CN110964162B - 一种基于吡唑脲基的聚脲氨酯及其制备方法和应用 - Google Patents
一种基于吡唑脲基的聚脲氨酯及其制备方法和应用 Download PDFInfo
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- CN110964162B CN110964162B CN201811160174.9A CN201811160174A CN110964162B CN 110964162 B CN110964162 B CN 110964162B CN 201811160174 A CN201811160174 A CN 201811160174A CN 110964162 B CN110964162 B CN 110964162B
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- pyrazole
- polyureaurethane
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- 229920000162 poly(ureaurethane) Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 pyrazole compound Chemical class 0.000 claims abstract description 65
- IQFIWJDBZRZLNO-UHFFFAOYSA-N 1h-pyrazole;urea Chemical compound NC(N)=O.C=1C=NNC=1 IQFIWJDBZRZLNO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000005549 heteroarylene group Chemical group 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 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 9
- 239000013638 trimer Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 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 4
- 238000004064 recycling Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 2
- LOCPTSFJZDIICR-UHFFFAOYSA-N 1,3-bis(3-isocyanato-4-methylphenyl)-1,3-diazetidine-2,4-dione Chemical compound C1=C(N=C=O)C(C)=CC=C1N1C(=O)N(C=2C=C(C(C)=CC=2)N=C=O)C1=O LOCPTSFJZDIICR-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical class O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 claims description 2
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims 1
- 238000004078 waterproofing Methods 0.000 claims 1
- 239000004202 carbamide Substances 0.000 abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 15
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 46
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 13
- 238000004364 calculation method Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 125000002619 bicyclic group Chemical group 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 9
- 238000010200 validation analysis Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 125000002950 monocyclic group Chemical group 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002396 Polyurea Polymers 0.000 description 5
- RIKMMFOAQPJVMX-UHFFFAOYSA-N fomepizole Chemical compound CC=1C=NNC=1 RIKMMFOAQPJVMX-UHFFFAOYSA-N 0.000 description 5
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- KACZQOKEFKFNDB-UHFFFAOYSA-N ethyl 1h-pyrazole-4-carboxylate Chemical compound CCOC(=O)C=1C=NNC=1 KACZQOKEFKFNDB-UHFFFAOYSA-N 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
