CN116987475B - 一种免保压且快速固化的聚氨酯胶及其制备方法 - Google Patents
一种免保压且快速固化的聚氨酯胶及其制备方法 Download PDFInfo
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- CN116987475B CN116987475B CN202310992048.4A CN202310992048A CN116987475B CN 116987475 B CN116987475 B CN 116987475B CN 202310992048 A CN202310992048 A CN 202310992048A CN 116987475 B CN116987475 B CN 116987475B
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- Prior art keywords
- polyurethane adhesive
- maintaining
- diisocyanate
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- free
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 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 abstract description 13
- 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 abstract description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 22
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 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 10
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 8
- 244000226021 Anacardium occidentale Species 0.000 claims description 8
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 8
- ZUFUSIMENKJSMG-UHFFFAOYSA-N 1-methyl-3,5-bis(methylsulfanyl)benzene Chemical compound CSC1=CC(C)=CC(SC)=C1 ZUFUSIMENKJSMG-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 4
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- 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 3
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- 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 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- HILAULICMJUOLK-UHFFFAOYSA-N 1,3-diethyl-5-methylbenzene Chemical compound CCC1=CC(C)=CC(CC)=C1 HILAULICMJUOLK-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 4
- 229960005150 glycerol Drugs 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- 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 2
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000845 maltitol Substances 0.000 description 2
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 2
- 235000010449 maltitol Nutrition 0.000 description 2
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- 239000004633 polyglycolic acid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229920001228 polyisocyanate Polymers 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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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- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- 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
-
- 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
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- 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
