CN116987473A - Functional polyurethane adhesive and preparation method thereof - Google Patents
Functional polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN116987473A CN116987473A CN202310990705.1A CN202310990705A CN116987473A CN 116987473 A CN116987473 A CN 116987473A CN 202310990705 A CN202310990705 A CN 202310990705A CN 116987473 A CN116987473 A CN 116987473A
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- polyurethane adhesive
- castor oil
- stirring
- polyphenyl ether
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 100
- 239000004814 polyurethane Substances 0.000 title claims abstract description 100
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 80
- 239000000853 adhesive Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- 239000004359 castor oil Substances 0.000 claims description 45
- 235000019438 castor oil Nutrition 0.000 claims description 45
- 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 claims description 45
- 238000003756 stirring Methods 0.000 claims description 41
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 40
- 239000004970 Chain extender Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 31
- 229920000570 polyether Polymers 0.000 claims description 31
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 30
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000008213 purified water Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000007599 discharging Methods 0.000 claims description 15
- 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 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000010008 shearing Methods 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920013638 modified polyphenyl ether Polymers 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 125000005543 phthalimide group Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 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 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 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 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- DUILGEYLVHGSEE-ZETCQYMHSA-N 2-[[(2s)-oxiran-2-yl]methyl]isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1C[C@H]1CO1 DUILGEYLVHGSEE-ZETCQYMHSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 238000007792 addition Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000001804 emulsifying effect Effects 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic groups
-
- 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
- C08G18/28—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
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
Landscapes
- 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 relates to the technical field of adhesives and discloses a functional polyurethane adhesive and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a functional polyurethane adhesive and a preparation method thereof.
Background
Polyurethane adhesives have good low temperature resistance, water resistance, oil resistance and mechanical properties, have been paid attention to since the advent, and the bonding process of the polyurethane adhesives is simple, so the polyurethane adhesives are widely applied in the fields of shoe industry, composite films, artificial leather, fabrics and the like. However, general polyurethane generally adopts polyether or polyester diol as a soft segment, and has a structure containing a large amount of ether bonds with low cohesive energy, so that the high temperature resistance of the polyurethane adhesive is poor, the viscosity of the polyurethane adhesive is easy to lose efficacy in a high temperature environment, generally, the long-term use temperature of the general polyurethane adhesive is not higher than 80 ℃, and the short-term use temperature of the general polyurethane adhesive is not higher than 120 ℃, so that the application range of the polyurethane adhesive is greatly limited. And because the heat resistance of polyurethane is poor, the polyurethane adhesive is easy to generate thermal aging, the polyurethane adhesive is yellow, the yellowing phenomenon is generated, the appearance of a bonding product is seriously influenced, the application of the polyurethane adhesive in a high-end product is directly hindered, and therefore, the polyurethane adhesive has important significance in properly improving the polyurethane.
The prior art is often to improve the high temperature resistance and other properties of polyurethane adhesives by means of functional additives, and the invention patent application with the application number of CN202010261731.7 discloses a polyurethane adhesive with higher temperature resistance, and by using phthalic anhydride acid ester as a raw material, a benzene ring with higher rigidity is introduced into a polyurethane molecular chain, so that the bond energy of decomposing C-N bonds is improved, and the effect of improving the temperature resistance of the polyurethane adhesive is achieved. Therefore, the polyurethane molecular chain structure can be optimized through designing the polyurethane molecular chain, the ether bond content is reduced, and the high-temperature-resistant modification of polyurethane is realized, but the scheme cannot solve the problem of thermal aging yellowing of the polyurethane adhesive, and the phenomenon of migration and precipitation is easy to occur in a conventional mode of adding a small molecular antioxidant, so that the durability is difficult to ensure.
Disclosure of Invention
The invention aims to provide a functional polyurethane adhesive and a preparation method thereof, which solve the problems that the polyurethane adhesive has poor high temperature resistance and is easy to cause thermo-oxidative aging yellowing.
The aim of the invention can be achieved by the following technical scheme:
the functional polyurethane adhesive comprises the following raw materials in parts by weight: 40-55 parts of polyether glycol, 5-12 parts of functionalized polyphenyl ether, 10-25 parts of diisocyanate, 0.05-0.15 part of organotin catalyst, 4-6 parts of castor oil-based chain extender and 80-100 parts of purified water;
the functionalized polyphenyl ether is low molecular weight polyphenyl ether grafted and modified by an antioxidant;
the castor oil-based chain extender is a castor oil derivative containing a rigid phthalimide structure in a molecular chain.