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- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 3
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- DYQFCTCUULUMTQ-UHFFFAOYSA-N 1-isocyanatooctane Chemical compound CCCCCCCCN=C=O DYQFCTCUULUMTQ-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明属于聚脲氨酯材料领域,提供了一种基于吡唑脲基的聚脲氨酯,其由吡唑类化合物,巯基类化合物和异氰酸酯类化合物反应得到,所述反应在室温条件下即可实现,方法简单、制备成本低,适合大规模工业化生产。本发明所述的含吡唑脲基的聚脲氨酯具有热可逆性,其在室温下较为稳定,当温度升至80℃以上时,可自发解离成含异氰酸酯和吡唑的化合物,并且可再次热压成型,反应得到基于吡唑脲基的聚脲氨酯;其相比于室温下就会解离的动态位阻脲键,耐水解性更高,大大提升了基于所述吡唑脲基的聚脲氨酯产品的实用性,可实现此类热固性聚脲氨酯的回收再利用。
Description
技术领域
本发明属于聚脲氨酯材料领域,具体涉及一种基于吡唑脲基的聚脲氨酯及其制备方法和应用。
背景技术
脲键可由异氰酸酯和有机胺的加成反应制备得到。由于羰基和氮原子的共振稳定作用,一般的脲键是一类十分稳定且不可逆的共价键,含脲键的化合物也是一类非常稳定的化合物。脲键的断裂通常需要十分苛刻的条件,比如酸或碱体系、高温、金属催化剂和酶等。聚脲在中性条件下的水解半衰期长达约1万年。
基于脲键构筑的聚合物为聚脲树脂。聚脲树脂是由多元胺和多异氰酸酯通过聚加成反应制备的一类聚合物,常被应用在涂层、粘结剂、纤维和弹性体等领域。多元胺商品主要有Huntsman公司的Jeffamine系列的端氨基聚醚。它和异氰酸酯的反应具有极高的活性,为喷涂聚脲弹性体的开发提供了原料。
脲键也经常用于构筑聚脲氨酯树脂。对于热固性的聚脲氨酯树脂,其化学交联过程一般是固定的,不具备回收和再加工的能力,不利于环保和能源的节约。基于动态可逆共价键构筑的聚脲氨酯可以解决这一问题。现有的动态可逆脲键技术为位阻脲键,即向其中一个氮原子引入大位阻的取代基(如叔丁基),可以阻碍氮原子p轨道和羰基π轨道的共平面作用,从而显著降低共振稳定作用,使得位阻脲键在室温可以发生解离反应。但是,解离产生的异氰酸酯中间体较活泼,对水分较为敏感,这在一定程度上限制了动态位阻脲键的应用。
发明内容
为了改善现有技术中的问题,本发明提供一种由下式I所示的吡唑类化合物,式II所示的巯基类化合物和式III所示的异氰酸酯类化合物反应得到的基于吡唑脲基的聚脲氨酯;
R2-(SH)x
II
其中,R1选自无取代或任选被一个、两个或更多个Ra取代的如下基团:C1-12亚烷基、C3-20亚环烷基、C6-20亚芳基、5-20元亚杂芳基、3-20元亚杂环基,及C1-12亚烷基、C3-20亚环烷基、C6-20亚芳基、5-20元亚杂芳基、3-20元亚杂环基中至少任意两种相连组成的基团、碳链中至少一个碳原子被O或S替代的C2-12亚烷基;
R2选自无取代或任选被一个、两个或更多个Rb取代如下基团:C1-12亚烷基、C3-20亚环烷基、C6-20亚芳基、5-20元亚杂芳基、3-20元亚杂环基、碳链中至少一个碳原子被O或S替代的C2-12亚烷基;
A选自无取代或任选被一个、两个或更多个Rc取代的如下基团:C1-12亚烷基、C3-20亚环烷基、3-20元亚杂环基、C6-20亚芳基、5-20元亚杂芳基,及C1-12亚烷基、C3-20亚环烷基、3-20元亚杂环基、C6-20亚芳基、5-20元亚杂芳基中至少任意两种相连组成的基团;
x、y相同或不同,彼此独立地选自2-10的整数;
Ra、Rb、Rc相同或不同,彼此独立地选自=O、卤素、C1-12烷基或C1-12烷氧基;
所述基于吡唑脲基的聚脲氨酯的重复单元中包括下式IV所示的吡唑脲基结构:
根据本发明的实施方式,式I中R1选自无取代或任选被一个、两个或更多个=O取代的如下基团:碳链中1至3个碳原子被O或S替代的C4-8亚烷基;
根据本发明的实施方式,式II中R2选自碳链中1至3个碳原子被O或S替代的C4-8亚烷基;
根据本发明的实施方式,式III中A选自无取代或任选被一个、两个或更多个=O或C1-6烷基取代的如下基团:C2-8亚烷基、C3-8亚环烷基、3-8元亚杂环基、C6-12亚芳基、及C2-8亚烷基、C3-8亚环烷基、3-8元亚杂环基、C6-12亚芳基中至少任意两种相连组成的基团。
作为实例,式III所示的异氰酸酯类化合物选自如下化合物中的至少一种:甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯、萘二异氰酸酯、对苯二异氰酸酯、二甲基联苯二异氰酸酯、多亚甲基多苯基异氰酸酯、1,6-己二异氰酸酯(HDI)、三甲基-1,6-六亚甲基二异氰酸酯、苯二亚甲基异氰酸酯、四甲基间苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、氢化亚甲基二苯基异氰酸酯、氢化甲苯二异氰酸酯、环己烷二亚甲基二异氰酸酯、降冰片烷二异氰酸酯、六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯二聚体、TDI-三羟甲基丙烷加成物、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体。
优选地,所述基于吡唑脲基的聚脲氨酯可以是无规共聚物或嵌段共聚物。
优选地,所述基于吡唑脲基的聚脲氨酯为热塑性或热固性的聚脲氨酯。
根据本发明的实施方式,所述基于吡唑脲基的聚脲氨酯具有如下结构:
