CN113831493B - 一种含有六重分子间氢键的自修复聚氨酯弹性体及其制备方法 - Google Patents
一种含有六重分子间氢键的自修复聚氨酯弹性体及其制备方法 Download PDFInfo
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- CN113831493B CN113831493B CN202111135738.5A CN202111135738A CN113831493B CN 113831493 B CN113831493 B CN 113831493B CN 202111135738 A CN202111135738 A CN 202111135738A CN 113831493 B CN113831493 B CN 113831493B
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 50
- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
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- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- HUQGLWLBOCSVMD-UHFFFAOYSA-N 4-methylpyridine-2,6-diamine Chemical compound CC1=CC(N)=NC(N)=C1 HUQGLWLBOCSVMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical group CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 claims 1
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
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- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- KMBMQZQZBOLJHN-UHFFFAOYSA-N 2-methyloxirane;oxolane Chemical compound CC1CO1.C1CCOC1 KMBMQZQZBOLJHN-UHFFFAOYSA-N 0.000 description 2
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- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JGYUBHGXADMAQU-UHFFFAOYSA-N 2,4,6-triethylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(CC)=C1N JGYUBHGXADMAQU-UHFFFAOYSA-N 0.000 description 1
- PTPIRFSXRFIROJ-UHFFFAOYSA-N 2-(3-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=CC(O)=C1 PTPIRFSXRFIROJ-UHFFFAOYSA-N 0.000 description 1
