CN116333665A - Thermoplastic polyurethane hot melt adhesive and preparation method thereof - Google Patents
Thermoplastic polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 71
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 34
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 42
- 239000004814 polyurethane Substances 0.000 claims abstract description 42
- 239000004970 Chain extender Substances 0.000 claims abstract description 40
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000001070 adhesive effect Effects 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- 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 10
- 150000002009 diols Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 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 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- TVFIYRKPCACCNL-UHFFFAOYSA-N furan-2-carboxamide Chemical group NC(=O)C1=CC=CO1 TVFIYRKPCACCNL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 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 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 claims description 2
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 claims 1
- 229920001748 polybutylene Polymers 0.000 claims 1
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 12
- 230000003993 interaction Effects 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 125000004429 atom Chemical group 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
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- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 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 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical group COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PMDHMYFSRFZGIO-UHFFFAOYSA-N 1,4,7-trioxacyclotridecane-8,13-dione Chemical compound O=C1CCCCC(=O)OCCOCCO1 PMDHMYFSRFZGIO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NOQGZXFMHARMLW-UHFFFAOYSA-N Daminozide Chemical compound CN(C)NC(=O)CCC(O)=O NOQGZXFMHARMLW-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000167686 Reichardia Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- VVWMIGDZTWDLTH-UHFFFAOYSA-N butane-2,3-diol hexanedioic acid Chemical compound C(CCCCC(=O)O)(=O)O.CC(C(C)O)O VVWMIGDZTWDLTH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940106012 diethylene glycol adipate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane hot melt adhesive and a preparation method thereof, wherein the thermoplastic polyurethane hot melt adhesive is prepared by synthesizing raw materials comprising polymer dihydric alcohol, diisocyanate and a chain extender containing furan amide groups. The invention introduces furan amide groups with both rigid structures and hydrogen bond interactions into the hard segment of polyurethane, and the hot melt adhesive can form various non-covalent bond interactions with metal atoms, ions and polar groups on the surface of a substrate through the amide groups and oxygen atoms on the furan ring. Has excellent comprehensive adhesive performance, good initial adhesive strength, good final adhesive strength and repeatable adhesive property, and can be suitable for adhesion of various materials including metal, composite materials and plastics.
Description
Technical Field
The invention belongs to the technical field of polyurethane hot melt adhesives, and particularly relates to a thermoplastic polyurethane hot melt adhesive and a preparation method thereof.
Background
The polyurethane hot melt adhesive is suitable for adhesion of various materials, and has the comprehensive advantages of high adhesion strength, high adhesive layer toughness, excellent low-temperature performance, excellent impact resistance, solvent resistance, no toxicity and the like. Polyurethane hot melt adhesives can be classified into reactive polyurethane hot melt adhesives and thermoplastic polyurethane hot melt adhesives. The reactive polyurethane HMA has higher bonding strength after curing than the thermoplastic polyurethane hot melt adhesive due to chemical reaction with moisture, and generally has higher final bonding strength and good chemical resistance. However, the curing process usually requires a long time for the reaction of the-NCO with moisture, so that the initial adhesive strength is poor, and a long positioning time is required, which is not suitable for the rapid adhesive scene. And the permanent chemical crosslinking structure generated after the reaction brings technical difficulties to the glue removal, disassembly and repair of the assembly, so that the lap joint cannot be de-glued and recycled as required. In addition, due to the high reactivity and moisture sensitivity of the-NCO, the reactive polyurethane HMA has a shorter shelf life and is subject to deterioration, and more stringent storage, transport and use conditions. The thermoplastic polyurethane hot melt adhesive has high initial adhesive strength and short positioning time, and is particularly suitable for quick adhesion. The linear structure and physical crosslinking of the thermoplastic polyurethane hot melt adhesive endow the thermoplastic property, and the thermoplastic polyurethane hot melt adhesive can be heated again for adhesion removal and adhesion, is convenient for secondary processing such as adhesive removal and repair, can be processed into various shapes, has long shelf life and is convenient for transportation, storage and use. But the linear structure also limits the final adhesive strength of the thermoplastic polyurethane hot melt adhesive. With the increasing emphasis on rapid assembly and rapid positioning of joints in the production process of electronic and mechanical products to optimize the production cycle, emphasis on higher strength adhesives to meet mechanical properties, there is a need to explore new ways to improve the adhesive strength of thermoplastic polyurethane hot melt adhesives, and the reusability of hot melt adhesives.