根据本发明的实施方式,所述热固性的基于吡唑脲基的聚脲氨酯具有如下结构:
进一步地,本发明还提供上述基于吡唑脲基的聚脲氨酯的制备方法,包括:将如上所述式I所示的吡唑类化合物、式II所示的巯基类化合物和式III所示的异氰酸酯类化合物进行反应。
所述反应在自由基引发反应体系中进行,例如可以在热引发、光引发(如蓝光引发)、氧化还原引发的条件下进行;
根据本发明的实施方式,所述反应在光引发剂的存在下进行,所述光引发剂可以选自苯偶酰双甲醚(DMPA)、安息香***、安息香异丙醚、二苯甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基环己基苯基甲酮中的至少一种。
根据本发明的实施方式,上述反应可以在有机溶剂中进行,所述有机溶剂选自醇类溶剂、卤代烷烃类溶剂、酮类溶剂、酯类溶剂、醚类溶剂、酰胺类溶剂、砜类溶剂、芳烃类溶剂或含硫的溶剂;例如所述有机溶剂选自甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、正戊醇、正辛醇、丙酮、丁酮、氯仿、二氯甲烷、***、丁醚、二硫化碳、1-甲基-2-吡咯烷酮、N,N'-二甲基甲酰胺、N,N'-二甲基乙酰胺、二甲基亚砜、四氢呋喃、乙酸乙酯、二氧六环、乙腈、苯、甲苯、或二甲苯中的一种、两种或多种。
根据本发明的实施方式,所述反应的温度为10~30℃。
根据本发明的实施方式,当所述聚脲氨酯为热固性时,其制备方法包括:
方案1.S1)将上述式I所示的吡唑类化合物、式II所示的巯基类化合物在光引发剂存在下,经紫外光照反应得到单体A;
S2)将式I所示的吡唑类化合物、式II所示的巯基类化合物在光引发剂存在下,经紫外光照反应得到单体B;
S3)将步骤S1)得到的单体A和步骤S2)得到的单体B与式III所示的异氰酸酯类化合物反应固化得到热固性聚脲氨酯;
其中步骤S1)和S2)中使用的式II所示的巯基类化合物相同或不同,条件是至少有一个为三个以上巯基取代;
或者,
方案2.将式I所示的吡唑类化合物、式II所示的巯基类化合物和式III所示的异氰酸酯类化合物进行反应固化;条件是式III所示的异氰酸酯类化合物包含至少三个异氰酸酯基。
根据本发明的实施方式,方案2中,式III所示的异氰酸酯类化合物与式I所示的吡唑类化合物摩尔比为100:(50~75)。
根据本发明的实施方式,固化的温度为25~40℃,固化的时间为1~3天。
根据本发明的实施方式,所述制备方法还包括固化完成后除去溶剂的步骤,包括:将固化产物在30~90℃条件下真空干燥1~3天。
本发明还提供所述基于吡唑脲基的聚脲氨酯的用途,其用于制备防水、防腐、医疗用具、防冲磨和表面装饰材料。
例如,用于制备管道防腐涂层、钢结构防腐涂层、弹性防撞材料、汽车连接件(如万向连接器)、胃镜软管或医用胶管等。
本发明还提供一种可用于制备如上所述基于吡唑脲基的聚脲氨酯的中间体,其由下式I所示的吡唑类化合物和式II所示的巯基类化合物反应得到,
R2-(SH)x
II
其中,R1、R2、x具有如上所述的定义。
本申请还提供如上所述中间体在制备基于吡唑脲基的聚脲氨酯中的用途。
本申请还提供如上所述中间体的制备方法,包括式I所示的吡唑类化合物和式II所示的巯基类化合物进行反应。
进一步地,本发明还提供一种上述基于吡唑脲基的聚脲氨酯实现回收重复利用的方法,包括:将所述热固性聚脲氨酯进行破碎,加热分解,再次热压成型制备所述聚脲氨酯。
根据本发明的实施方式,破碎的方法可以为将聚脲氨酯切成碎块。
根据本发明的实施方式,加热的温度为80℃以上,例如为80℃~120℃,如100℃。
根据本发明的实施方式,可以在加热的同时进行加压,加压的压力为1~20MPa,例如为1~10MPa,如5MPa。
本发明还提供如下式11bc,或11ac,或S7,或S9所示的化合物,
本发明还提供式11bc,或11ac,或S7,或S9所示化合物的用途,其用于验证如上所述基于吡唑脲基的聚脲氨酯的稳定性和/或耐水解性。
本发明还提供如上所述式11bc,或11ac,或S7,或S9所示化合物的制备方法,包括:
将4-甲基吡唑与正辛基异氰酸酯反应得到式11bc所示化合物;或者,
将苯乙基异氰酸酯与4-甲基吡唑反应得到式11ac所示化合物;或者,
将1-异氰酸酯-3-三氟甲基苯与4-甲基吡唑反应得到式S7所示化合物;或者,
将4-吡唑酸乙酯与正辛基异氰酸酯反应得到式S9所示化合物。
本发明的有益效果:
本发明提供一种由吡唑类化合物、巯基类化合物和异氰酸酯类化合物反应得到的基于吡唑脲基的聚脲氨酯。所述吡唑类化合物与所述巯基类化合物制备得到的高活性多官能团吡唑,在室温无催化剂条件下即可与所述异氰酸酯类化合物聚合获得基于吡唑脲基的聚脲氨酯产品,方法简单、制备成本低,适合大规模工业化生产。
本发明所述的含吡唑脲基的聚合物具有热可逆性,其在室温下较为稳定,当温度升至80℃以上时,可自发地解离成含异氰酸酯和吡唑的化合物;所述聚合物的室温稳定性可通过含吡唑脲基的小分子化合物进行验证。所得的聚合物相比于室温下就会解离的含动态位阻脲键的聚合物,耐水解性更强,大大提升了基于所述吡唑脲基的聚脲氨酯产品的实用性。并且相对于常规含脲键的聚合物,无需十分苛刻的条件,例如酸或碱体系、高温、金属催化剂和酶等,利用高温便可分解,因此应用范围相对于常规含脲键和动态位阻脲键的聚合物,可开发利用性更高。
本发明制备的聚脲氨酯结构基于具有热可逆性的动态吡唑脲基,在加热条件下可以实现此类热固性聚脲氨酯的回收再利用。这主要是由于动态化学键的引入对聚合加工性能起决定性作用,从而使聚合物对外界的刺激做出响应,赋予了热固性材料自修复和再加工性能。
本申请制备得到的聚合物的稳定性和耐水解性可以通过含吡唑脲基的小分子化合物进行验证。使用小分子进行验证可节约成本。
附图说明
图1中(A)为正常脲键,(B)为位阻脲键和(C)为吡唑脲基的化学结构。
图2为基于吡唑脲基的聚脲氨酯(PPzU)的制备流程。
图3中(A)11bc和乙基吡唑-4-羧酸酯的交换反应图谱,表明吡唑脲基在室温下是不可逆的;(B)11ac的水解实验,表明其耐水解性优异。