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—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
- 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
- C08G18/755—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 and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- 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
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- 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
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明提供了一种免保压且快速固化的聚氨酯胶及其制备方法，该聚氨酯胶可实现快速固化，常温下具有较长的开放时间。本发明是通过异佛尔酮二异氰酸酯、甲苯二异氰酸酯和苯基甲烷二异氰酸酯的复配，能显著性提高聚氨酯胶的初强度和终强度。经高温高湿、冷热冲击处理下，本发明的聚氨酯胶仍具备较高的终强度，凸显其良好的耐湿热、耐高低温冲击性能，能够达到免保压/短保压，用于电子产品中实现电子产品的高效生产。
Description
技术领域
本发明涉及高分子技术领域，特别涉及一种免保压且快速固化的聚氨酯胶及其制备方法。
背景技术
聚氨酯胶是以多异氰酸酯和聚氨酯为主体材料的胶粘剂，由于在它们的分子链中含有异氰酸酯基(-NCO)和氨基甲酸酯基(-NH-COO-)，因而具有高度的极性和活泼性。不仅对多种材料具有极高的黏附性能，而且自身内聚能较大，具有相当高的强度。不仅可以胶接多孔性的材料，而且可以胶接表面光洁的材料。
但聚氨酯传统的原料来源于石油，原料不可再生，具有剧毒，同时，废聚氨酯降解困难，污染环境。生物基聚氨酯材料具有很好的生物可降解性，原料来源广泛，对环境负荷小。生物基聚氨酯材料的合成主要是通过共混或共聚的方法引入生物降解成分或基团，如聚乳酸/聚丙交酯(PLA)、聚羟基乙酸(PGA)等。然而，现有的聚氨酯胶初粘力小，在电子器件制造过程中需要较长的保压时间，大大降低了生产效率，无法满足快速装配的要求，增加生产成本。
因此，如何提供一种免保压且快速固化，具备短保压或免保压，且具有极高初强度和终强度的反应型聚氨酯热熔胶是本领域技术人员亟需解决的问题。
发明内容
针对现有技术所存在的技术问题，本发明提供了一种免保压且快速固化的聚氨酯胶及其制备方法。该聚氨酯胶可实现快速固化，在常温下具有较长的开放时间，具备良好的初强度和终强度。经高温高湿、冷热冲击处理下，本发明的聚氨酯胶仍具备较高的终强度，凸显其良好的耐湿热、耐高低温冲击性能，能够达到免保压或短保压，用于电子产品中实现电子产品的高效生产。
具体而言，本发明首先提供了一种免保压且快速固化的聚氨酯胶，其特征在于，所述免保压且快速固化聚氨酯胶的配方包括多元醇、二异氰酸酯和固化剂组成，其中所述多元醇选自腰果壳油聚醚多元醇、蓖麻油多元醇、山梨醇、木糖醇、甘露醇、麦芽糖醇、甘油和乙二醇的一种或多种；所述二异氰酸酯选自甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中的一种或多种；所述固化剂是选自二醇类固化剂或二胺类固化剂。
优选地，所述多元醇选自腰果壳油聚醚多元醇、山梨醇和木糖醇的组合。
优选地，所述腰果壳油聚醚多元醇、山梨醇和木糖醇的用量比为1:1:1。
优选地，所述二异氰酸酯选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的组合。
优选地，所述异佛尔酮二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的用量比为1:1:1。
优选地，所述二醇类固化剂是选自对苯二酚二羟乙基醚、间苯二酚双羟乙基醚、对羟乙基双酚A中的一种或多种；所述二胺类固化剂是选自3,5-二甲硫基甲苯二胺、3,3'-二氯-4,-4'二苯基甲烷二胺、3,5二乙基甲苯二胺的一种或多种。
优选地，所述二醇类固化剂是选自对苯二酚二羟乙基醚、3,5-二甲硫基甲苯二胺的组合。
优选地，所述对苯二酚二羟乙基醚、3,5-二甲硫基甲苯二胺的用量比为1：1:1。
优选地，所述多元醇、二异氰酸酯和固化剂的用量配比为30:10:3。
本发明的另一目的在于提供了一种免保压且快速固化的聚氨酯胶的制备方法，其包括如下步骤：
1)在干燥氮气保护下，将多元醇加入反应容器中，于120±10℃下减压除水2-3h，接着将体系温度降低至40-70℃；
2)向所述反应容器中加入异氰酸酯、固化剂和催化剂，混合均匀后，使用稀释剂调节混合液的粘度，于40-70℃反应6-8h；
3)待步骤S2反应结束后加入扩链剂进行交联反应，搅拌，使所述聚合物乳化形成乳液；
4)蒸馏回收所述乳液中的稀释剂，即得到所述免保压且快速固化的聚氨酯胶。
其中，步骤1)中的多元醇是选自腰果壳油聚醚多元醇、蓖麻油多元醇、山梨醇、木糖醇、甘露醇、麦芽糖醇、甘油和乙二醇的一种或多种；
优选地，所述多元醇是选自腰果壳油聚醚多元醇、山梨醇和木糖醇；
进一步优选地，所述多元醇中腰果壳油聚醚多元醇、山梨醇和木糖醇的质量比为1:1:1；
其中，步骤2)中采用的二异氰酸酯选自甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯(LDI)中的一种或多种；
优选地，所述二异氰酸酯是选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的组合；
进一步优选地，所述二异氰酸酯中异佛尔酮二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的质量比为1:1:1；
其中，步骤2)中的固化剂是选自二醇类固化剂或二胺类固化剂；
优选地，所述二醇类固化剂是选自对苯二酚二羟乙基醚、间苯二酚双羟乙基醚、对羟乙基双酚A中的一种或多种；
优选地，所述二胺类固化剂是选自3,5-二甲硫基甲苯二胺、3,3'-二氯-4,-4'二苯基甲烷二胺、3,5二乙基甲苯二胺的一种或多种；
