CN113072465A - 一种碳化二亚胺改性多异氰酸酯及其制备方法,及催化剂体系 - Google Patents
一种碳化二亚胺改性多异氰酸酯及其制备方法,及催化剂体系 Download PDFInfo
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- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 51
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 150000001718 carbodiimides Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- -1 phosphate ester compound Chemical class 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 4
- 150000002291 germanium compounds Chemical class 0.000 claims abstract description 3
- 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 25
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 11
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 11
- QQXSEZVCKAEYQJ-UHFFFAOYSA-N tetraethylgermanium Chemical compound CC[Ge](CC)(CC)CC QQXSEZVCKAEYQJ-UHFFFAOYSA-N 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- 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 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ZRLCXMPFXYVHGS-UHFFFAOYSA-N tetramethylgermane Chemical compound C[Ge](C)(C)C ZRLCXMPFXYVHGS-UHFFFAOYSA-N 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 claims description 2
- GCFDVEHYSAUQGL-UHFFFAOYSA-J fluoro-dioxido-oxo-$l^{5}-phosphane;tin(4+) Chemical compound [Sn+4].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O GCFDVEHYSAUQGL-UHFFFAOYSA-J 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- PPMWWXLUCOODDK-UHFFFAOYSA-N tetrafluorogermane Chemical compound F[Ge](F)(F)F PPMWWXLUCOODDK-UHFFFAOYSA-N 0.000 claims description 2
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims description 2
- RDQCXMUEJJIHQT-UHFFFAOYSA-N trichloro(phosphoroso)methane Chemical compound ClC(Cl)(Cl)P=O RDQCXMUEJJIHQT-UHFFFAOYSA-N 0.000 claims description 2
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 16
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 38
- 239000012948 isocyanate Substances 0.000 description 20
- 150000002513 isocyanates Chemical class 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- 230000004048 modification Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
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- 230000006978 adaptation Effects 0.000 description 2