There are few reports of improving performance by introducing a furan amide structure into a thermoplastic polyurethane hot melt adhesive. The Ningbo material technology and engineering research of China academy of sciences report that a 2, 5-furan dicarboxamide diamine compound, a preparation method and application thereof, disclosed that furan dicarboxamide diamine can be used for synthesizing polyurethane [ CN105985302A,2016.10.05], but for the synthesis of thermoplastic polyurethane adhesives, diamine is adopted to make the polymerization reaction process difficult to control, and cross-linked structures such as allophanate, biuret and the like are easy to form in the repeated heating and melting process during preparation and application, so that the repeated use and high adhesiveness of the thermoplastic polyurethane hot melt adhesive are not facilitated. Patent [ US20080182944a1, 2008.07.31] reports a process for preparing prepolymers or binders using polyols having a furan amide structure and polyacids, or with polynitriles, wherein the polyol has a functionality of greater than 3, and wherein the prepolymer or binder forms permanent chemical crosslinks after formation, which do not meet the reusable requirements of thermoplastic polyurethane hot melt adhesives.
Many research results indicate that the introduction of dynamic covalent bonds or non-covalent interactions between polymer molecular chains and between polymer subbing layer molecular chains and substrate surfaces to increase the adhesive strength of adhesives is a very effective strategy. In the polyurethane hot melt colloid system, the regulation and control of the chain extender can endow polyurethane with unique soft and hard chain segment structure, microphase separation characteristic, dynamic bond groups and the like. In addition, chain extenders and soft segments also have an important effect on the regulation of the molecular chain interactions of polyurethane adhesives and the interactions of colloids with substrate surfaces. However, some current dynamic bond introduction strategies often accompany complex dynamic bond module chemistry [ Acs Materials Letters,2021,3 (7), 1003-1009], or require the addition of metal ions and special fillers [ Science Advances,2021,7 (42): eabk2451], which limits the industrial application of this type of adhesive.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a thermoplastic polyurethane hot melt adhesive based on a furan amide chain extender and a preparation method thereof, and the obtained thermoplastic polyurethane hot melt adhesive has good adhesive strength to metal, epoxy resin, polycarbonate (PC) and the like, has thermoplasticity and can be heated again for adhesion removal and adhesion.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the thermoplastic polyurethane hot melt adhesive is prepared by synthesizing raw materials comprising polymer dihydric alcohol, diisocyanate and a furan amide group-containing chain extender, wherein the furan amide group-containing chain extender is one or more of compounds shown in the following formula:
the ratio of the amounts of the polymer diol and the substance of the furanamide group-containing chain extender is 1:1 to 5, preferably 1:
1 to 3; the ratio of the sum of the amounts of the total substances of the polymer diol, the furan amide group-containing chain extender and the amount of the diisocyanate substance is 1:1.
the number average molecular weight of the polymer diol is 1000 to 5000g/mol, preferably 1000 to 2000g/mol.
The polymer glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol, polyethylene oxide-propylene oxide glycol, polytetrahydrofuran-ethylene oxide glycol, poly (neopentyl glycol adipate) glycol (PNA), poly (1, 4-butylene glycol adipate) glycol (PBA), poly (1, 6-hexanediol adipate) glycol, poly (ethylene glycol adipate) glycol, poly (methyl propylene glycol adipate), poly (diethylene glycol adipate) glycol or poly (butylene glycol methyl propylene glycol adipate).
The diisocyanate is one or more of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI) and 4,4' -methylenebis (phenyl isocyanate) (MDI).
The chain extender containing furan amide groups can be compounded by adopting a plurality of chain extenders with different carbon chain length chemical formulas.
The invention also provides a preparation method of the thermoplastic polyurethane hot melt adhesive, which comprises the following steps: adding a catalyst into a chain extender raw material containing a furan amide group, namely polymer dihydric alcohol, diisocyanate and the furan amide group to react to prepare the thermoplastic polyurethane hot melt adhesive; the catalyst is one or more of dibutyl tin dilaurate, di-n-butyl tin dilaurate and dibutyl tin dilaurate.
Preferably, the mass of the catalyst is 0.01 to 0.1 percent of the total mass of the polymer diol, the diisocyanate and the chain extender containing furan amide groups.