进一步优选地，所述固化剂是选自对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺；
进一步优选地，所述固化剂中对苯二酚二羟乙基醚和3,5-二甲硫基甲苯二胺的质量比为1:1；
其中，步骤2)中的催化剂是选自辛酸亚锡、二月桂酸二丁基锡、有机铋催化剂中的一种或多种；
优选地，所述催化剂是辛酸亚锡；
其中，步骤2)中的稀释剂是选自丙酮；
其中，步骤3)中的扩链剂是选自三羟甲基丙烷、甘油、二乙醇胺、三乙醇胺、乙醇胺中的一种或多种；
优选地，所述扩链剂是三羟甲基丙烷；
本发明的优点在于：本发明的免保压且快速固化的聚氨酯胶常温下具有较长的开放时间，经异佛尔酮二异氰酸酯、甲苯二异氰酸酯和苯基甲烷二异氰酸酯复配后，能显著性提高聚氨酯胶的初强度和终强度，而单一组分制备的聚氨酯胶的强度却一般，不能达到快速固化的目的。并且，经高温高湿、冷热冲击处理下，本发明的聚氨酯胶仍具备较高的终强度，凸显其良好的耐湿热、耐高低温冲击性能，能够达到免保压，用于电子产品中实现电子产品的高效生产。
具体实施方式
下面结合具体实施例对本发明作进一步的详细说明，以使本领域的技术人员更加清楚地理解本发明。
以下各实施例，仅用于说明本发明，并不用来限制本发明的范围。基于本发明中的具体实施例，本领域普通技术人员在没有做出创造性劳动的情况下，所获得的其他所有实施例，都属于本发明的保护范围。
在本发明实施例中，若无特殊说明，所有原料组分均为本领域技术人员熟知的市售产品；在本发明实施例中，若未具体指明，所用的技术手段均为本领域技术人员所熟知的常规手段。
实施例1-5一种免保压且快速固化的聚氨酯胶及其制备
一种免保压且快速固化的聚氨酯胶的制备方法，其包括如下步骤：
1)在干燥氮气保护下，将多元醇加入反应容器中，于120±10℃下减压除水2-3h，接着将体系温度降低至40-70℃；
2)向所述反应容器中加入异氰酸酯、固化剂和催化剂，混合均匀后，使用稀释剂调节混合液的粘度，于40-70℃反应6-8h；
3)待步骤S2反应结束后加入扩链剂进行交联反应，搅拌，使所述聚合物乳化形成乳液；
4)蒸馏回收所述乳液中的稀释剂，即得到所述免保压且快速固化的聚氨酯胶。
表1.实施例1-5的免保压且快速固化的聚氨酯胶的合成配方
本发明实施例制备得到的免保压且快速固化的聚氨酯胶基本性能的测试方法如下所述:
粘度测试：使用Brookfield旋转粘度计110℃测试，27#转子。
开放时间：将本发明实施例制备得到的聚氨酯胶于130℃下熔融20min，在光滑的平板上涂布0.1mm厚的胶，记录胶层表面具有粘性的时间。
剪切强度：将本发明实施例制备得到的聚氨酯胶在130℃下熔融20min，施胶于PC试片上，放置不同时间，按照GB/T7124-2008进行制作样件和测试。
冷热冲击：将本发明实施例制备得到的聚氨酯胶经固化24h后，温度循环-40℃到80℃，2h/cycle，100cycle后室温下测试剪切强度。
高温高湿：将本发明实施例制备得到的聚氨酯胶经固化24h后，将其置于85℃、85％RH下，放置100h后室温下测试剪切强度。
结果如下表2所示。
表2.物理性能表征
从表2中可以看出，本发明的免保压且快速固化的聚氨酯胶可实现快速固化，在常温下具有较长的开放时间，经异佛尔酮二异氰酸酯、甲苯二异氰酸酯和苯基甲烷二异氰酸酯复配后，能显著性提高聚氨酯胶的初强度和终强度，而单一组分制备的聚氨酯胶的强度却一般，不能达到快速固化的目的。并且，经高温高湿、冷热冲击处理下，本发明的聚氨酯胶仍具备较高的终强度，凸显其良好的耐湿热、耐高低温冲击性能，能够达到免保压，用于电子产品中实现电子产品的高效生产。
在此有必要指出的是，以上实施例仅限于对本发明的技术方案做进一步的阐述和说明，并不是对本发明的技术方案的进一步的限制，本发明的方法仅为较佳的实施方案，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (6)
1.一种免保压且快速固化的聚氨酯胶，其特征在于，所述免保压且快速固化聚氨酯胶的配方包括多元醇、二异氰酸酯和固化剂组成，其中所述多元醇选自腰果壳油聚醚多元醇、山梨醇和木糖醇的组合；所述二异氰酸酯选自异佛尔酮二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的组合；所述固化剂是选自对苯二酚二羟乙基醚、3,5-二甲硫基甲苯二胺的组合。
2.如权利要求1所述的免保压且快速固化的聚氨酯胶，其特征在于，所述多元醇中，腰果壳油聚醚多元醇、山梨醇和木糖醇的用量比为1:1:1。
3.如权利要求1所述的免保压且快速固化的聚氨酯胶，其特征在于，所述二异氰酸酯中，异佛尔酮二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的用量比为1:1:1。
4.如权利要求1所述的免保压且快速固化的聚氨酯胶，其特征在于，所述固化剂中，对苯二酚二羟乙基醚、3,5-二甲硫基甲苯二胺的用量比为1：1。
5.如权利要求1所述的免保压且快速固化的聚氨酯胶，其特征在于，所述多元醇、二异氰酸酯和固化剂的用量配比为30:10:3。
6.权利要求1-5任一项所述免保压且快速固化的聚氨酯胶的制备方法，其特征在于，包括如下步骤：
1）在干燥氮气保护下，将多元醇加入反应容器中，于120±10℃下减压除水2-3h，接着将体系温度降低至40-70℃；
2）向所述反应容器中加入二异氰酸酯、固化剂和催化剂，混合均匀后，使用稀释剂调节混合液的粘度，于40-70℃反应6-8h；所述催化剂是选自辛酸亚锡、二月桂酸二丁基锡、有机铋催化剂中的一种或多种；所述稀释剂是选自丙酮；
3）待步骤2反应结束后加入扩链剂进行交联反应，搅拌，使聚合物乳化形成乳液；所述扩链剂是选自三羟甲基丙烷、甘油、二乙醇胺、三乙醇胺、乙醇胺中的一种或多种；
4）蒸馏回收所述乳液中的稀释剂，即得到所述免保压且快速固化的聚氨酯胶。
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| CN113801619A (zh) * | 2021-09-29 | 2021-12-17 | 韦尔通(厦门)科技股份有限公司 | 一种含异山梨醇的生物基反应型聚氨酯热熔胶及其制备方法 |
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