Further, the polyether glycol is polyoxypropylene glycol having a molecular weight of 1000; the diisocyanate is any one or more of diphenylmethane diisocyanate, xylylene diisocyanate or cyclohexane dimethylene diisocyanate; the organotin catalyst is any one of stannous octoate or dibutyltin dilaurate.
Further, the functionalized polyphenyl ether is prepared by the following preparation method:
step one: mixing polyphenyl ether and N, N-dimethylformamide, stirring and dissolving, introducing nitrogen, adding epichlorohydrin and stannic chloride, uniformly mixing, stirring at 60-65 ℃ for 12-16 hours, evaporating the solvent, and separating out solid materials to obtain an epoxy modified polyphenyl ether intermediate;
step two: mixing the epoxy modified polyphenyl ether intermediate with 1, 4-dioxane, stirring to form a uniform solution, adding 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and a catalyst A into the solution, reacting for 4-8 hours at 60-70 ℃ under the protection of nitrogen, cooling and discharging to obtain the functionalized polyphenyl ether.
Further, in the first step, the molecular weight of the polyphenylene ether is 1600.
Further, in the second step, the catalyst a is triethylamine.
According to the technical scheme, tin tetrachloride is used as a catalyst, epichlorohydrin is used as an electrophile, a Friedel-crafts alkylation reaction is carried out on a benzene ring of a polyphenyl ether skeleton to prepare an epoxy modified polyphenyl ether intermediate, and under the catalysis of triethylamine, an epoxy group in the structure of the epoxy modified polyphenyl ether intermediate can carry out a ring-opening esterification reaction with a carboxyl group in a 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid structure, so that a hindered phenol group with the effect of resisting thermal oxidative aging is grafted in a polyphenyl ether molecular chain to prepare the functional polyphenyl ether.
Further, the preparation method of the castor oil-based chain extender specifically comprises the following steps:
mixing castor oil, (S) -N-glycidol phthalimide with toluene, stirring uniformly, adding a catalyst B, mixing uniformly, introducing nitrogen for protection, raising the temperature of the system to 65-75 ℃, stirring at constant temperature for 6-12h, evaporating the solvent, cooling and discharging to obtain the castor oil-based chain extender.
Further, the mass ratio of the castor oil to the (S) -N-glycidylphthalimide is 1:0.65-0.7.
Further, the catalyst B is any one of tetraethylammonium bromide, tetrabutylammonium bromide or tetrabutylammonium bisulfate.
In the technical scheme, the castor oil structure contains three equivalent active hydroxyl groups, and can be subjected to ring-opening addition reaction with epoxy groups in the (S) -N-glycidol phthalimide structure under the action of a catalyst, so that the phthalimide structure is introduced into a molecular chain of the castor oil, and in addition, the active hydroxyl groups can be generated during the ring-opening addition reaction, so that the prepared product can be used as a chain extender of a polyurethane adhesive, namely a castor oil-based chain extender.
A preparation method of a functional polyurethane adhesive comprises the following steps:
the first step: stirring and mixing polyether glycol and functionalized polyphenyl ether in parts by weight, dehydrating in vacuum for 1h, reducing the temperature to 55-60 ℃, adding diisocyanate and an organotin catalyst in parts by weight, uniformly mixing, raising the temperature to 70-75 ℃, and carrying out heat preservation and stirring for 2-4h to form a polyurethane prepolymer;
and a second step of: the temperature of the system is reduced to 55-60 ℃ again, castor oil-based chain extender with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after the completion of the addition and the stirring reaction for 1-2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, carrying out high-speed shearing and emulsification for 1-2h, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Further, in the first step, the temperature at the time of vacuum dehydration is 90-120 ℃.
In the technical scheme, polyether glycol and functionalized polyphenyl ether are used as soft segments, diisocyanate is used as hard segments, hydroxyl groups in the polyether glycol and functionalized polyphenyl ether structure and diisocyanate are subjected to amine esterification reaction under the action of an organotin catalyst and gradually polymerized to form an isocyanate-terminated polyurethane prepolymer with a linear chain structure, the isocyanate-terminated polyurethane prepolymer can react with hydroxyl groups in a castor oil-based chain extender structure to realize chain extension polymerization, and a polyurethane polymer is prepared and is subjected to shearing emulsification to obtain the polyurethane adhesive.