图4中(A)PPzU18的红外光谱;(B)PPzU18的动态解聚和再聚合的GPC曲线。
图5为(A)17a,(B)17b和(C)17c的原始和再循环应力-应变曲线(插图显示17c的热压成型过程)。
图6为(A)线性PPzU16在普通溶剂中的溶解性;(B)为线性PPzU16水降解实验中各样品的GPC曲线。
术语定义和说明
除非另有说明,本说明书和权利要求书记载的数值范围相当于至少记载了其中每一个具体的整数数值。例如,数值范围“2-10”相当于记载了数值范围“2-10”中的每一个整数数值即2、3、4、5、6、7、8、9、10。应当理解,本文在描述取代基时使用的一个、两个或更多个中,“更多个”应当是指≥3的整数,例如3、4、5、6、7、8、9或10。
术语“卤素”表示氟、氯、溴和碘。
术语“C1-12亚烷基”应理解为优选表示具有1~12个碳原子的直链或支链饱和亚烃基,优选为C1-10亚烷基。“C1-10亚烷基”应理解为优选表示具有1、2、3、4、5、6、7、8、9或10个碳原子的直链或支链饱和亚烃基。所述亚烷基是例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚异丙基、亚异丁基、亚仲丁基、亚叔丁基、亚异戊基。特别地,所述基团具有1、2、3、4、5、6个碳原子(“C1-6亚烷基”),例如亚甲基、亚乙基、亚丙基、亚丁基。
术语“C3-20亚环烷基”应理解为表示饱和的单环、双环烃环或桥环,其具有3~20个碳原子,优选“C3-10亚环烷基”。术语“亚C3-10环烷基”应理解为表示饱和的单环或双环烃环,其具有3、4、5、6、7、8、9或10个碳原子。所述亚C3-10环烷基可以是单环烃基,如亚环丙基、亚环丁基、亚环戊基、亚环己基、亚环庚基、亚环辛基、亚环壬基或环癸基,或者是双环烃基如十氢化萘环。
术语“3-20元亚杂环基”意指饱和的单环或双环烃环,其包含1-5个独立选自N、O和S的杂原子,优选“3-10元亚杂环基”。术语“3-10元杂环基”意指饱和的单环或双环烃环,其包含1-5个,优选1-3个选自N、O和S的杂原子。所述亚杂环基可以通过所述碳原子中的任两个或氮原子(如果存在的话)与分子的其余部分连接。特别地,所述杂环基可以包括但不限于:4元环,如亚氮杂环丁烷基、亚氧杂环丁烷基;5元环,如亚四氢呋喃基、亚二氧杂环戊烯基、亚吡咯烷基、亚咪唑烷基、亚吡唑烷基、亚吡咯啉基;或6元环,如亚四氢吡喃基、亚哌啶基、亚吗啉基、亚二噻烷基、亚硫代吗啉基、亚哌嗪基或亚三噻烷基;或7元环,如亚二氮杂环庚烷基。任选地,所述亚杂环基可以是苯并稠合的。所述亚杂环基可以是双环的,例如但不限于5,5元环,如亚六氢环戊并[c]吡咯-2(1H)-基环,或者亚5,6元双环,如亚六氢吡咯并[1,2-a]吡嗪-2(1H)-基环。含氮原子的环可以是部分不饱和的,即它可以包含一个或多个双键,例如但不限于亚2,5-二氢-1H-吡咯基、亚4H-[1,3,4]噻二嗪基、亚4,5-二氢噁唑基或亚4H-[1,4]噻嗪基,或者,它可以是苯并稠合的,例如但不限于亚二氢异喹啉基。根据本发明,所述亚杂环基是无芳香性的。
术语“C6-20亚芳基”应理解为优选表示具有6~20个碳原子的芳香性或部分芳香性的单环、双环或三环烃环,优选“亚C6-14芳基”。术语“亚C6-14芳基”应理解为优选表示具有6、7、8、9、10、11、12、13或14个碳原子的芳香性或部分芳香性的单环、双环或三环烃环(“C6-14芳基”),特别是具有6个碳原子的环(“C6亚芳基”),例如亚苯基;或亚联苯基,或者是具有9个碳原子的环(“C9亚芳基”),例如亚茚满基或亚茚基,或者是具有10个碳原子的环(“C10亚芳基”),例如亚四氢化萘基、亚二氢萘基或亚萘基,或者是具有13个碳原子的环(“亚C13芳基”),例如亚芴基,或者是具有14个碳原子的环(“C14亚芳基”),例如亚蒽基。
术语“5-20元亚杂芳基”应理解为包括这样的单环、双环或三环芳族环系:其具有5~20个环原子且包含1-5个独立选自N、O和S的杂原子,例如“5-14元亚杂芳基”。术语“5-14元亚杂芳基”应理解为包括这样的单环、双环或三环芳族环系:其具有5、6、7、8、9、10、11、12、13或14个环原子,特别是5或6或9或10个碳原子,且其包含1-5个,优选1-3各独立选自N、O和S的杂原子。并且,另外在每一种情况下可为苯并稠合的。特别地,杂芳基选自亚噻吩基、亚呋喃基、亚吡咯基、亚噁唑基、亚噻唑基、亚咪唑基、亚吡唑基、亚异噁唑基、亚异噻唑基、亚噁二唑基、亚***基、亚噻二唑基、亚噻-4H-吡唑基等以及它们的苯并衍生物等。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
实施例1含吡唑脲基化合物的制备
将4-甲基吡唑1c溶于5mL无水DCM,加入正辛基异氰酸酯,室温反应1h,浓缩,柱层析(正己烷/EtOAc=80:1至30:1)得白色固体11bc(3.37g,99%收率)。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ7.95(s,1H),7.38(s,1H),7.10(br,s,1H),3.37(q,J=6.7Hz,2H),2.07(s,3H),1.63-1.54(m,2H),1.31-1.25(m,10H),0.86(t,J=6.5Hz,3H);13C NMR(75MHz,CDCl3,ppm)δ149.8,142.9,126.6,118.6,40.2,31.7,29.6,29.1,29.1,26.7,22.5,14.0,8.7;IR(neat,cm-1)3352,3121,2951,2921,2852,1707,1525,1468,1389,1271,1010,836,754;ESI-HRMS计算值C13H23N3NaO[M+Na]+:260.1733,实验值:260.1735,误差((计算值-实验值)/计算值):-0.8ppm.