- ZBUIOKOKFSYRFY-UHFFFAOYSA-N 2-[2-(4-aminobenzoyl)oxyethoxy]ethyl 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1C(=O)OCCOCCOC(=O)C1=CC=C(N)C=C1 ZBUIOKOKFSYRFY-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical group CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- SWHBLYRMSOEGCY-UHFFFAOYSA-N 2-[2-[4-[2-(2-aminophenyl)sulfanylethoxy]phenoxy]ethylsulfanyl]aniline Chemical compound NC1=C(C=CC=C1)SCCOC1=CC=C(OCCSC2=C(C=CC=C2)N)C=C1 SWHBLYRMSOEGCY-UHFFFAOYSA-N 0.000 description 1
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 description 1
- DMGFVJVLVZOSOE-UHFFFAOYSA-N 3-amino-4-chlorobenzoic acid Chemical compound NC1=CC(C(O)=O)=CC=C1Cl DMGFVJVLVZOSOE-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- XRBXGZZMKCBTFP-UHFFFAOYSA-N 4-(2,2-dihydroxyethoxycarbonyl)benzoic acid Chemical compound OC(O)COC(=O)C1=CC=C(C(O)=O)C=C1 XRBXGZZMKCBTFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CMTWHLCDLXMRBS-UHFFFAOYSA-N NC(C=CC=C1)=C1SCCOC(C1=CC=CC=C1)=O Chemical compound NC(C=CC=C1)=C1SCCOC(C1=CC=CC=C1)=O CMTWHLCDLXMRBS-UHFFFAOYSA-N 0.000 description 1
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- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- DFCSFNUXZBPPTD-UHFFFAOYSA-N benzene-1,3-dicarbonyl isocyanate Chemical compound O=C=NC(=O)C1=CC=CC(C(=O)N=C=O)=C1 DFCSFNUXZBPPTD-UHFFFAOYSA-N 0.000 description 1
- DHZIIRMIXLYCRQ-UHFFFAOYSA-N benzene-1,4-dicarbonyl isocyanate Chemical compound O=C=NC(=O)C1=CC=C(C(=O)N=C=O)C=C1 DHZIIRMIXLYCRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
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- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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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- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明公开了一种含有六重分子间氢键的自修复聚氨酯弹性体,该聚氨酯弹性体制备工艺简单、以2,6‑二氨基吡啶或2,6‑二氨基吡啶的衍生物为扩链剂,制备得到的聚氨酯弹性体具有良好的机械性能,最大拉伸量达到2500%以上,且弹性滞后较小、耐疲劳,将含该有六重分子间氢键的自修复聚氨酯弹性体反复拉伸100次,瞬时形变恢复率达到98%,反复拉伸1×104次后,形变恢复率仍大于95%;此外,含有六重分子间氢键的自修复聚氨酯弹性体在2s内可实现深30μm宽20μm划痕的100%自修复,而且修复后的聚氨酯弹性体力学性能优异,在柔性电子、表面镀层保护、生物医药材料、新能源以及航空航天等领域具有巨大的应用前景。