Further, the preparation method is preferably as follows: under the protection of nitrogen, polymer glycol, diisocyanate and a catalyst are reacted for 2 to 4 hours at the temperature of 70 to 90 ℃ to obtain a prepolymer mixture, and the prepolymer mixture is heated to 90 to 120 ℃; and then adding a chain extender containing furan amide groups into the prepolymer mixture at 90-120 ℃ for chain extension reaction for 18-30 hours, and discharging to obtain the polyurethane hot melt adhesive.
Further, it is preferable that the polymer diol is first dehydrated by vacuum stirring at 120-140 ℃ for 1-4 hours, then the temperature is reduced to 70-90 ℃, nitrogen is introduced to replace vacuum, and diisocyanate and a catalyst are added to react under the protection of nitrogen.
The chain extender containing furan amide groups provided by the invention can be prepared by the following method:
adding dimethyl furan-2, 5-dicarboxylate into methanol solvent, adding HO- (CH) 2 ) a -NH 2 Stirring the compound at 50-60 ℃ for 20-30 hours, steaming to remove a methanol solvent, washing with acetone, filtering, and drying to obtain the chain extender containing furan amide groups; dimethyl furan-2, 5-dicarboxylate, HO- (CH) 2 ) a -NH 2 The ratio of the amounts of the substances of the compounds is 1:2-5. a=1, 2, 3, 4, or 5.
The viscosity flow transition temperature of the thermoplastic polyurethane hot melt adhesive prepared by the invention is 70-120 ℃ by adopting a temperature rheology scanning test. The number average molecular weight of the gel permeation chromatography test is 10000-45000 g/mol.
Compared with the prior art, the invention has the following beneficial effects: the introduction of furan amide groups in the hard segment improves the rigidity of polyurethane molecular chains, improves the physical crosslinking degree of polyurethane, and endows the polyurethane adhesive layer with good mechanical properties, and particularly shows that the modulus, the strength and the toughness of the adhesive layer are obviously improved. The good mechanical properties are the basis for achieving good adhesion between the glue layer and the substrate. In addition, the furan amide group and the oxygen atom on the furan ring introduced by the chain extender can form various non-covalent interactions with free radicals and atoms on the surface of the substrate, such as hydrogen bonds or metal-ion coordination bonds, and the like, which are beneficial to the improvement of the bonding strength. The thermoplastic polyurethane hot melt adhesive based on the furan amide chain extender provided by the invention is green and degradable, has excellent mechanical properties, has excellent comprehensive adhesive properties, good initial adhesive strength and final adhesive strength, and repeatable adhesive property, and can realize strong adhesion of various materials such as metal, composite materials, plastics and the like.
Drawings
FIG. 1 is a chart of nuclear magnetic resonance spectra of N, N-bis (2-hydroxyethyl) -2, 5-furandicarboxamide containing a furanamide group chain extender used in the examples of the present invention.
FIG. 2 is a chart of nuclear magnetic resonance spectra of comparative example 1 of the present invention using a control chain extender.
FIG. 3 is a chart showing nuclear magnetic resonance spectra of polyurethane hot melt adhesives prepared based on furan amide chain extender in examples 1-4 of the present invention.
FIG. 4 is a chart of the IR spectra of the polyurethane hot melt adhesives of examples 1 to 4 and comparative example 1 according to the present invention.
FIG. 5 is a graph showing stress strain curves of the polyurethane hot melt adhesives of examples 1 to 4 and comparative example 1 according to the present invention.
FIG. 6 is a graph showing the change in storage modulus (G ') and loss modulus (G') with temperature of the polyurethane hot melt adhesives of examples 1 to 4 and comparative example 1 of the present invention.
FIG. 7 is a bar graph showing the results of lap shear tests of the polyurethane hot melt adhesive of example 3 of the present invention with commercial hot melt adhesives 3M-2665, loctite-3542, TPU-Lubrizol-5713.
FIG. 8 is a schematic representation of the non-covalent interactions of the furan amide chain extender-based polyurethane hot melt adhesive of the present invention with metal atoms, ions or polar groups on the substrate surface to enhance adhesion.
