然后降温到70℃,加入50g异佛尔酮二异氰酸酯(IPDI),真空搅拌下反应2h,然后降温出料,得到所述异氰酸酯封端聚合物。
制备例4
一种异氰酸酯封端聚合物,其制备方法包括:将100g聚醚二元醇(DL-2000D)在120℃真空脱水2h,然后降温到70℃,加入50g二苯基甲烷二异氰酸酯(MDI-50),真空搅拌下反应2h,然后降温出料,得到所述异氰酸酯封端聚合物。
制备例5
一种促粘接剂,其制备方法包括:将255g N-苯基-γ-氨丙基三甲氧基硅烷加入到三口烧瓶中,搅拌、升温到40℃,加入164g对甲苯基缩水甘油醚在40℃搅拌反应2h,然后降温出料,得到所述促粘接剂。
制备例6
一种促粘接剂,其制备方法包括:将297g N-苯基-γ-氨丙基三甲氧基硅烷加入到三口烧瓶中,搅拌、升温到50℃,加入164g邻甲苯基缩水甘油醚在50℃搅拌反应1h,然后降温出料,得到所述促粘接剂。
制备例7
一种促粘接剂,其制备方法包括:将297g N-苯基-γ-氨丙基三甲氧基硅烷加入到三口烧瓶中,搅拌、升温到60℃,加入111g间苯二酚二缩水甘油醚在60℃搅拌反应0.5h,然后降温出料,得到所述促粘接剂。
实施例1
一种双组分聚氨酯灌封胶,其由A组分和B组分组成;
A组分的制备方法包括:将130g多亚甲基多苯基多异氰酸酯PM100、50g异氰酸酯封端聚合物(制备例1)和20g磷酸三甲苯酯加入到三口烧瓶中,真空搅拌分散1h,得到A组分,粘度约360CPS;
B组份的制备方法包括:将640g油脂多元醇(凡特鲁斯DB oil)、140g聚醚多元醇(东大DL2000)、1200g氧化铝导热粉(金戈JAZ213)在110℃真空脱水2h,降温至60℃,然后加入20g促粘接剂(制备例5)和0.2g异辛酸铋在真空状态下搅拌1h,得到B组分,粘度约4200CPS。
本实施例提供的双组分聚氨酯灌封胶的制备方法包括:将质量比为20:100的A组分和B组分混合,得到所述双组分聚氨酯灌封胶。
实施例2
一种双组分聚氨酯灌封胶,其由A组分和B组分组成;
A组分的制备方法包括:将100g多亚甲基多苯基多异氰酸酯PM200、50g异氰酸酯封端聚合物(制备例2)和30g磷酸三甲苯酯加入到三口烧瓶中,真空搅拌分散1h,得到A组分,粘度约310CPS;
B组份的制备方法包括:将720g蓖麻油改性多元醇(凡特鲁斯D120)、100g聚醚多元醇(东大DL1000)、1160g氢氧化铝(D90为10μm)在110℃真空脱水2h,降温至60℃,然后加入20g促粘接剂(制备例6)和0.1g异辛酸铋在真空状态下搅拌1h,得到B组分,粘度约3900CPS。
本实施例提供的双组分聚氨酯灌封胶的制备方法包括:将质量比为18:100的A组分和B组分混合,得到所述双组分聚氨酯灌封胶。
实施例3
一种双组分聚氨酯灌封胶,其由A组分和B组分组成;
A组分的制备方法包括:将180g多亚甲基多苯基多异氰酸酯PM300、50g异氰酸酯封端聚合物(制备例3)和20g磷酸三甲苯酯加入到三口烧瓶中,真空搅拌分散1h,得到A组分,粘度约340CPS;
B组份的制备方法包括:将520g蓖麻油改性多元醇(凡特鲁斯D290)、160g聚醚多元醇(东大DL2000)、1304g氧化铝导热粉(金戈JAZ213)在110℃真空脱水2h,降温至60℃,然后加入16g促粘接剂(制备例7)和0.1g月桂酸铋在真空状态下搅拌1h,得到B组分,粘度约4700CPS。
本实施例提供的双组分聚氨酯灌封胶的制备方法包括:将质量比为25:100的A组分和B组分混合,得到所述双组分聚氨酯灌封胶。
实施例4
一种双组分聚氨酯灌封胶,其与实施例1的区别仅在于,采用制备例4得到的异氰酸酯封端聚合物替换制备例1得到的异氰酸酯封端聚合物,其他组分、用量和制备方法均与实施例1相同。
对比例1
一种双组分聚氨酯灌封胶,其由A组分和B组分组成;
A组分的制备方法包括:将145g多亚甲基多苯基多异氰酸酯PM100和55g磷酸三甲苯酯加入到三口烧瓶中,真空搅拌分散1h,得到A组分,粘度约190CPS;