Description
技术领域
本发明属于自修复弹性体材料的技术领域,尤其涉及一种含有六重分子间氢键的自修复聚氨酯弹性体及其制备方法。
背景技术
材料实现弹性化、多功能化是现今材料创新发展的核心挑战之一。现有的弹性体材料普遍存在缺口敏感、耐疲劳性差,弹性滞后严重的问题,因此迫切需要开发一类弹性体材料能够解决这些问题。
自修复材料作为一种智能材料,能修复在使用过程中产生的裂纹或局部损伤,从而恢复原有功能,延长使用寿命。自修复材料主要分为复合型自修复材料和本征型自修复材料两种。复合型自修复材料通过微囊结构设计实现,本征型自修复材料通过分子结构设计构建非共价键或动态共价键来实现自修复。而基于非共价键的本征型自修复材料在加工生产、抗缺口敏感、耐疲劳性等方面具有较大的优势。因此通过分子结构设计开发一种非共价键型自修复弹性体具有重要意义。
聚氨酯弹性体的聚集态结构包括硬段相、软段相及中间相。低聚物多元醇或低聚多元胺构成软段相,异氰酸酯及小分子扩链剂形成硬段相,在分子链中软段与硬段相互交替,形成嵌段结构,由于硬段与软段在热力学上的不相容性导致了微相分离。硬段间存在分子氢键键合。
公开号为CN112794979A的中国专利文献中公开了一种仿生启发的具有超韧、超拉伸及自修复高回弹性聚氨酯弹性体的制备方法:(1)以2-乙酰丁内酯,碳酸胍、三乙胺和1,6-己二异氰酸酯等为原料合成多重氢键单体;(2)以多重氢键单体、三氯化铁等为原料制备含有多重氢键及金属络合键的弹性体;制备得到的弹性体超韧、超拉伸、可自修复、且具有高回弹性能。但是该聚氨酯弹性体制备方法复杂、原料种类繁多、不利于大规模生产。
公开号为CN110790888A的中国专利文献中公开了一种基于多重动态可逆作用的高强度室温自修复聚氨酯弹性体及其制备与应用:(1)二元醇与二异氰酸酯在催化剂的作用下反应,获得预聚物;所述二元醇为聚醚二元醇和/或聚硅氧烷二元醇;(2)将扩链剂与预聚物反应,得到聚氨酯,所述的扩链剂为二羧酸扩链剂和二胺扩链剂,含有二硫键和吡啶基;(3)在有机溶剂中,将聚氨酯与金属盐交联剂反应,去除溶剂,获得高强度室温自修复聚氨酯弹性体。该发明原料种类繁多,制备过程稍复杂。
发明内容
本发明提供了一种含有六重分子间氢键的自修复聚氨酯弹性体,该聚氨酯弹性体制备工艺简单、具有良好的机械性能、弹性滞后较小、室温下自修复性能优异、耐疲劳,且自修复后机械性能优异,易于加工成型。
具体采用的技术方案如下:
一种含有六重分子间氢键的自修复聚氨酯弹性体,结构式如式(I)所示:
其中,m和n为正整数;R1为氢原子、卤素原子、C1-C30的烃基或C1-C30取代的烃基;R2为-o-R3-o-或R3和R4均为C1-C30的烃基或低聚杂链基团;X1为 X2为 R5和R6均为碳链聚合物基团、杂链聚合物基团、元素有机聚合物基团或无机聚合物基团,R7为二异氰酸酯残基。
所述的含有六重分子间氢键的自修复聚氨酯弹性体具有如下结构的分子间氢键:
所述的含有六重分子间氢键的自修复聚氨酯弹性体的制备方法可采用以下二种方法,第一种方法包括以下步骤:
(1)活性氢封端聚合物与二异氰酸酯在催化剂的作用下反应得到预聚体;
(2)将预聚体与扩链剂A和扩链剂B继续反应得到所述的含有六重分子间氢键的自修复聚氨酯弹性体。
第二种方法包括以下步骤:
(a)扩链剂A、扩链剂B和二异氰酸酯反应合成前驱体;
(b)在催化剂的作用下,将前驱体与活性氢封端聚合物混合,反应制得所述的含有六重分子间氢键的自修复聚氨酯弹性体。
所述的活性氢封端聚合物为羟基封端聚合物或氨基封端聚合物,分子量≥650g/mol。