Detailed Description
In order to better illustrate the technical scheme and advantages of the present invention, the present invention will be further described below with reference to specific examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following raw materials are used for experiments in the examples and comparative examples of the present invention, but are not limited to the following raw materials, and the present invention is merely specific examples to further specifically illustrate the effects of the furan amide-based chain extender polyurethane hot melt adhesive described in the present invention.
Polytetrahydrofuran-ethylene oxide diol: PTMG-1000, number average molecular weight 1000, shanghai Michlin Biochemical technology Co., ltd; polytetrahydrofuran-ethylene oxide diol: PTMG-2000, number average molecular weight 2000, shanghai Michlin Biochemical technology Co., ltd; a diisocyanate: isophorone diisocyanate IPDI, a company of alas Ding Shiji, inc; catalyst: dibutyl tin dilaurate DBTDL, alar Ding Shiji limited; dimethyl furan-2, 5-dicarboxylate (FDE), a company of ala Ding Shiji, inc; ethanolamine, ala Ding Shiji limited.
Hydrogen nuclear magnetic resonance (1H-NMR) testing was performed on a Bruker Avance DMX MHz spectrometer using deuterated DMSO as solvent and tetramethyl silicon as internal standard; infrared Spectroscopy (FT-IR) testing was performed on a Paragon 1000 spectrometer (Perkinelmer), with a 4000cm polyurethane hot melt adhesive -1 -500cm -1 The wavenumber range passes the total reflection mode test.
The rheological behaviour of the polymers was tested by means of an ARES-G2 rheometer. A25 mm parallel plate clamp is used for temperature scanning test, the strain is 0.1%, the angular frequency is 1rad/s, and the heating rate is 5 ℃/min.
Mechanical property test, polyurethane samples were prepared into films with a thickness of 1mm by a hot-pressing method at 120 ℃. Dumbbell-shaped bars were prepared by a cutter, and the test specimens had a length of 35mm, a width of 2mm and a thickness of 1mm. Tensile strength and elongation at break were tested on a 1000N sensor equipped universal stretcher Suns Technology Stock Co.Ltd at a tensile rate of 50mm/min. At least 3 replicates were performed for each sample and the Young's modulus was calculated from the initial linear phase slope of the stress-strain curve.
Single lap shear Strength test polyurethane hot melt adhesives and commercial TPU-Lubrizol-5713 hot melt adhesives were pressed into films of 0.2mm thickness at 120℃using a hot press. The hot melt adhesive film was cut into a rectangle (25 mm. Times.12.5 mm) and placed between two substrates (100 mm. Times.25 mm. Times.1.5 mm) to form an overlap region of 25 mm. Times.12.5 mm. The substrate was held in place with two clips and placed in an oven at a set temperature for 10 minutes of heat treatment. The samples were required to be cured at 25℃for 24 hours prior to testing. Lap shear strength tests were performed on a universal stretcher, suns Technology stock co.ltd equipped with a 5000N sensor, with at least 3 replicates per sample. For commercial 3M-2665 and Loctite-3542 adhesives, pre-heated in an oven at 120deg.C for 20 minutes, then coated onto a substrate, and finally cured at 25deg.C for 7 days.
Examples 1-5 were set up in the present invention.
First, a furan amide group-containing chain extender N, N-bis (2-hydroxyethyl) -2, 5-furandicarboxamide was prepared according to the following procedure: dimethyl furan-2, 5-dicarboxylate (7.37 g,40 mmol) was dissolved in 100mL of methanol at 50℃and then ethanolamine (9.77 g,160 mmol) was added to the solution, the mixed solution was stirred at 50℃for 24 hours, the solvent methanol was removed by rotary evaporator, and then the product and the starting material were repeatedly washed and filtered with acetone by virtue of the solubility difference in acetone, and dried in a vacuum oven to give the white solid product N, N-bis (2-hydroxyethyl) -2, 5-furandicarboxamide (HO-FDAM-OH), the nuclear magnetic resonance spectrum of which is shown in FIG. 1. The molecular formula is shown as follows:
in addition, the preparation of the furan amide chain extender polyurethane hot melt adhesive is carried out, examples 1-5 are arranged, the equivalent parts of the materials are shown in table 1, and the molecular weight and viscosity-to-transition temperature information of the prepared polyurethane hot melt adhesive are also shown in table 1:
table 1:
the polyurethane hot melt adhesives of examples 1-4 were prepared as follows:
PTMG-1000 (10 g,10 mmol) was added to a 250mL three-necked flask with mechanical stirring and the water was removed in vacuo at 120℃for 2 hours. The temperature was then reduced to 70℃and nitrogen was purged to replace the vacuum. Adding corresponding amount of IPDI and 0.01g of DBTDL into a flask, gradually heating, and sequentially reacting at 70 ℃, 80 ℃ and 90 ℃ for 1 hour; then continuously heating to 110 ℃, adding the HO-FDAM-OH with the corresponding amount into the prepolymer mixture, reacting for 24 hours at 110 ℃, and discharging to obtain the polyurethane hot melt adhesive PUFD-x (x is the molar ratio of the chain extender to PTMG-1000). The nuclear magnetic resonance spectra of the polyurethane hot melt adhesives prepared in examples 1 to 4 are shown in FIG. 3.
