CN117025158A - Anti-aging polyurethane adhesive and preparation method and application thereof - Google Patents
Anti-aging polyurethane adhesive and preparation method and application thereof Download PDFInfo
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- CN117025158A CN117025158A CN202311297298.2A CN202311297298A CN117025158A CN 117025158 A CN117025158 A CN 117025158A CN 202311297298 A CN202311297298 A CN 202311297298A CN 117025158 A CN117025158 A CN 117025158A
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- polyurethane adhesive
- aging
- polycarbonate
- hindered phenol
- fluorine
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 63
- 239000004814 polyurethane Substances 0.000 title claims abstract description 63
- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 58
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 42
- 239000004417 polycarbonate Substances 0.000 claims abstract description 41
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 41
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 22
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 22
- 229960000281 trometamol Drugs 0.000 claims description 22
- 150000002009 diols Chemical class 0.000 claims description 18
- -1 phenol diol Chemical class 0.000 claims description 17
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 11
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 claims description 10
- AQQBRCXWZZAFOK-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(Cl)=O AQQBRCXWZZAFOK-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 2
- 229920006351 engineering plastic Polymers 0.000 claims description 2
- 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 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000010248 power generation Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000012745 toughening agent Substances 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
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to an anti-aging polyurethane adhesive, a preparation method and application thereof, wherein the anti-aging polyurethane adhesive comprises the following components: the polyurethane adhesive comprises a polycarbonate type polyurethane prepolymer, a catalyst and an organic solvent, wherein the polycarbonate type polyurethane prepolymer consists of polycarbonate dihydric alcohol, fluorine-chain-containing hindered phenol dihydric alcohol, ternary alcohol and benzene-containing diisocyanate, and the fluorine-chain-containing hindered phenol dihydric alcohol is introduced into the polyurethane chain, so that on one hand, the oxidation resistance of the polyurethane adhesive is enhanced, and on the other hand, the longer fluorine chains can be intertwined in a polyurethane network, so that the mechanical property of the polyurethane adhesive is improved. The special polyurethane adhesive with excellent ageing resistance and higher mechanical property can be widely applied to industries such as industry, health and leisure, advertising and sports, new energy automobiles, electronic communication, modern transportation, photovoltaic power generation and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an anti-aging polyurethane adhesive and a preparation method and application thereof.
Background
Along with the progress of modernization, people have high requirements on engineering application and high performance requirements on materials, and recently, the development of new materials is increasingly emphasized in our country, and the polyurethane adhesive is a high polymer material containing carbamate groups, and mainly consists of polyether or polyester polyol, isocyanate, small molecular chain extender and other raw materials, and is generally divided into a single-component polyurethane adhesive and a double-component polyurethane adhesive, so that the polyurethane adhesive has excellent mechanical properties, good adhesive force and low temperature resistance, and has wide application in a plurality of fields.
The invention effectively improves the cross-linking between thermoplastic polyurethane elastomer molecules and improves the impact resistance and ageing resistance of the thermoplastic polyurethane elastomer by grafting hindered phenol in the polyurethane prepolymer and modifying the toughening agent, but more polar groups in the polyurethane are still easy to absorb water and hydrolyze under a damp and hot environment, and the damp and hot oxidation resistance of the thermoplastic polyurethane elastomer is still required to be further improved. Therefore, how to develop a novel special polyurethane adhesive resistant to humid heat aging is a technical problem to be solved.
Disclosure of Invention
In view of the above, the invention aims to provide an anti-aging polyurethane adhesive, and a preparation method and application thereof, so as to solve the problem of poor wet heat aging resistance of the polyurethane adhesive.
Based on the purposes, the invention provides an anti-aging polyurethane adhesive, which comprises the following components in parts by weight: 80-100 parts of polycarbonate polyurethane prepolymer, 2-5 parts of catalyst and 15-20 parts of organic solvent. The polycarbonate polyurethane prepolymer comprises the following raw materials in parts by weight: 50-70 parts of polycarbonate diol, 10-20 parts of fluorine chain-containing hindered phenol diol, 3-5 parts of triol and 15-22 parts of benzene-containing diisocyanate.