合成操作与11bc类似,得白色固体11bd(99%收率)。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ8.20(d,J=2.7Hz,1H),7.55(d,J=1.2Hz,1H),7.20(br,s,1H),6.34(dd,J=2.6Hz,J=1.7Hz,1H),3.38(q,J=6.8Hz,2H),1.64-1.54(m,2H),1.30-1.24(m,10H),0.85(t,J=6.8Hz,3H);13C NMR(75MHz,CDCl3,ppm)δ149.6,141.8,128.5,108.0,40.3,31.7,29.5,29.1,29.1,26.7,22.5,14.0;IR(neat,cm-1)3345,2928,2857,1725,1527,1386,1334,1257,1209,1037,761;ESI-HRMS计算值C12H21N3NaO[M+Na]+:246.1577,实验值:246.1580,误差:1.2ppm.
合成操作与11bc类似,得白色固体11ac(98%收率)。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ7.96(s,1H),7.34(s,1H),7.32-7.19(m,6H),3.66-3.59(m,2H),2.89(t,J=7.2Hz,2H),2.06(s,3H);13C NMR(75MHz,CDCl3,ppm)δ149.7,143.0,138.4,128.6,128.5,126.5,126.4,118.7,41.4,35.8,8.7;IR(neat,cm-1)3367,3112,3030,2938,1712,1534,1454,1390,1357,1236,1193,967,747,697;ESI-HRMS计算值C13H15N3NaO[M+Na]+:252.1107,实验值:252.1108,误差:-0.4ppm.
合成操作与11bc类似,得白色固体11ad(97%收率)。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ8.21(d,J=2.7Hz,1H),7.53(d,J=0.9Hz,1H),7.34-7.20(m,6H),6.34(dd,J=2.6Hz,J=1.5Hz,1H),3.69-3.62(m,2H),2.91(t,J=7.2Hz,2H);13C NMR(75MHz,CDCl3,ppm)δ149.6,142.0,138.3,128.6,128.6,128.4,126.5,108.1,41.5,35.8;IR(neat,cm-1)3342,2937,1724,1524,1387,1334,1256,1207,1036,946,755,699;ESI-HRMS计算值C13H13N3NaO[M+Na]+:238.0951,实验值:238.0953,误差:-0.9ppm.
将芳基异氰酸酯(3.50mmol)溶解于无水DCM,0℃下加入4-甲基吡唑(3.50mmol),撤去冰水浴,室温反应10min。浓缩,柱层析,以定量产率获得固体S3-S7。S3-S7的表征数据如下:
1H NMR(300MHz,CDCl3,ppm)δ8.91(br,s,1H),8.05(s,1H),7.51-7.48(m,3H),6.92-6.89(m,2H),3.81(s,3H),2.13(s,3H);13C NMR(75MHz,CDCl3,ppm)δ156.6,147.1,143.3,129.7,126.7,121.4,119.5,114.3,55.5,8.9;IR(neat,cm-1)3338,3118,2933,1709,1597,1520,1424,1390,1266,1210,974,823,755;ESI-HRMS计算值C12H14N3O2[M+H]+:232.1081,实验值:232.1083,误差:-0.9ppm.
1H NMR(300MHz,CDCl3,ppm)δ8.97(br,s,1H),8.05(s,1H),7.49-7.47(m,3H),7.17(d,J=8.1Hz,2H),2.34(s,3H),2.13(s,3H);13C NMR(75MHz,CDCl3,ppm)δ146.9,143.3,134.1,134.1,129.6,126.6,119.6,119.5,20.8,8.9;IR(neat,cm-1)3329,3096,2923,1721,1595,1539,1416,1391,1211,969,811,773;ESI-HRMS计算值C12H14N3O2[M+H]+:216.1131,实验值:216.1133,误差:-0.8ppm.
1H NMR(300MHz,d6-DMSO,ppm)δ10.44(s,1H),8.18(s,1H),7.78-7.72(m,3H),7.23-7.17(m,2H),2.09(s,3H);13C NMR(75MHz,d6-DMSO,ppm)δ158.1(d,J=239.3Hz),147.5,143.7,134.0(d,J=2.5Hz),127.2,122.6(d,J=8.0Hz),119.1,115.3(d,J=22.1Hz),8.6;IR(neat,cm-1)3341,3119,1711,1614,1557,1386,1214,974,825,773;ESI-HRMS计算值C11H11FN3O[M+H]+:220.0881,实验值:220.0882,误差:0.8ppm.
1H NMR(300MHz,CDCl3,ppm)δ9.04(br,s,1H),8.03(s,1H),7.57-7.52(m,2H),7.47(s,1H),7.35-7.30(m,2H),2.13(s,3H);13C NMR(75MHz,CDCl3,ppm)δ146.8,143.6,135.3,129.5,129.2,126.6,120.7,119.8,8.9;IR(neat,cm-1)3341,3121,1713,1603,1552,1387,1102,977,819,739;ESI-HRMS计算值C11H11ClN3O[M+H]+:236.0585,实验值:236.0587,误差:-0.9ppm.