PTMG-2000 (20 g,10 mmol) was added to a 250mL three-necked flask with mechanical stirring and the water was removed in vacuo at 120℃for 2 hours. The temperature was then reduced to 70℃and nitrogen was purged to replace the vacuum. IPDI (8.89 g,40 mmol) and 0.015g DBTDL were added to the flask, gradually warmed up, and reacted sequentially at 70℃and 80℃and 90℃for 1 hour each; then, the temperature was further raised to 110℃and HO-FDAM-OH (7.27 g,30 mmol) was added to the prepolymer mixture, the reaction was carried out at 110℃for 24 hours, and the polyurethane hot melt adhesive PUFD-2000-3 was obtained by discharging.
Comparative example 1
The synthesis of the para-benzamide diol chain extender (referred to as control chain extender) was similar to HO-FDAM-OH. The dimethyl furan-2, 5-dicarboxylate was replaced with dimethyl terephthalate, and the rest of the synthesis steps were the same. The molecular formula of the control chain extender is shown as the following formula
Comparative example 1 preparation of polyurethane. HO-
The FDAM-OH is replaced by the para-benzamide diol chain extender to obtain polyurethane PUET-1, and the nuclear magnetic resonance spectrum is shown in figure 2.
The infrared spectrum diagrams of the polyurethane hot melt adhesives of examples 1 to 4 and comparative example 1 are shown in FIG. 4. FT-for all products
No IR spectrum is shown at 2276cm -1 The left and right isocyanate group absorption peaks indicate that IPDI has been completely converted. 1658cm with increasing amount of furan amide chain extender -1 The amide c=o absorption peak and the telescopic vibration absorption peak of-NH at 3300cm "1 were enhanced, indicating that more hydrogen bond associations were formed. The benzene ring is adopted by the PUET-1 to replace furan rings, and the hydrogen bond association of the sites which lack oxygen hetero atoms as hydrogen bonds is weakened. It is demonstrated that the chain extender adopting the furan amide structure is effective for enhancing the molecular chain hydrogen bonding effect of the polyurethane hot melt adhesive.
Stress strain graphs of the polyurethane hot melt adhesives of examples 1 to 4 and comparative example 1 are shown in fig. 5. The PUFD-l has the elongation rate and breaking strength of quite bright eyes, the breaking elongation rate can reach more than 2500%, the breaking strength can reach 37MPa, and the high toughness of the adhesive layer is significant for realizing strong adhesion.
The storage modulus (G ') and loss modulus (G') of the polyurethane hot melt adhesives of examples 1 to 4 and comparative example 1 are plotted as a function of temperature, as shown in FIG. 6.
The polyurethane hot melt adhesives obtained in examples 1 to 5 and comparative example 1 were subjected to performance test, and the test results are shown in Table 2:
table 2:
a bar chart of the results of the lap shear test of the polyurethane hot melt adhesive PUFD-1.5 of example 3 with the commercial hot melt adhesives 3M-2665, loctite-3542, TPU-Lubrizol-5713 is shown in FIG. 7.
As can be seen from the comprehensive performance evaluation of Table 2 and FIG. 7, examples 2 to 4 exhibited excellent adhesion properties to aluminum, copper, epoxy resin, PC, and example 3 had adhesion properties to each material superior to that of the conventional commercial hot melt adhesive. While comparative example 1 has not the same adhesive properties and mechanical properties as examples 2-4.