B组份的制备方法包括:将640g油脂多元醇(凡特鲁斯DB oil)、140g聚醚多元醇(东大DL2000)、1200g氧化铝导热粉(金戈JAZ213)在110℃真空脱水2h,降温至60℃,然后加入20g促粘接剂(制备例5)和0.2g异辛酸铋在真空状态下搅拌1h,得到B组分,粘度约4200CPS。
本对比例提供的双组分聚氨酯灌封胶的制备方法包括:将质量比为20:100的A组分和B组分混合,得到所述双组分聚氨酯灌封胶。
对比例2
一种双组分聚氨酯灌封胶,其与实施例1的区别仅在于,采用20g KH560替换20g制备例5得到的促粘接剂,其他组分、用量和制备方法均与实施例1相同。
对比例3
一种双组分聚氨酯灌封胶,其与实施例1的区别仅在于,油脂多元醇的添加量为440g,聚醚多元醇的添加量为340g,其他组分、用量和制备方法均与实施例1相同。
对比例4
一种双组分聚氨酯灌封胶,其与实施例1的区别仅在于,B组分不添加促粘接剂,其他组分、用量和制备方法均与实施例1相同。
性能测试:
(1)黏度:按照《GB/T 2794-2013》测试标准,采用DV2T型黏度计,在20~75%的扭矩范围条件下进行测定;
(2)可操作时间:标准条件下,将A组分和B组分按比例混合,然后按《GB/T 2794-2013》标准,测试混合后粘度上升到6000cps的时间;
(3)断裂伸长率:按《GB/T 528-2009》标准进行测定;样品厚度为2mm,表面平整、光滑、无污染,测试在25℃环境下,固化7天后用2型哑铃裁刀裁切出标准样条,拉伸速率为(100±10)mm/min;
(4)剪切强度:按《GB/T 7124-2008》标准进行测定;基材尺寸为100mm×25mm×2.5mm,粘接模块尺寸为25mm×25mm×1mm,测试基材为6061AL(酒精处理),样品在25℃环境下,固化7d后测试,测试速度5mm/min;
(5)阻燃性:制备长为125±5mm、宽为13.0±0.5mm、厚为2.0±0.2mm的样片;按《UL-94》标准方法制样测试。
按照上述测试方法对实施例1~3和对比例1~5提供的双组分聚氨酯灌封胶进行测试,测试结果如表1所示:
表1
根据表1数据可以看出:
本发明提供的双组分聚氨酯灌封胶粘度低,完全固化后粘接性高、断裂伸长率高、可操作时间长,且阻燃性能好;具体而言,实施例1~3提供的双组分混合后粘度1420~1600CPS,可操作时间大于40min,双组分聚氨酯灌封胶完全固化后的剪切强度大于2MPa,断裂伸长率大于180%,阻燃性均可达到V0等级。
从实施例1和对比例1的数据比较可知,A组分不添加异氰酸酯封端聚合物会导致最终制备得到的聚氨酯灌封胶的可操作时间显著降低,同时剪切强度与断裂伸长率也显著下降。
由实施例1和对比例2、4的数据对比可知,B组分不添加促粘接剂或者使用KH560替代促粘接剂,均会导致粘接强度的显著下降,特别是使用KH560替代促粘接剂时,断裂伸长率也将大大降低。
由实施例1和对比例3的数据对比可知,B组分聚醚多元醇比例增加时,聚氨酯灌封胶的粘接强度将大幅降低,并且阻燃性也由V0降低到V1。
综上,异氰酸酯封端聚合物、促粘接剂、油脂多元醇与聚醚多元醇的比例均对聚氨酯灌封胶的剪切强度、断裂伸长率等具有重要影响,各个组分之间相互配合,任一个组分的缺失或者含量的变化均会对本发明的技术效果产生不可预知的影响。
申请人声明,本发明通过上述实施例来说明一种双组分聚氨酯灌封胶及其制备方法和应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
2.根据权利要求1所述的双组分聚氨酯灌封胶,其特征在于,所述稀释剂包括磷酸三甲苯酯和/或磷酸甲酚二苯酯;
优选地,所述异氰酸酯封端聚合物的制备原料包括异氰酸酯和聚酯多元醇;
优选地,所述聚酯多元醇包括聚碳酸酯二元醇和/或聚己内酯二元醇;
优选地,所述聚酯多元醇的羟值为30~120mgKOH/g;
优选地,所述异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯或二苯基甲烷二异氰酸酯中的任意一种或至少两种的组合;
优选地,所述异氰酸酯封端聚合物的R值大于2.5;