1H NMR(300MHz,d6-DMSO,ppm)δ10.72(s,1H),8.19(s,1H),8.00(d,J=8.5Hz,2H),7.74(s,1H),7.70(d,J=8.6Hz,2H),2.08(s,3H);13C NMR(75MHz,d6-DMSO,ppm)δ147.4,144.0,141.5,127.3,125.9(q,J=3.5Hz),124.3(q,J=269.7Hz),124.1(q,J=31.8Hz),120.5,119.5,8.5;IR(neat,cm-1)3331,3123,1711,1600,1551,1418,1331,1158,1112,1008,973,827,736;ESI-HRMS计算值C12H11F3N3O[M+H]+:270.0849,实验值:270.0851,误差:0.8ppm.
将4-吡唑甲酸乙酯(0.663g,4.64mmol)溶解于4mL无水CHCl3,加入正辛基异氰酸酯(0.720g,4.64mmol),室温反应过夜。浓缩,柱层析(正己烷:EtOAc=30:1)得白色固体S9(1.34g,98%收率)。1H NMR(300MHz,CDCl3,ppm)δ8.67(s,1H),7.96(s,1H),7.19(br,s,1H),4.32(q,J=7.1Hz,2H),3.42(q,J=6.8Hz,2H),1.68-1.58(m,2H),1.38-1.27(m,13H),0.87(t,J=6.7Hz,3H);13C NMR(75MHz,CDCl3,ppm)δ162.2,148.8,142.5,131.6,117.5,60.6,40.6,31.7,29.5,29.1,29.1,26.7,22.6,14.3,14.0;IR(neat,cm-1)3352,3117,2921,2851,1719,1528,1279,1194,1113,1030,971,840,775;ESI-HRMS计算值C15H26N3O3[M+H]+:296.1969,实验值:296.1971,误差:0.8ppm.
实施例2
将4-吡唑甲酸12(29.97g,262mmol)和2-烯丙氧基乙醇(35.53g,341mmol)溶解于180mL无水DMF,依次加入EDCI(55.25g,288mmol)和DMAP(12.8g,105mmol),室温搅拌反应3d。在70℃将溶液浓缩除去DMF,再加入200mL水,Et2O(3×300mL)萃取,合并有机相,依次用10wt%柠檬酸(4×100mL),饱和NaHCO3和饱和食盐水洗,Na2SO4干燥,浓缩。110℃减压蒸馏20min,除去2-烯丙氧基乙醇,得淡黄色液体化合物13(31.05g,60%收率)。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ11.52(br,s,1H),8.07(s,2H),5.97-5.84(m,1H),5.29(dq,J=17.2Hz,J=1.6Hz,1H),5.20(dq,J=10.4Hz,J=1.3Hz,1H),4.42(t,J=4.8Hz,2H),4.06(dt,J=5.6Hz,J=1.3Hz,2H),3.75(t,J=4.8Hz,2H);13CNMR(75MHz,CDCl3,ppm)δ163.1,136.5,134.2,117.5,114.4,72.1,68.0,63.4;IR(neat,cm-1)3253,2955,2868,1717,1563,1403,1326,1225,1157,992,768;ESI-HRMS计算值C9H12N2NaO3[M+Na]+:219.0740,实验值:219.0742,误差:-0.8ppm.
将化合物13(14.13g,72mmol)和2,2'-(乙二基双氧代)双乙硫醇(6.84g,36mmol)溶解于30mL DCM,加入0.5mol%(对于双键)DMPA(0.091g,0.36mmol)。反应体系于365nm的紫外灯下照射,室温搅拌反应60min。浓缩除去溶剂,再加入21mL丙酮溶解。将该溶液滴入正己烷/Et2O(80mL/120mL)的混合溶剂,静置分层,取下层有机物,浓缩得淡黄色液体14(19.50g,95%收率)。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ9.40(br,s,2H),8.03(s,4H),4.22(t,J=6.2Hz,4H),3.62-3.58(m,8H),2.67(t,J=6.9Hz,4H),2.56(t,J=7.1Hz,4H),1.81-1.73(m,4H),1.71-1.63(m,4H);13C NMR(75MHz,CDCl3,ppm)δ163.2,136.3,114.5,70.7,70.1,63.7,31.9,31.2,27.6,26.1;ESI-HRMS计算值C24H38N4NaO8S2[M+Na]+:597.2023,实验值:597.2029,误差:-0.8ppm.
将化合物13(20.29g,71mmol)和三羟基丙烷三(3-巯基丙酸酯)(TTMP)(14.31g,23.5mmol)溶解于50mL DCM,加入0.5mol%(对于双键)DMPA(0.132g,0.35mmol)。反应体系于365nm的紫外灯下照射,室温搅拌反应60min。浓缩除去溶剂,再加入35mL丙酮溶解。将该溶液滴入正己烷/Et2O(70mL/280mL)的混合溶剂,静置分层,取下层有机物,浓缩得淡黄色液体15(32.82g,97%收率)。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ10.82(br,s,3H),8.06(s,6H),4.37(t,J=4.6Hz,6H),4.01(s,6H),3.70(t,J=4.6Hz,6H),3.56(t,J=6.0Hz,6H),2.69(t,J=6.8Hz,6H),2.59-2.54(m,12H),1.86-1.77(m,6H),1.44(q,J=7.4Hz,2H),0.83(t,J=7.5Hz,3H);13C NMR(75MHz,CDCl3,ppm)δ171.7,163.0,136.5,114.4,69.3,68.7,63.8,63.3,40.6,34.5,29.3,28.5,26.8,22.8,7.2;ESI-HRMS计算值C42H63N6O15S3[M+H]+:987.3508,实验值:987.3498,误差:-1.0ppm.