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- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
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Abstract
本发明涉及一种碳化二亚胺改性多异氰酸酯及其制备方法,及催化剂体系。使用有机锡化合物和/或有机锗化合物,和磷酸酯复配催化剂;所制备的碳化二亚胺改性多异氰酸酯中包含
Description
技术领域
本发明涉及改性异氰酸酯领域,具体涉及碳化二亚胺改性多异氰酸酯。
背景技术
异氰酸酯可以在一定的条件下缩聚释放CO2后生成碳化二亚胺(CDI)类衍生物,碳化二亚胺基团可以同异氰酸酯进行加合反应形成脲酮亚胺(UTI),通过此方法使异氰酸酯中含有CDI和UTI类物质,这种改性异氰酸酯凝固点降低,在常温下呈液态,其良好的储存稳定性有利于长途运输及下游应用,而且由这种改性异氰酸酯制备的制品在耐光、耐燃、耐水解、增加初始强度等性能方面得到一定的改善。专利US2853473A、US5610408A、US6362247B对异氰酸酯的碳化二亚胺化均有报道。
用于制备碳化二亚胺改性异氰酸酯的催化剂主要是磷杂环类催化剂和磷酸酯类催化剂。磷杂环类催化剂催化效力较高,改性异氰酸酯中残留的磷杂环催化剂在运输及储存过程中持续催化NCO所合并产品CO2,影响产品储存稳定性并带来一定安全风险。磷酸酯类催化剂仅在较高温度下才能催化缩合反应,因此采用磷酸酯类催化剂制造的改性异氰酸酯具有良好的储存稳定性。
碳化二亚胺改性异氰酸酯解决了4,4’-二苯基甲烷二异氰酸酯室温下为固态的问题,然而在冬季使用过程中,仍会出现储存数天析出主要成分为4,4’-MDI的晶体,造成使用困难。结晶后的碳化二亚胺改性异氰酸酯相比于4,4’-MDI存在更难化料的情况,目前仍鲜有对于制造低温条件不结晶的碳化二亚胺改性异氰酸酯的技术报道。
CN104945585A中公开通过加入适量2,4’-二苯基甲烷二异氰酸酯的方式制造低温储存稳定的多异氰酸酯组合物。由于2,4’-MDI的化学反应活性与4,4’-MDI存在较大区别,该技术将导致多异氰酸酯组合物整体活性变化而应用下游使用效果。
在保证产品自身组成无明显变化且不改变产品应用性能的前提下,有效降低产品结晶点的方法,相关技术仍未有报道。
发明内容
本发明提供一种碳化二亚胺改性多异氰酸酯及其制备方法,及催化剂体系。本发明的方法能够提升碳化二亚胺改性多异氰酸酯的低温储存性能,降低碳化二亚胺改性多异氰酸酯结晶点,同时缩短产品的生产时间,对产品下游应用性能基本无影响。
为实现以上的技术效果,本发明采用如下的技术方案:
一种碳化二亚胺改性多异氰酸酯,包含以下组分:
(a)多异氰酸酯;
(b)含碳化二亚胺及脲酮亚胺基改性多异氰酸酯;
其中R表示多异氰酸酯的残基。
作为一个优选的方案,所述R表示以下基团中的一种或多种:
作为一个优选的方案,一种碳化二亚胺改性多异氰酸酯,包含以下组分:
(a)多异氰酸酯:65~75wt%,优选65~70wt%;
(b)含碳化二亚胺及脲酮亚胺基改性多异氰酸酯:15~25wt%,优选20~25wt%;
其中R表示以下基团中的一种或多种:
一种用于制备本发明所述的碳化二亚胺改性多异氰酸酯的催化剂体系,包含以下组分:(1)有机锡化合物和/或有机锗化合物,和(2)磷酸酯;所述有机锡化合物或有机锗化合物的用量为磷酸酯的0.1~10wt%,优选0.1~1wt%,更优选0.3~0.5wt%。
在一个具体的实施方案中,所述的有机锡化合物选自辛酸亚锡、二月桂酸二丁基锡、二丁基锡、二甲基锡、二辛基锡、二氯化锡、三丁基锡、三苯基锡、四苯基锡、三苯基氟化锡、氟磷酸锡中的一种或多种,优选辛酸亚锡。
在一个具体的实施方案中,所述的有机锗化合物选自四甲基锗、四乙基锗、四氯化锗、四氟化锗中的一种或多种,优选四乙基锗。
在一个具体的实施方案中,所述的磷酸酯选自磷酸三丁酯、磷酸三乙酯、三氯甲基氧化磷中的一种或多种;优选为磷酸三乙酯。
一种制备本发明所述碳化二亚胺改性多异氰酸酯的方法,包括以下步骤:(1)在所述催化剂体系的存在下,多异氰酸酯进行碳化二亚胺化反应,(2)向步骤(1)所得产物中加入多异氰酸酯降温使催化剂失活。
在一个具体的实施方案中,所述多异氰酸酯选自芳族、芳脂族、脂族、脂环族多异氰酸酯中的一种或多种。具体的实例包括但不限于:二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯中的一种或多种。
在一个具体的实施方案中,所述的多异氰酸酯为二苯基甲烷二异氰酸酯,该二苯基甲烷二异氰酸酯含有96-100wt%4,4’-异构体、0-1wt%2,2’-异构体和0.1-4wt%2,4’-异构体。
在一个具体的实施方案中,所述的催化剂体系的用量为原料多异氰酸酯重量的1%~10%,优选3%~5%。
在一个具体的实施方案中,所述碳化二亚胺反应的温度为150-200℃,优选180-200℃,更优选190-195℃。
由于碳化二亚胺反应是NCO缩聚反应,过程伴随有CO2的产生,所以该反应过程可以通过测量CO2释放量来进行监控;或者通过连续测定反应液的折光率变化来反映NCO含量的变化。