The invention has the beneficial effects that:
1) According to the invention, starting from the polyurethane structure, the functionalized polyphenyl ether is used as one of the soft segments, so that the prepared polyurethane molecular main chain structure contains more rigid benzene ring structures, and the stability of polyurethane molecular chains is improved, thereby effectively enhancing the high temperature resistance of the polyurethane adhesive. Meanwhile, the cohesion of polyurethane molecules is controlled by controlling the proportion of polyether glycol and functionalized polyphenyl ether, so that the phenomenon that the adhesive strength of the polyurethane adhesive is greatly reduced due to the addition of the functionalized polyphenyl ether is avoided. In addition, the functionalized polyphenyl ether structure also contains hindered phenol antioxidant groups, so that the oxidation resistance of the polyurethane adhesive can be effectively enhanced, the phenomenon of thermal oxidation aging yellowing of the polyurethane adhesive is avoided, and the phenomenon of migration and precipitation of the antioxidant groups which are chemically connected can be avoided, so that the oxidation durability of the polyurethane adhesive is ensured.
2) According to the invention, the castor oil-based chain extender is prepared to chain extend the polyurethane prepolymer, under the action of the castor oil-based chain extender, the binding force among polyurethane molecular chains is enhanced, the cohesive energy is improved, and the castor oil structure contains ester groups which can generate hydrogen bonds with an adhered substrate, so that the problems of reduced ether bond content and reduced adhesive property caused by using functionalized polyphenyl ether as a soft segment can be solved. In addition, the castor oil-based chain extender contains a phthalimide structure, so that the purpose of introducing a rigid group into a side chain of a polyurethane molecule can be realized, the high temperature resistance of the polyurethane adhesive is further enhanced, and the unsaturated alkenyl in the castor oil structure can generate a conjugation effect with a benzene ring in the phthalimide structure to form a large pi bond, so that the rigidity of the polyurethane molecule chain is further enhanced, and the continuous use of the polyurethane adhesive in a high temperature environment is facilitated.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of castor oil-based chain extenders used in examples and comparative examples of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. 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 functionalized polyphenylene ether used in the following examples and comparative examples was prepared by the following steps:
step one: mixing 1.2g of polyphenyl ether with molecular weight of 1600 with N, N-dimethylformamide, stirring and dissolving, introducing nitrogen, adding 2.5g of epichlorohydrin and 2g of stannic chloride, uniformly mixing, stirring at 65 ℃ for 12 hours, evaporating the solvent, and separating out solid materials to prepare an epoxy modified polyphenyl ether intermediate;
step two: mixing 1g of epoxy modified polyphenyl ether intermediate with 1, 4-dioxane, stirring to form a uniform solution, adding 5g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and triethylamine into the solution, and carrying out heat preservation reaction for 6 hours at 65 ℃ under the protection of nitrogen, cooling and discharging to obtain the functionalized polyphenyl ether.
0.3g of the functionalized polyphenyl ether is accurately weighed as a test sample, the content of ester groups in the test sample is tested by a soap back titration method, and the content of the ester groups is 4.819mmo l/g, so that the ester groups can be reasonably speculated to be formed by ring-opening esterification reaction of epoxy groups in an epoxy modified polyphenyl ether intermediate structure and carboxyl groups in a 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid structure.
The castor oil-based chain extenders used in the following examples and comparative examples were prepared by the following methods:
mixing 1.6g of castor oil and 1.05g of (S) -N-glycidol phthalimide with toluene, uniformly stirring, adding tetrabutylammonium bromide, uniformly mixing, introducing nitrogen for protection, raising the temperature of the system to 70 ℃, stirring at constant temperature for 9 hours, evaporating the solvent, cooling and discharging to obtain the castor oil-based chain extender.
Infrared test samples of castor oil-based chain extenders were prepared using potassium bromide tabletting and infrared analytical testing was performed with results shown in FIG. 1, in which 3429cm -1 Is the stretching vibration peak of hydroxyl group, 3078cm -1 Is C-H telescopic vibration peak in benzene ring skeleton, 3026cm -1 Is a C-H telescopic vibration peak in carbon-carbon double bonds in castor oil, 2855 cm to 2940cm -1 Is C-H stretching vibration peak in methyl and methylene, 1741cm -1 The stretching vibration peak of the ester group C=O in castor oil is 1653cm -1 Is C=0 stretching vibration peak in imide structure, 1055-1090 cm -1 Is characterized by an ether bond C-O-C characteristic absorption peak.