实施例3基于吡唑脲基结构的聚脲氨酯的制备
将上述实施例2制备的二吡唑类化合物14(2.501g,1当量)溶于6mL无水CHCl3,加入HDI(0.725g,1当量),室温反应10h。将反应溶液于室温挥发16小时,再于70℃真空48h。将所得白色固体16热压30min(130℃,10MPa),可得完整的薄膜样品,保存于干燥器内。
结构确证数据如下:1H NMR(300MHz,CDCl3,ppm)δ8.70(s,2H),7.98(s,2H),7.25(t,J=5.9Hz,2H),4.41(t,J=4.5Hz,4H),3.72(t,J=4.7Hz,4H),3.65-3.56(m,12H),3.44(q,J=6.7Hz,4H),2.70(t,J=6.9Hz,4H),2.63(t,J=7.2Hz,4H),1.91-1.82(m,4H),1.70-1.62(4H),1.48-1.42(4H).
实施例4热固性聚脲氨酯的制备
以PPzU 17c为例,制备操作为:将三吡唑类化合物15(2.507g,1当量)溶解于无水CHCl3(2.5mL),向其中加入HDI(0.634g,1.5当量),室温搅拌混合2min。将反应溶液浇铸于铝制模具(50mm L×50mm W),在干燥器中放置24小时,脱模,再于70℃真空干燥箱中48小时,以完全除去溶剂。所得样品17c保存于干燥器中。按照相同方法,调节三吡唑类化合物15、HDI和二吡唑类化合物14的比例同样制备得到样品17a和17b。
所制备的PPzUs的性能表征数据如表1所示。
表1所制备PPzUs的性能表征
将二吡唑类化合物14(0.83mmol)溶解于无水CHCl3(4mL),向其中加入1,3-二(异氰酸根合甲基)环己烷(0.83mmol),室温搅拌反应10h。除去溶剂,直接用于表征测试。1HNMR(300MHz,CDCl3,ppm)δ8.70(2H),7.99(2H),7.33(2H),4.42-4.39(4H),3.74-3.71(4H),3.66-3.56(12H),3.50-3.28(4H),2.70(t,J=7.0Hz,4H),2.63(t,J=7.2Hz,4H),1.91-1.82(7H),1.68-1.24(5H),1.02-0.71(2H).
实施例5热固性吡唑脲基聚氨酯再加工实验
热固性聚脲氨酯的回收实验:将实施例4制备得到的热固性聚脲氨酯切成小碎块,放置于正方形的模具(长50mm×宽50mm),在100℃,5MPa的条件下,热压60min,然后,利用冷凝水在大约10min内将模具冷至室温,脱模得回收样品。样品可反复热压成型。对回收后的样品进行机械性能测试,结果如表2所示。
表2
实施例6含吡唑脲基化合物的室温稳定性和耐水解性测试
6.1化合物11bc室温稳定性实验
本发明制备的聚合物中的吡唑脲基具有室温稳定性。所述稳定性可以通过含吡唑脲基的小分子化合物的交换反应和水解反应进行验证。将实施例1制备的含吡唑脲基的化合物11bc和4-吡唑甲酸乙酯以摩尔比1:2混合,室温反应3d后,未观察交换产物的生成。进一步升温至37℃,反应20d,仅能检测到1%的交换产物(参见图3A)。这表明吡唑脲基在室温条件下是不可逆的,即含吡唑脲基的化合物(聚合物)在室温下稳定性优异。
6.2化合物11ac水解稳定性实验
本发明制备的含吡唑脲基的化合物(聚合物)具有耐水解性。验证方法如下:0.1M实施例1制备的含吡唑脲基的化合物11ac在d6-DMSO/D2O(v:v=5:1)混合溶液在37℃反应1d后,可观察到水解产物二苯乙基脲的生成,转化率约为2%;168h后,水解转化率可达6%(参见图3B)。由于吡唑脲基在室温是不可逆的,我们推测该水解反应是通过水分子催化的加成-消除机理进行的,而不是脲键解离形成异氰酸酯的水解过程。因此,本申请含吡唑脲基的化合物(聚合物)相对于含位阻脲键的化合物(聚合物)(>55%水解转化率),具有优异的水解稳定性。
实施例7线性PPzU16的稳定性实验
于室温下测试了实施例3制备得到的线性PPzU 16在普通溶剂中的溶解性(参见图6A),其溶解性结果为:在CHCl3中的溶解性最优,DCM次之,在二氧六环、二氯乙烷、N-甲基吡咯烷酮、四氯化碳、甲酰胺、乙醇、甲醇中能部分溶解,几乎不溶于二甲基亚砜、乙腈、乙酸乙酯、丙酮、四氢呋喃和N,N-二甲基甲酰胺。
对线性PPzU16进行了水降解实验,方法如下:在37℃下,取0.1M的PPzU16在d6-DMSO和D2O(v/v=19:1)的混合物中分别反应0h、28h、48h、78h、100h、144h的样品,进行GPC测试(参见图6B),实验表明PPzU16的分子量在6天后没有变化,同样说明基于吡唑脲基的聚脲氨酯具有良好的稳定性。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种基于吡唑脲基的聚脲氨酯,其特征在于,由式I所示的吡唑类化合物,式II所示的巯基类化合物和式III所示的异氰酸酯类化合物反应得到;