根据本发明,一般将原料异氰酸酯的NCO基团的5~20%,优选10~15%发生碳化二亚胺化反应,当碳化二亚胺化反应时间达到1-3h,优选2-2.5h,此时,反应液中式I结构含量为20~40%,NCO含量为20~24wt%,快速加入原料多异氰酸酯。
有机异氰酸酯的结晶过程分为两种情况,一种为组成中线型分子规则排布形成晶格,表现为以结晶的状态;另一种为例如十环以上大分子结构(当原料为二苯基甲烷二异氰酸酯时,含有十个苯环以上)在有机异氰酸酯中相容性不佳,在低温状态下更容易析出,析出后作为晶核促进产品中的单体析出。本发明通过式I结构组分,降低产品的结晶点。
当原料多异氰酸酯为二苯基甲烷二异氰酸酯时,碳化二亚胺改性有机异氰酸酯组合物为含有不同多环结构,不同分子量的混合物。组合物中碳化二亚胺结构和脲酮亚胺结构分子分别呈线形和面形状态,倾向于规则排列形成晶格,表现为易结晶的状态;十环以上等分子量较大结构分子,由于其体积较大,在体系中相容性不佳,低温条件下易析出形成晶核促进4,4’-MDI结晶。式I结构组分分子在异氰酸酯组合物中既可提供空间位阻,同时在体系中具有良好的溶解度,有利于降低异氰酸酯组合物的结晶点。
本发明所述步骤(2)中,使用的多异氰酸酯优选为含有96~100wt%4,4’-异构体、0~1wt%2,2’-异构体和0.1~4wt%2,4’-异构体的二苯基甲烷二异氰酸酯。
本发明所述步骤(2)中,根据目标NCO含量要求,所加入的多异氰酸酯的质量为反应液质量的20~50%,优选40~50%。
产品碳化二亚胺改性多异氰酸酯中式I结构含量为5%~10%,优选8%~10%;NCO含量为24~32wt%,优选26~31wt%;粘度为10~200cp,优选20~60cp;色数为30~80APHA,优选40~50APHA。
产品中式I结构组分含量与催化剂体系中有机金属化合物占比呈正相关,提高催化剂体系中有机金属化合物含量可以提高式I结构组分含量。由于考虑到产品中金属残留问题,优选催化剂体系中有机金属化合物的用量为磷酸酯重量的0.3~0.5%。
本发明通过采用上述技术方案,获得了如下的有益效果:
(1)本发明开发了有机金属复配催化剂进行碳化二亚胺改性的方法,有针对性地提高了改性多异氰酸酯中式I结构的含量,通过抑制产品低温储存过程中分子规则排布后析出的过程,降低了改性多异氰酸酯的结晶点,使产品在-15℃保持液体状态稳定储存180天以上。
(2)本发明通过改变催化剂的方式降低产品结晶点,产品在外观、NCO含量、反应活性方面与现有产品基本一致,在鞋底原液、胶黏剂预聚体应用过程中可实现良好切换。
(3)使用金属复配催化剂提高了磷酸酯催化剂的催化活性,碳化二亚胺反应时间可缩短1~3h,减少反应过程中较高分子量多环结构的形成,产品中异氰酸酯二聚体含量明显降低,使制造的改性多异氰酸酯在常温下保质期由6个月延长至9个月。
具体实施方式
为了更好的理解本发明的技术方案,下面的实施例将对本发明所提供的方法予以进一步的说明,但本发明不限于所列出的实施例,还应包括在本发明的权利要求范围内其他任何公知的改变。
下面通过更具体的实施例进一步说明本发明,但不对本发明的范围构成任何的限制。
原料:
二苯基甲烷二异氰酸酯单体,其中二苯基甲烷二异氰酸酯含有99wt%4,4-异构体、0.1wt%2,2-异构体以及0.9wt%2,4-异构体,NCO含量为33.6wt%;
催化剂:
磷酸三乙酯(TCI,99%)。
有机金属化合物:
辛酸亚锡(麦克林,97%)
二月桂酸二丁基锡(麦克林,97%)
四乙基锗(麦克林,97%)
四甲基锗(麦克林,97%)
测试仪器包括DV-79数字式粘度计,LC-MS 6800液相色谱质谱联用仪器,DSC 3500差示扫描量热仪。
实施例1
将四甲基锗和磷酸三乙酯按照质量比1:1000,在45℃条件下混合均匀作为复配催化剂备用。将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加1wt%的复配催化剂,均匀混合后快速加热至150℃,反应3h后快速加入120g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为75%,碳化二亚胺及脲酮亚胺组成为20%,式I结构组分含量为5%,产品在-15℃条件下可维持液态储存180天。
式I结构式:
式I的质谱结果如下:
Chemical Formula:C73H50N10O6
Exact Mass:1162.39
Molecular Weight:1163.24
m/z:1162.39(100.0%),1163.39(82.6%),1164.40(32.6%),
1165.40(10.3%),1164.39(3.0%),1166.40(2.2%)
Elemental Analysis:C,75.37;H,4.33;N,12.04;O,8.25
实施例2
将二月桂酸二丁基锡和磷酸三乙酯按照质量比3∶1000,在45℃条件下混合均匀作为复配催化剂备用。将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加3wt%的复配催化剂,均匀混合后快速加热至180℃,反应2.5h后快速加入180g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为72%,碳化二亚胺及脲酮亚胺组成为22%,式I结构组分含量为6%,产品在-15℃条件下可维持液态储存200天。