Example 1
The functional polyurethane adhesive comprises the following raw materials in parts by weight: 40 parts of polyether glycol, 5 parts of functionalized polyphenyl ether, 10 parts of cyclohexane dimethylene diisocyanate, 0.05 part of stannous octoate, 4 parts of castor oil-based chain extender and 80 parts of purified water.
The preparation method of the polyurethane adhesive comprises the following steps:
the first step: stirring and mixing polyether glycol and functionalized polyphenyl ether in parts by weight, vacuum dehydrating at 90 ℃ for 1h, reducing the temperature to 55 ℃, adding cyclohexane dimethylene diisocyanate and stannous octoate in parts by weight, uniformly mixing, raising the temperature to 70 ℃, and carrying out heat preservation and stirring for 2h to form a polyurethane prepolymer, wherein the polyether glycol is polyoxypropylene glycol with the molecular weight of 1000;
and a second step of: the temperature of the system is reduced to 55 ℃ again, castor oil-based chain extender with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after the completion of the addition and the stirring reaction for 1 hour;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, shearing and emulsifying for 1h at high speed, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Example 2
The functional polyurethane adhesive comprises the following raw materials in parts by weight: 50 parts of polyether glycol, 6 parts of functionalized polyphenyl ether, 20 parts of diphenylmethane diisocyanate, 0.1 part of dibutyltin dilaurate, 5 parts of castor oil-based chain extender and 95 parts of purified water.
The preparation method of the polyurethane adhesive comprises the following steps:
the first step: stirring and mixing polyether glycol and functionalized polyphenyl ether in parts by weight, vacuum dehydrating at 100 ℃ for 1h, reducing the temperature to 60 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate in parts by weight, uniformly mixing, raising the temperature to 75 ℃, and carrying out heat preservation and stirring for 3h to form a polyurethane prepolymer, wherein the polyether glycol is polyoxypropylene glycol with the molecular weight of 1000;
and a second step of: the temperature of the system is reduced to 60 ℃ again, castor oil-based chain extender with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after the completion of the addition and the stirring reaction for 2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, shearing and emulsifying for 2 hours at high speed, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Example 3
The functional polyurethane adhesive comprises the following raw materials in parts by weight: 55 parts of polyether glycol, 12 parts of functionalized polyphenyl ether, 25 parts of xylylene diisocyanate, 0.15 part of stannous octoate, 6 parts of castor oil-based chain extender and 100 parts of purified water.
The preparation method of the polyurethane adhesive comprises the following steps:
the first step: stirring and mixing the polyether glycol and the functionalized polyphenyl ether in parts by weight, vacuum dehydrating for 1h at the temperature of 120 ℃, reducing the temperature to 60 ℃, adding the xylylene diisocyanate and the stannous octoate in parts by weight, uniformly mixing, and then raising the temperature to 75 ℃, preserving heat and stirring for 4h to form a polyurethane prepolymer, wherein the polyether glycol is polyoxypropylene glycol with the molecular weight of 1000;
and a second step of: the temperature of the system is reduced to 60 ℃ again, castor oil-based chain extender with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after the completion of the addition and the stirring reaction for 2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, shearing and emulsifying for 2 hours at high speed, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Comparative example 1
The polyurethane adhesive comprises the following raw materials in parts by weight: 50 parts of polyether glycol, 6 parts of polyphenyl ether, 20 parts of diphenylmethane diisocyanate, 0.1 part of dibutyltin dilaurate, 5 parts of castor oil-based chain extender and 95 parts of purified water.
The preparation method of the polyurethane adhesive comprises the following steps:
the first step: stirring and mixing polyether glycol and polyphenyl ether in parts by weight, vacuum dehydrating at 100 ℃ for 1h, reducing the temperature to 60 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate in parts by weight, uniformly mixing, and then raising the temperature to 75 ℃, and carrying out heat preservation and stirring for 3h to form a polyurethane prepolymer, wherein the polyether glycol is polyoxypropylene glycol with the molecular weight of 1000;
and a second step of: the temperature of the system is reduced to 60 ℃ again, castor oil-based chain extender with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after the completion of the addition and the stirring reaction for 2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, shearing and emulsifying for 2 hours at high speed, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Comparative example 2
The polyurethane adhesive comprises the following raw materials in parts by weight: 50 parts of polyether glycol, 20 parts of diphenylmethane diisocyanate, 0.1 part of dibutyltin dilaurate, 5 parts of castor oil-based chain extender and 95 parts of purified water.