所述的羟基封端聚合物为聚己二酸乙二醇酯、聚氧化丙烯醚多元醇、聚四氢呋喃、聚四氢呋喃多元醇、四氢呋喃-环氧丙烷二元共聚醚、聚己内酯多元醇、聚烯烃多元醇、聚碳酸酯多元醇或聚丙烯酸酯多元醇。
所述的氨基封端聚合物为二氨基封端四氢呋喃-环氧丙烷二元共聚醚、二氨基封端聚乙烯或二氨基封端聚硅氧烷。
优选的,所述的活性氢封端聚合物的分子量为650~5000g/mol。
优选的,所述的二异氰酸酯为4,4’-亚甲基-1,1’-二异氰酸苯酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、1,5-萘二异氰酸酯、间苯二异氰酸酯或对苯二异氰酸酯。
所述的扩链剂A为2,6-二氨基吡啶或2,6-二氨基吡啶的衍生物。
优选的,所述的扩链剂B为小分子二醇扩链剂或小分子二胺扩链剂。
所述的小分子二醇扩链剂包括但不限于1,4-丁二醇、乙二醇、丙二醇、1,6-己二醇、1,4-环己二醇、氢醌双(β-羟乙基)醚、氢化双酚A、对苯二甲酸二羟乙酯、间苯二酚二羟乙基醚、α-烯丙甘油基醚。
所述的小分子二胺扩链剂包括但不限于3,3'-二氯-4,4'-二氨基二苯基甲烷、3,5-二乙基-2,4-甲苯二胺、3,5-二乙基-2,6-甲苯二胺、2,4,6-三乙基苯-1,3-二胺、3,5-二甲硫基-2,4-甲苯二胺、3,5-二甲硫基-2,6-甲苯二胺、4,4'-亚甲基双(3-氯-2,6-二乙基苯胺)、二乙二醇双(4-氨基苯甲酸酯)、3,5-二氨基-4三氟甲基苯乙醚、3,5-二氨基-4-氯苯乙酸异丙酯、1,4-双(2-氨基苯基硫代乙氧基)苯、1,4-双(2-氨基苯基硫代乙基)苯甲酸酯、3-氨基-4-氯苯甲基-4'-氨基苯甲酸、亚甲基双(4-氨基-3-苯甲酸酯)、丙二醇双(对氨基苯甲酸酯)、4,4'-亚甲基双(2,6-二乙基-3-氯苯胺)、亚乙基双(2-氨基苯硫醚)。
所述的催化剂为双二甲氨基乙基醚、五甲基二乙烯三胺、二甲基环己胺、二月桂酸二丁基锡或有机铋等。
优选的,所述的活性封端聚合物、二异氰酸酯、扩链剂A和扩链剂B的摩尔比为1:2:k1:k2,其中,k1+k2=1且0≤k2<1。
优选的,所述的反应条件为80~90℃,所述的反应总时间为6~11h。
所述的含有六重分子间氢键的自修复聚氨酯弹性体制备方法简单,具有良好的拉伸性、较小的弹性滞后、优异的自修复性能,且主链为线性结构,玻璃化温度较低,易于加工成型,可根据不同的应用场景对制得的产物溶液进行模塑、涂覆加工。
即所述的含有六重分子间氢键的自修复聚氨酯弹性体在柔性电子、表面镀层保护、生物医药材料、新能源以及航空航天等领域具有巨大的应用前景。
与现有技术相比,本发明的有益效果在于:
(1)本发明公开的含有六重分子间氢键的自修复聚氨酯弹性体制备工艺简单、拉伸性能可调、最大拉伸量达到2500%以上、由于六重分子间动态氢键的存在,增加了分子间的交联密度,同时柔性链段较短,从而制得的聚氨酯弹性体弹性滞后较小、自修复性能优异、耐疲劳。
(2)本发明公开的含有六重分子间氢键的自修复聚氨酯弹性体反复拉伸100次,瞬时形变恢复率达到98%;反复拉伸1×104次后,形变恢复率仍大于95%。
(3)本发明公开的含有六重分子间氢键的自修复聚氨酯弹性体在2s内可实现深30μm宽20μm划痕的100%自修复,而且修复后的聚氨酯弹性体力学性能优异。
(4)本发明公开的含有六重分子间氢键的自修复聚氨酯弹性体能适用于多种复杂的使用环境,能够在多种环境下实现自修复。
附图说明
图1为实施例1制备得到的含有六重分子间氢键的自修复聚氨酯弹性体的应力-应变曲线图。
图2为实施例2制备得到的含有六重分子间氢键的自修复聚氨酯弹性体的应力-应变曲线图。
图3为实施例3制备得到的含有六重分子间氢键的自修复聚氨酯弹性体自修复前后的应力-应变曲线图。
图4为实施例3制备得到的含有六重分子间氢键的自修复聚氨酯弹性体的自修复性能图,其中左侧为自修复前的图片,右侧为自修复2s后的图片。
图5为实施例3制备得到的含有六重分子间氢键的自修复聚氨酯弹性体拉伸回复应力-应变图。
图6为实施例3制备得到的含有六重分子间氢键的自修复聚氨酯弹性体耐疲劳性测试图。