The preparation method of the fluorine chain-containing hindered phenol dihydric alcohol comprises the following steps:
s1: adding tromethamine and Triethylamine (TEA) into Dichloromethane (DCM), uniformly mixing, adding perfluorooctanoyl chloride at 0-5 ℃, stirring for reaction for 12-18h, washing and distilling under reduced pressure after the reaction is finished to obtain tromethamine containing fluorine chains;
s2: adding 3, 5-di-tert-butyl-4-hydroxybenzoic acid and tromethamine containing fluorine chain into dichloromethane, stirring and dissolving, adding Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP), stirring and reacting for 10-15h at room temperature, washing and distilling under reduced pressure after the reaction is finished to obtain the hindered phenol dihydric alcohol containing fluorine chain.
Preferably, the catalyst is dibutyltin dilaurate or stannous octoate.
Preferably, the organic solvent is acetone or ethyl acetate.
Preferably, the molecular weight of the polycarbonate diol is 1500-2500.
Preferably, the triol is trimethylolpropane.
Preferably, the benzene-containing diisocyanate is diphenylmethane diisocyanate or toluene diisocyanate.
Preferably, in the step S1, the weight ratio of the tromethamine, the triethylamine, the dichloromethane and the perfluorooctanoyl chloride is 3-6:2.8-6:10-25:11.5-22.5.
Preferably, in the step S2, the weight ratio of the 3, 5-di-tert-butyl-4-hydroxybenzoic acid, the fluorine-containing chain tromethamine, the methylene dichloride, the dicyclohexylcarbodiimide and the 4-dimethylaminopyridine is 5-10:11-22:20-40:4.2-8.5:0.6-1.
Further, the invention also provides a preparation method of the anti-aging polyurethane adhesive, which comprises the following specific preparation steps:
(1) Respectively placing polycarbonate dihydric alcohol, fluorine chain-containing hindered phenol dihydric alcohol and trihydric alcohol into a vacuum drying oven, and dehydrating and drying at 85-90 ℃ for 3-4 h for later use;
(2) Adding the polycarbonate diol, the fluorine chain-containing hindered phenol diol and the triol which are treated in the step (1) into a reaction kettle in a nitrogen atmosphere, and stirring and reacting for 1-3h at 75-85 ℃ to obtain a polycarbonate polyurethane prepolymer;
(3) And (3) adding a catalyst and an organic solvent into the polycarbonate polyurethane prepolymer prepared in the step (2) under the nitrogen atmosphere, and stirring for 15-30min at room temperature to obtain the anti-aging polyurethane adhesive.
Furthermore, the anti-aging polyurethane adhesive provided by the invention is mainly applied to the adhesion of engineering plastics and composite materials thereof.
The invention has the beneficial effects that:
the invention provides an anti-aging polyurethane adhesive which consists of a polycarbonate polyurethane prepolymer, a catalyst and an organic solvent. The polycarbonate polyurethane prepolymer consists of polycarbonate diol, fluorine chain-containing hindered phenol diol, triol and benzene-containing diisocyanate. Among other things, the use of polycarbonate diols helps to increase the strength and stability of the polyurethane adhesive.