The preparation method of the polyurethane adhesive comprises the following steps:
the first step: placing polyether glycol in parts by weight at a temperature of 100 ℃ for vacuum dehydration for 1h, reducing the temperature to 60 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate in parts by weight, uniformly mixing, raising the temperature to 75 ℃, and carrying out heat preservation and stirring for 3h to form a polyurethane prepolymer, wherein the polyether glycol is polyoxypropylene glycol with a molecular weight of 1000;
and a second step of: the temperature of the system is reduced to 60 ℃ again, castor oil-based chain extender with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after the completion of the addition and the stirring reaction for 2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, shearing and emulsifying for 2 hours at high speed, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Comparative example 3
The functional polyurethane adhesive comprises the following raw materials in parts by weight: 50 parts of polyether glycol, 6 parts of functionalized polyphenyl ether, 20 parts of diphenylmethane diisocyanate, 0.1 part of dibutyltin dilaurate, 5 parts of castor oil and 95 parts of purified water.
The preparation method of the polyurethane adhesive comprises the following steps:
the first step: stirring and mixing polyether glycol and functionalized polyphenyl ether in parts by weight, vacuum dehydrating at 100 ℃ for 1h, reducing the temperature to 60 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate in parts by weight, uniformly mixing, raising the temperature to 75 ℃, and carrying out heat preservation and stirring for 3h to form a polyurethane prepolymer, wherein the polyether glycol is polyoxypropylene glycol with the molecular weight of 1000;
and a second step of: the temperature of the system is reduced to 60 ℃ again, castor oil with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after stirring reaction for 2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, shearing and emulsifying for 2 hours at high speed, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Comparative example 4
The functional polyurethane adhesive comprises the following raw materials in parts by weight: 50 parts of polyether glycol, 6 parts of functionalized polyphenyl ether, 20 parts of diphenylmethane diisocyanate, 0.1 part of dibutyltin dilaurate, 5 parts of 1, 4-butanediol and 95 parts of purified water.
The preparation method of the polyurethane adhesive comprises the following steps:
the first step: stirring and mixing polyether glycol and functionalized polyphenyl ether in parts by weight, vacuum dehydrating at 100 ℃ for 1h, reducing the temperature to 60 ℃, adding diphenylmethane diisocyanate and dibutyltin dilaurate in parts by weight, uniformly mixing, raising the temperature to 75 ℃, and carrying out heat preservation and stirring for 3h to form a polyurethane prepolymer, wherein the polyether glycol is polyoxypropylene glycol with the molecular weight of 1000;
and a second step of: the temperature of the system is reduced to 60 ℃ again, 1, 4-butanediol with the weight part is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after stirring and reacting for 2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, shearing and emulsifying for 2 hours at high speed, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
Coating the polyurethane adhesives prepared in the invention examples 1-3 and comparative examples 1-4 on the surface of an aluminum foil, covering the aluminum foil by using a nylon layer, controlling the thickness of the adhesive layer to be 20um, standing for 24 hours, preparing a sample to be tested meeting the specification, performing a peel strength test by referring to a standard GB/T2791-1995, placing the sample in a heat aging box after the test is completed, setting the temperature to 160 ℃ and the humidity to 90%, taking out the sample after an accelerated aging test is performed for 12 hours, testing the peel strength again, testing the color difference value of the sample before and after aging by using a CS-200 type color difference meter, evaluating the aging resistance, and recording the test results in the following table:
as can be seen from the data recorded in the table, the polyurethane adhesives prepared in the examples 1 to 3 have good bonding strength at normal temperature, and after heat aging treatment, the peeling force is not obviously reduced, and the color difference value is low, so that the polyurethane adhesive has good high temperature resistance and aging yellowing resistance.
The polyphenyl ether used in the polyurethane adhesive prepared in the comparative example 1 is not modified, and the structure does not contain hindered phenol antioxidant functional groups, so that the aging and yellowing resistance performance is poor, but the high temperature resistance performance is good.
The polyurethane adhesive prepared in comparative example 2 does not use polyphenyl ether as a soft segment, and has a large ether bond content in the structure, so that the adhesive performance is optimal, but the polyurethane adhesive prepared by the rigid structure and the lack of an antioxidant functional group has poor high temperature resistance and aging yellowing resistance.