具体实施方式
实施例1
在一支安装有机械搅拌器和回流冷管的25mL圆底三口烧瓶中加入8mmoL聚四氢呋喃(分子量为:650g/mol)和3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯16mmoL,8mL N,N-二甲基甲酰胺,以及0.225g二月桂酸二丁基锡作为催化剂,85℃持续搅拌反应3.5h;继续向反应釜内加入0.4mmoL 2,6-二氨基吡啶、7.6mmoL 1,4-丁二醇和8mL N,N-二甲基甲酰胺,85℃持续搅拌继续反应3h,再加入2mL甲醇,将反应后的产物用甲醇析出,以甲醇作为洗脱剂,用索氏提取器进行纯化,80℃鼓风烘箱中干燥6~10h,得到含有六重分子间氢键的自修复聚氨酯弹性体。
本实施例制得的含有六重分子间氢键的自修复聚氨酯弹性体的应力-应变曲线图如图1所示,该自修复聚氨酯弹性体的最大拉伸量达到2500%。
实施例2
在一支安装有机械搅拌器和回流冷管的25mL圆底三口烧瓶中加入8mmoL聚四氢呋喃(分子量为:650g/mol)和3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯16mmoL,8mL N,N-二甲基甲酰胺,以及0.225g二月桂酸二丁基锡作为催化剂,85℃持续搅拌反应3.5h;继续向反应釜内加入5.6mmoL 2,6-二氨基吡啶、2.4mmoL 1,4-丁二醇和8mL N,N-二甲基甲酰胺,85℃持续搅拌继续反应4h,再加入2mL甲醇,将反应后的产物用甲醇析出,以甲醇作为洗脱剂,用索氏提取器进行纯化,80℃鼓风烘箱中干燥6~10h,得到含有六重分子间氢键的自修复聚氨酯弹性体。
本实施例制得的含有六重分子间氢键的自修复聚氨酯弹性体的应力-应变曲线图如图2所示,该自修复聚氨酯弹性体的最大拉伸应变为2520%、最大拉伸强度为30.69MPa。
实施例3
在一支安装有机械搅拌器和回流冷管的25mL圆底三口烧瓶中加入8mmoL聚四氢呋喃(分子量为:650g/mol)和3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯16mmoL,8mL N,N-二甲基甲酰胺,以及0.225g二月桂酸二丁基锡作为催化剂,85℃持续搅拌反应3.5h;继续向反应釜内加入4mmoL 2,6-二氨基吡啶、4mmoL 1,4-丁二醇和8mL N,N-二甲基甲酰胺,85℃持续搅拌继续反应4h,再加入2mL甲醇,将反应后的产物用甲醇析出,以甲醇作为洗脱剂,用索氏提取器进行纯化,80℃鼓风烘箱中干燥6~10h,得到含有六重分子间氢键的自修复聚氨酯弹性体。
本实施例制得的含有六重分子间氢键的自修复聚氨酯弹性体自修复前后的应力-应变曲线图如图3所示,自修复前后该聚氨酯弹性体的力学性能差别不大,修复后的聚氨酯弹性体力学性能优异。
本实施例制得的含有六重分子间氢键的自修复聚氨酯弹性体的自修复性能图如图4所示,该聚氨酯弹性体在2s内可实现深30μm宽20μm划痕的100%自修复,自修复性能优异。
本实施例制得的含有六重分子间氢键的自修复聚氨酯弹性体拉伸回复应力-应变图如图5所示,耐疲劳性测试图如图6所示,将该含有六重分子间氢键的自修复聚氨酯弹性体拉伸100次后,瞬时形变恢复率达到98%;反复拉伸1×104次后连续测试七次,形变恢复率仍在98%以上。
实施例4
在一支安装有机械搅拌器和回流冷管的25mL圆底三口烧瓶中加入2,6-二氨基吡啶4mmoL、4mmoL 1,4-丁二醇和4,4′-亚甲基-1,1′-二异氰酸苯酯16mmoL,8mL N,N-二甲基甲酰胺,85℃持续搅拌反应3h;然后停止加热冷却至室温,然后在搅拌的条件下,向反应釜内加入8mL N,N-二甲基甲酰胺,8mmoL聚四氢呋喃(分子量为:1200g/mol),以及0.225g二月桂酸二丁基锡作为催化剂,85℃持续搅拌继续反应3h;再加入2mL甲醇,将反应后的产物用甲醇析出,以甲醇作为洗脱剂,用索氏提取器进行纯化,80℃鼓风烘箱中干燥6~10h,得到含有六重分子间氢键的自修复聚氨酯弹性体。