A schematic diagram of non-covalent interaction between the polyurethane hot melt adhesive based on the furan amide chain extender and metal atoms, ions or polar groups on the surface of a substrate for adhesion enhancement is shown in fig. 8, and the furan amide groups can form hydrogen bonds or metal-ion coordination bonds with free groups and atoms on the surface of the substrate, so that the adhesion strength can be improved.
The benzene ring in the molecular chain structure of the chain extender of comparative example 1 does not participate in the non-covalent interaction of the glue layer and the substrate like a furan ring, and the mechanical properties of the PUET-1 glue layer are obviously inferior to those of PUFD-1. The above results fully demonstrate that the furan ring is critical for improving adhesion properties.
Claims (10)
1. The thermoplastic polyurethane hot melt adhesive is characterized by being prepared by synthesizing raw materials comprising polymer dihydric alcohol, diisocyanate and a furan amide group-containing chain extender, wherein the furan amide group-containing chain extender is one or more of compounds shown in the following formula:
2. the thermoplastic polyurethane hot melt adhesive according to claim 1, wherein the ratio of the amounts of the substances of the polymer diol and the furanamide group-containing chain extender is 1:1-5, the ratio of the sum of the amounts of the total substances of the polymer diol, the furanamide group-containing chain extender to the amount of the diisocyanate being 1:1.
3. the thermoplastic polyurethane hot melt adhesive of claim 1, wherein the number average molecular weight of the polymeric diol is 1000 to 5000g/mol.
4. The thermoplastic polyurethane hot melt adhesive of claim 3, wherein the polymer glycol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol, polyethylene oxide-propylene oxide glycol, polytetrahydrofuran-ethylene oxide glycol, neopentyl glycol adipate glycol, poly 1, 4-butanediol adipate glycol, poly 1, 6-hexanediol adipate glycol, polyethylene adipate glycol, polymethyl adipate glycol, polyethylene glycol adipate glycol, or polybutylene glycol methyl adipate glycol.
5. The thermoplastic polyurethane hot melt adhesive of claim 1, wherein the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4' -methylenebis (phenyl isocyanate).
6. The thermoplastic polyurethane hot melt adhesive according to claim 1, wherein the adhesive flow transition temperature of the thermoplastic polyurethane hot melt adhesive is 70-120 ℃ and the number average molecular weight is 10000-45000 g/mol.
7. The process for preparing a thermoplastic polyurethane hot melt adhesive according to one of claims 1 to 6, characterized in that it comprises the steps of: adding a catalyst into a chain extender raw material containing a furan amide group, namely polymer dihydric alcohol, diisocyanate and the furan amide group to react to prepare the thermoplastic polyurethane hot melt adhesive; the catalyst is one or more of dibutyl tin dilaurate, di-n-butyl tin dilaurate and dibutyl tin dilaurate.
8. The method for preparing a thermoplastic polyurethane hot melt adhesive according to claim 7, wherein the mass amount of the catalyst is 0.01 to 0.1% of the total mass of the polymer diol, the diisocyanate and the chain extender containing furan amide groups.
9. The method for preparing a thermoplastic polyurethane hot melt adhesive according to claim 7 or 8, wherein the preparation method comprises the following steps: under the protection of nitrogen, polymer glycol, diisocyanate and a catalyst are reacted for 2 to 4 hours at the temperature of 70 to 90 ℃ to obtain a prepolymer mixture, and the prepolymer mixture is heated to 90 to 120 ℃; and then adding a chain extender containing furan amide groups into the prepolymer mixture at 90-120 ℃ for chain extension reaction for 18-30 hours, and discharging to obtain the polyurethane hot melt adhesive.
10. The method for preparing the thermoplastic polyurethane hot melt adhesive according to claim 9, wherein the polymer diol is firstly subjected to vacuum stirring at 120-140 ℃ for removing water for 1-4 hours, then the temperature is reduced to 70-90 ℃, nitrogen is introduced for replacing vacuum, and diisocyanate and a catalyst are added for reaction under the protection of nitrogen.
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| CN117551413A (en) * | 2024-01-10 | 2024-02-13 | 信泰永合(烟台)新材料有限公司 | Polyurethane hot melt adhesive for nylon bonding and preparation method thereof |
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| CN117551413B (en) * | 2024-01-10 | 2024-05-10 | 信泰永合(烟台)新材料有限公司 | Polyurethane hot melt adhesive for nylon bonding and preparation method thereof |
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