The polyurethane adhesive prepared in comparative example 3 uses castor oil as a chain extender, so that the side chain does not contain a rigid phthalimide structure, and meanwhile, a large pi bond cannot be formed, so that the high temperature resistance is poor.
The polyurethane adhesive prepared in comparative example 4 uses conventional 1, 4-butanediol as a chain extender, so that the cohesion of polyurethane molecular chains is reduced, and the high temperature resistance of the polyurethane adhesive is further reduced.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. The functional polyurethane adhesive is characterized by comprising the following raw materials in parts by weight: 40-55 parts of polyether glycol, 5-12 parts of functionalized polyphenyl ether, 10-25 parts of diisocyanate, 0.05-0.15 part of organotin catalyst, 4-6 parts of castor oil-based chain extender and 80-100 parts of purified water;
the functionalized polyphenyl ether is low molecular weight polyphenyl ether grafted and modified by an antioxidant;
the castor oil-based chain extender is a castor oil derivative containing a rigid phthalimide structure in a molecular chain.
2. The functional polyurethane adhesive of claim 1, wherein the polyether glycol is a polyoxypropylene glycol having a molecular weight of 1000; the diisocyanate is any one or more of diphenylmethane diisocyanate, xylylene diisocyanate or cyclohexane dimethylene diisocyanate; the organotin catalyst is any one of stannous octoate or dibutyltin dilaurate.
3. The functional polyurethane adhesive of claim 1, wherein the functionalized polyphenylene ether is prepared by the following preparation method:
step one: mixing polyphenyl ether and N, N-dimethylformamide, stirring and dissolving, introducing nitrogen, adding epichlorohydrin and stannic chloride, uniformly mixing, stirring at 60-65 ℃ for 12-16 hours, evaporating the solvent, and separating out solid materials to obtain an epoxy modified polyphenyl ether intermediate;
step two: mixing the epoxy modified polyphenyl ether intermediate with 1, 4-dioxane, stirring to form a uniform solution, adding 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and a catalyst A into the solution, reacting for 4-8 hours at 60-70 ℃ under the protection of nitrogen, cooling and discharging to obtain the functionalized polyphenyl ether.
4. A functional polyurethane adhesive according to claim 3, wherein in step one, the polyphenylene ether has a molecular weight of 1600.
5. A functional polyurethane adhesive according to claim 3, wherein in step two, the catalyst a is triethylamine.
6. The functional polyurethane adhesive according to claim 1, wherein the castor oil-based chain extender is prepared by a method comprising the following steps:
mixing castor oil, (S) -N-glycidol phthalimide with toluene, stirring uniformly, adding a catalyst B, mixing uniformly, introducing nitrogen for protection, raising the temperature of the system to 65-75 ℃, stirring at constant temperature for 6-12h, evaporating the solvent, cooling and discharging to obtain the castor oil-based chain extender.
7. The functional polyurethane adhesive according to claim 6, wherein the mass ratio of the castor oil to the (S) -N-glycidylphthalimide is 1:0.65-0.7.
8. The functional polyurethane adhesive according to claim 6, wherein the catalyst B is any one of tetraethylammonium bromide, tetrabutylammonium bromide or tetrabutylammonium bisulfate.
9. A method for preparing a functional polyurethane adhesive according to any one of claims 1-8, comprising the steps of:
the first step: stirring and mixing polyether glycol and functionalized polyphenyl ether in parts by weight, dehydrating in vacuum for 1h, reducing the temperature to 55-60 ℃, adding diisocyanate and an organotin catalyst in parts by weight, uniformly mixing, raising the temperature to 70-75 ℃, and carrying out heat preservation and stirring for 2-4h to form a polyurethane prepolymer;
and a second step of: the temperature of the system is reduced to 55-60 ℃ again, castor oil-based chain extender with the weight parts is added into the polyurethane prepolymer, and the polyurethane prepolymer is formed after the completion of the addition and the stirring reaction for 1-2 hours;
and a third step of: adding purified water in parts by weight into the polyurethane polymer, carrying out high-speed shearing and emulsification for 1-2h, discharging, packaging, sealing and preserving to obtain the polyurethane adhesive.
10. The method for preparing a functional polyurethane adhesive according to claim 9, wherein in the first step, the temperature during vacuum dehydration is 90-120 ℃.
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