实施例5
在一支安装有机械搅拌器和回流冷管的50mL圆底三口烧瓶中加入8mmoL氨丙基封端聚二甲基硅氧烷(分子量为:3000g/mol)和4,4’-亚甲基-1,1’-二异氰酸苯酯16mmoL,10mL N,N-二甲基甲酰胺,以及0.4g二月桂酸二丁基锡作为催化剂,85℃持续搅拌反应4h;继续向反应釜内加入4mmoL 2,6-二氨基吡啶、4mmoL 3,5-二乙基-2,4-甲苯二胺和8mL N,N-二甲基甲酰胺,85℃持续搅拌继续反应5h,再加入2mL甲醇,将反应后的产物用甲醇析出,以甲醇作为洗脱剂,用索氏提取器进行纯化,85℃鼓风烘箱中干燥6~10h,得到含有六重分子间氢键的自修复聚氨酯弹性体。
实施例6
在一支安装有机械搅拌器和回流冷管的50mL圆底三口烧瓶中加入8mmoL氨丙基封端聚二甲基硅氧烷(分子量为:2500g/mol)和4,4’-亚甲基-1,1’-二异氰酸苯酯16mmoL,10mL N,N-二甲基甲酰胺,以及0.4g二月桂酸二丁基锡作为催化剂,85℃持续搅拌反应4h;继续向反应釜内加入4mmoL 4-甲基-2,6-吡啶二胺、4mmoL 3,5-二甲硫基-2,6-甲苯二胺和8mL N,N-二甲基甲酰胺,85℃持续搅拌继续反应5h,再加入2mL甲醇,将反应后的产物用甲醇析出,以甲醇作为洗脱剂,用索氏提取器进行纯化,85℃鼓风烘箱中干燥6~10h,得到含有六重分子间氢键的自修复聚氨酯弹性体。
实施例7
在一支安装有机械搅拌器和回流冷管的25mL圆底三口烧瓶中加入8mmoL聚四氢呋喃(分子量为:650g/mol)和3-异氰酸酯基亚甲基-3,5,5-三甲基环己基异氰酸酯16mmoL,8mL N,N-二甲基甲酰胺,以及0.225g二月桂酸二丁基锡作为催化剂,85℃持续搅拌反应3.5h;继续向反应釜内加入8mmoL 2,6-二氨基吡啶、8mL N,N-二甲基甲酰胺,85℃持续搅拌继续反应4h,再加入2mL甲醇,将反应后的产物用甲醇析出,以甲醇作为洗脱剂,用索氏提取器进行纯化,80℃鼓风烘箱中干燥6~10h,得到含有六重分子间氢键的自修复聚氨酯弹性体。
Claims (3)
1.一种含有六重分子间氢键的自修复聚氨酯弹性体的制备方法,其特征在于,包括以下步骤:
(1)活性氢封端聚合物与二异氰酸酯在催化剂的作用下反应得到预聚体;
(2)将预聚体与扩链剂A和扩链剂B继续反应得到所述的含有六重分子间氢键的自修复聚氨酯弹性体;
或者,
包括以下步骤:
(a)扩链剂A、扩链剂B和二异氰酸酯反应合成前驱体;
(b)在催化剂的作用下,将前驱体与活性氢封端聚合物混合,反应制得所述的含有六重分子间氢键的自修复聚氨酯弹性体;
所述的活性氢封端聚合物为聚四氢呋喃,分子量≥650 g/mol;
所述的扩链剂A为2,6-二氨基吡啶或4-甲基-2,6-吡啶二胺;
所述的扩链剂B为1,4-丁二醇;
所述的活性封端聚合物、二异氰酸酯、扩链剂A和扩链剂B的摩尔比为1:2:k1:k2,其中,k1+k2=1且0<k2<1;
所述的反应条件为80~90℃,所述的反应总时间为6~11 h;
所述的含有六重分子间氢键的自修复聚氨酯弹性体的结构式如式(I)所示:
其中,m和n为正整数;R1为氢原子或C1-C30的烃基;R2为X1为X2为/>R5为聚四氢呋喃残基,R7为二异氰酸酯残基。
2.根据权利要求1所述的含有六重分子间氢键的自修复聚氨酯弹性体的制备方法,其特征在于,所述的二异氰酸酯为4,4’-亚甲基-1,1’-二异氰酸苯酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯、1,5-萘二异氰酸酯、间苯二异氰酸酯或对苯二异氰酸酯。
3.根据权利要求1所述的含有六重分子间氢键的自修复聚氨酯弹性体的制备方法,其特征在于,所述的催化剂为双二甲氨基乙基醚、五甲基二乙烯三胺、二甲基环己胺、二月桂酸二丁基锡或有机铋。
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