R2-(SH)x
II
其中,R1选自无取代或任选被一个、两个或更多个Ra取代的如下基团:C1-12亚烷基、C3-20亚环烷基、C6-20亚芳基、5-20元亚杂芳基、3-20元饱和亚杂环基、3-20元不饱和且不具备芳香性的亚杂环基,及C1-12亚烷基、C3-20亚环烷基、C6-20亚芳基、5-20元亚杂芳基、3-20元饱和亚杂环基和3-20元不饱和且不具备芳香性的亚杂环基中至少任意两种相连组成的基团、碳链中至少一个碳原子被O或S替代的C2-12亚烷基;
R2选自无取代或任选被一个、两个或更多个Rb取代如下基团:C1-12亚烷基、C3-20亚环烷基、C6-20亚芳基、5-20元亚杂芳基、3-20元饱和亚杂环基、3-20元不饱和且不具备芳香性的亚杂环基、碳链中至少一个碳原子被O或S替代的C2-12亚烷基;
A选自无取代或任选被一个、两个或多个Rc取代的如下基团:C1-12亚烷基、C3-20亚环烷基、3-20元饱和亚杂环烷基、C6-20亚芳基、5-20元亚杂芳基、3-20元不饱和且不具备芳香性的亚杂环基及C1-12亚烷基、C3-20亚环烷基、3-20元饱和亚杂环烷基、C6-20亚芳基、5-20元亚杂芳基和3-20元不饱和且不具备芳香性的亚杂环基中至少任意两种相连组成的基团;
x、y相同或不同,彼此独立地选自2-10的整数;
Ra、Rb、Rc相同或不同,彼此独立地选自=O、卤素、C1-12烷基或C1-12烷氧基;
所述基于吡唑脲基的聚脲氨酯的重复单元中包括下式IV所示的吡唑脲基结构:
2.根据权利要求1所述的基于吡唑脲基的聚脲氨酯,其特征在于,式I中R1选自无取代或任选被一个、两个或多个=O取代的如下基团:碳链中1至3个碳原子被O或S替代的C4-8亚烷基;
式II中R2选自碳链中1至3个碳原子被O或S替代的C4-8亚烷基;
式III中A选自无取代或任选被一个、两个或多个=O或C1-6烷基取代的如下基团:C2-8亚烷基、C3-8亚环烷基、3-8元饱和亚杂环烷基、C6-12亚芳基、及C2-8亚烷基、C3-8亚环烷基、3-8元饱和亚杂环烷基、3-8元不饱和且不具备芳香性的亚杂环基、C6-12亚芳基中至少任意两种相连组成的基团。
3.根据权利要求1所述的基于吡唑脲基的聚脲氨酯,其特征在于,
式III所示的异氰酸酯类化合物选自如下化合物中的至少一种:甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯、萘二异氰酸酯、对苯二异氰酸酯、二甲基联苯二异氰酸酯、多亚甲基多苯基异氰酸酯、1,6-己二异氰酸酯、三甲基-1,6-六亚甲基二异氰酸酯、苯二亚甲基异氰酸酯、四甲基间苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、氢化亚甲基二苯基异氰酸酯、氢化甲苯二异氰酸酯、环己烷二亚甲基二异氰酸酯、降冰片烷二异氰酸酯、六亚甲基二异氰酸酯三聚体、甲苯二异氰酸酯二聚体、TDI-三羟甲基丙烷加成物、甲苯二异氰酸酯三聚体、二苯基甲烷二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体。
4.根据权利要求1-3任一项所述的基于吡唑脲基的聚脲氨酯,其特征在于,所述基于吡唑脲基的聚脲氨酯是无规共聚物或嵌段共聚物。
5.根据权利要求4所述的基于吡唑脲基的聚脲氨酯,其特征在于,所述基于吡唑脲基的聚脲氨酯为热塑性或热固性。
8.根据权利要求7所述的制备方法,其特征在于,所述聚脲氨酯为热固性,其制备方法包括:
方案1.S1)将式I所示的吡唑类化合物、式II所示的巯基类化合物在光引发剂存在下,经紫外光照反应得到单体A;
S2)将式I所示的吡唑类化合物、式II所示的巯基类化合物在光引发剂存在下,经紫外光照反应得到单体B;
S3)将步骤S1)得到的单体A和步骤S2)得到的单体B与式III所示的异氰酸酯类化合物反应固化得到热固性聚脲氨酯;
其中步骤S1)和S2)中使用的式II所示的巯基类化合物相同或不同,条件是至少有一个为三个以上巯基取代;
或者,
方案2.将式I所示的吡唑类化合物、式II所示的巯基类化合物和式III所示的异氰酸酯类化合物进行反应固化;条件是式III所示的异氰酸酯类化合物包含至少三个异氰酸酯基。
9.权利要求1~6任一项所述基于吡唑脲基的聚脲氨酯实现回收重复利用的方法,其特征在于,所述聚脲氨酯为热固性,所述方法包括:将所述热固性聚脲氨酯进行破碎,加热分解,再次热压成型制备所述聚脲氨酯。
10.权利要求1~6任一项所述基于吡唑脲基的聚脲氨酯在制备防水、防腐、医疗用具、防冲磨和表面装饰材料方面的应用。
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