实施例3
将四乙基锗和磷酸三乙酯按照质量比5:1000,在45℃条件下混合均匀作为复配催化剂备用。将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加5wt%的复配催化剂,均匀混合后快速加热至195℃,反应2h后快速加入200g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为69%,碳化二亚胺及脲酮亚胺组成为23%,式I结构组分含量为8%,产品在-15℃条件下可维持液态储存220天。
实施例4
将辛酸亚锡和磷酸三乙酯按照质量比1:10,在45℃条件下混合均匀作为复配催化剂备用。将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加10wt%的复配催化剂,均匀混合后快速加热至200℃,反应1h后快速加入300g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为65%,碳化二亚胺及脲酮亚胺组成为25%,式I结构组分含量为10%,产品在-15℃条件下可维持液态储存250天。
对比例1
将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加1wt%的磷酸三乙酯,均匀混合后快速加热至150℃,反应3h后快速加入120g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为74.9%,碳化二亚胺及脲酮亚胺组成为25%,式I结构组分含量为0.1%,产品在-15℃条件下可维持液态储存5天。
对比例2
将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加3wt%的磷酸三乙酯,均匀混合后快速加热至180℃,反应2.5h后快速加入180g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为72.5%,碳化二亚胺及脲酮亚胺组成为27%,式I结构组分含量为0.5%,产品在-15℃条件下可维持液态储存20天。
对比例3
将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加0.025wt%的四乙基锗,均匀混合后快速加热至195℃,反应2h后快速加入200g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为99.9%,产品在室温条件下为固态。
对比例4
将600g二苯基甲烷二异氰酸酯在N2氛围中搅拌,添加1wt%的辛酸亚锡,均匀混合后快速加热至200℃,反应1h后快速加入300g二苯基甲烷二异氰酸酯,同时通循环水降温至80℃,继续搅拌30min后得到最终产品。此时产品中单体含量为99.9%,产品在室温条件下为固态。
实施例和对比例产品储存稳定性和指标对比见表1。
表1产品储存稳定性和指标
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但应当认识到上述的描述不应被认为是对本发明的限制。本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (10)
4.一种用于制备权利要求1-3任一项所述的改性多异氰酸酯的催化剂体系,包含以下组分:(1)有机锡化合物和/或有机锗化合物,和(2)磷酸酯;所述有机锡化合物或有机锗化合物的用量为磷酸酯的0.1~10wt%,优选0.1~1wt%,更优选0.3~0.5wt%。
5.根据权利要求4所述的催化剂体系,其特征在于,所述的有机锡化合物选自辛酸亚锡、二月桂酸二丁基锡、二丁基锡、二甲基锡、二辛基锡、二氯化锡、三丁基锡、三苯基锡、四苯基锡、三苯基氟化锡、氟磷酸锡中的一种或多种,优选辛酸亚锡。
6.根据权利要求4所述的催化剂体系,其特征在于,所述的有机锗化合物选自四甲基锗、四乙基锗、四氯化锗、四氟化锗中的一种或多种,优选四乙基锗。
7.根据权利要求4所述的催化剂体系,其特征在于,所述的磷酸酯选自磷酸三丁酯、磷酸三乙酯、三氯甲基氧化磷中的一种或多种;优选为磷酸三乙酯。
8.一种制备权利要求1-3任一项所述的改性多异氰酸酯的方法,包括以下步骤:(1)在权利要求3所述催化剂体系的存在下,多异氰酸酯进行碳化二亚胺化反应,(2)向步骤(1)所得产物中加入多异氰酸酯降温使催化剂失活。
9.根据权利要求8所述的方法,其特征在于,所述多异氰酸酯选自芳族、芳脂族、脂族、脂环族多异氰酸酯中的一种或多种,优选二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯中的一种或多种。
10.根据权利要求7所述的方法,其特征在于,所述的催化剂体系的用量为原料多异氰酸酯重量的1%~10%,优选3%~5%。
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