优选地,所述异氰酸酯封端聚合物通过如下方法制备得到,所述方法包括:将聚酯多元醇和异氰酸酯进行反应,得到所述异氰酸酯封端聚合物;
优选地,所述反应的温度为60~80℃;
优选地,所述反应的时间为1~3h;
优选地,所述反应在真空条件下进行。
3.根据权利要求1或2所述的双组分聚氨酯灌封胶,其特征在于,所述油脂多元醇包括菜籽油改性多元醇、蓖麻油改性多元醇、大豆油改性多元醇或棕榈油改性多元醇中的任意一种或至少两种的组合;
优选地,所述油脂多元醇的官能度为2~3;
优选地,所述油脂多元醇的羟值为100~300mgKOH/g;
优选地,所述聚醚多元醇包括聚环氧丙烷醚二元醇和/或聚环氧丙烷醚三元醇;
优选地,所述聚醚多元醇的羟值为20~120mgKOH/g。
4.根据权利要求1~3任一项所述的双组分聚氨酯灌封胶,其特征在于,所述导热填料包括氢氧化铝、氢氧化镁、氧化铝、氧化镁或氮化硅中的任意一种或至少两种的组合;
优选地,所述导热填料的D90粒径<20μm;
优选地,所述催化剂包括新癸酸铋、月桂酸铋、异辛酸铋或环烷酸铋中的任意一种或至少两种的组合。
5.根据权利要求1~4任一项所述的双组分聚氨酯灌封胶,其特征在于,所述促粘接剂的制备原料包括氨苯基硅烷和硅烷改性剂;
优选地,所述氨苯基硅烷包括N-苯基-γ-氨丙基三甲氧基硅烷、N-苯基-γ-氨丙基三乙氧基硅烷、N-苯氨基甲基三甲氧基硅烷或N-苯氨基甲基三乙氧基硅烷中的任意一种或至少两种的组合;
优选地,所述硅烷改性剂包括邻甲苯基缩水甘油醚、对甲苯基缩水甘油醚、苯基缩水甘油醚、三苯甲基-(S)-缩水甘油醚或间苯二酚二缩水甘油醚中的任意一种或至少两种的组合;
优选地,所述氨苯基硅烷中仲氨基与所述硅烷改性剂中缩水甘油醚基团的摩尔比为1:(0.5~1.5);
优选地,所述促粘接剂通过如下方法制备得到,所述方法包括:将氨苯基硅烷和硅烷改性剂进行反应,得到所述促粘接剂;
优选地,所述反应的温度为30~70℃;
优选地,所述反应的时间为1~3h。
6.根据权利要求1~5任一项所述的双组分聚氨酯灌封胶,其特征在于,其特征在于,所述A组分和B组分的质量比为(10~30):100;
优选地,所述A组分的粘度为100~500CPS;
优选地,所述B组分的粘度为2000~6000CPS。
7.一种如权利要求1~6任一项所述双组分聚氨酯灌封胶的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)将稀释剂、多亚甲基多苯基多异氰酸酯和异氰酸酯封端聚合物进行混合,得到A组分;
将油脂多元醇、聚醚多元醇、导热填料、促粘接剂和催化剂进行混合,得到B组分;
(2)将步骤(1)得到的A组分和B组分混合,得到所述双组分聚氨酯灌封胶。
8.根据权利要求7所述的制备方法,其特征在于,步骤(1)所述将稀释剂、多亚甲基多苯基多异氰酸酯和异氰酸酯封端聚合物进行混合的混合温度为20~70℃,混合时间为1~3h。
9.根据权利要求7或8所述的制备方法,其特征在于,步骤(1)所述将油脂多元醇、聚醚多元醇、导热填料、促粘接剂和催化剂进行混合的具体方法包括:将油脂多元醇、聚醚多元醇和导热填料在100~140℃下搅拌脱水1~3h,降温到100℃以下,加入促粘接剂和催化剂进行混合0.5~2h。
10.一种如权利要求1~6任一项所述的双组分聚氨酯灌封胶在新能源电池中的应用。
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CN111303820A (zh) * | 2020-03-09 | 2020-06-19 | 杭州之江新材料有限公司 | 一种动力电池粘接用双组分聚氨酯结构胶及其制备方法 |
CN112608707A (zh) * | 2020-12-15 | 2021-04-06 | 广东普赛达密封粘胶有限公司 | 一种双组分聚氨酯结构胶及其制备方法 |
CN113667443A (zh) * | 2021-09-15 | 2021-11-19 | 杭州之江新材料有限公司 | 一种双组分聚氨酯导热结构胶及其制备方法 |
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