The invention innovatively synthesizes the fluorine-chain-containing hindered phenol dihydric alcohol, and introduces the fluorine-chain-containing hindered phenol dihydric alcohol into the polyurethane chain, so that the polyurethane thermal oxidation reaction can be effectively inhibited, the aging process of the adhesive is delayed, the polyurethane has certain hydrophobicity due to the fluorine chain, the aging resistance of the polyurethane adhesive in a damp-heat environment is obviously improved, and the fluorine chain has a certain improvement effect on the mechanical property of the polyurethane adhesive.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or of the prior art, the drawings used in the description of the embodiments or of the prior art will be briefly described,
FIG. 1 is a schematic diagram of the synthesis scheme of a fluorine chain-containing hindered phenol diol of example 2 of the present invention.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1: the preparation method of the anti-aging polyurethane adhesive comprises the following specific preparation steps:
(1) Adding 3g of tromethamine and 2.8g of triethylamine into 10g of dichloromethane, uniformly mixing, adding 11.5g of perfluorooctanoyl chloride at 0 ℃, stirring for reacting for 12 hours, washing and distilling under reduced pressure after the reaction is finished to obtain the tromethamine containing fluorine chains;
(2) 5g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 11g of tromethamine containing fluorine chains are added into 20g of methylene dichloride, after stirring and dissolving, 4.2g of dicyclohexylcarbodiimide and 0.6g of 4-dimethylaminopyridine are added, and then stirring and reacting for 10 hours at room temperature, after the reaction is finished, washing and reduced pressure distillation are carried out, thus obtaining the hindered phenol dihydric alcohol containing fluorine chains;
(3) Respectively placing the polycarbonate diol with molecular weight of 1500, the hindered phenol diol with fluorine chain and the trimethylolpropane into a vacuum drying oven, and dehydrating and drying the materials at 85 ℃ for 3h for later use;
(4) Under the nitrogen atmosphere, 50g of polycarbonate diol with molecular weight of 1500, 10g of hindered phenol diol with fluorine chain, 3g of trimethylolpropane and 15g of diphenylmethane diisocyanate which are treated in the step (3) are added into a reaction kettle and stirred and reacted for 1h at 75 ℃ to obtain polycarbonate polyurethane prepolymer;
(5) 2g of dibutyltin dilaurate and 15g of ethyl acetate were added to 80g of the polycarbonate polyurethane prepolymer prepared in the step (4) under a nitrogen atmosphere, and the mixture was stirred at room temperature for 15min to obtain an anti-aging polyurethane adhesive.
Example 2: the preparation method of the anti-aging polyurethane adhesive comprises the following specific preparation steps:
(1) Adding 4.5g of tromethamine and 4.6g of triethylamine into 18g of dichloromethane, uniformly mixing, adding 17g of perfluorooctanoyl chloride at 3 ℃, stirring for reaction for 15 hours, washing and distilling under reduced pressure after the reaction is finished to obtain the tromethamine containing fluorine chains;
(2) Adding 7.5g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 16.5g of tromethamine containing fluorine chains into 30g of dichloromethane, stirring and dissolving, adding 6.4g of dicyclohexylcarbodiimide and 0.8g of 4-dimethylaminopyridine, stirring and reacting at room temperature for 13 hours, washing and distilling under reduced pressure after the reaction is finished to obtain hindered phenol dihydric alcohol containing fluorine chains;
(3) Respectively placing the polycarbonate diol with the molecular weight of 2000, the hindered phenol diol with fluorine chain and the trimethylolpropane into a vacuum drying oven, and dehydrating and drying the materials at 90 ℃ for 4 h for later use;
(4) Under the nitrogen atmosphere, 60g of polycarbonate diol with the molecular weight of 2000, 15g of hindered phenol diol with fluorine chains, 4g of trimethylolpropane and 18g of diphenylmethane diisocyanate which are treated in the step (3) are added into a reaction kettle and stirred and reacted for 2 hours at the temperature of 80 ℃ to obtain a polycarbonate type polyurethane prepolymer;
(5) 3.5g of dibutyltin dilaurate and 17.5g of ethyl acetate were added to 90g of the polycarbonate type polyurethane prepolymer prepared in the step (4) under a nitrogen atmosphere, and stirred at room temperature for 22min to obtain an anti-aging polyurethane adhesive.
Example 3: the preparation method of the anti-aging polyurethane adhesive comprises the following specific preparation steps:
(1) Adding 6g of tromethamine and 6g of triethylamine into 25g of dichloromethane, uniformly mixing, adding 22.5g of perfluorooctanoyl chloride at 5 ℃, stirring for reaction for 18 hours, washing and distilling under reduced pressure after the reaction is finished to obtain the tromethamine containing fluorine chains;
(2) 10g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 22g of tromethamine containing fluorine chains are added into 40g of methylene dichloride, 8.5g of dicyclohexylcarbodiimide and 1g of 4-dimethylaminopyridine are added after stirring and dissolution, stirring reaction is carried out at room temperature for 15 hours, after the reaction is finished, washing and reduced pressure distillation are carried out, and thus the hindered phenol dihydric alcohol containing fluorine chains is obtained;
(3) Respectively placing the polycarbonate diol with the molecular weight of 2500, the hindered phenol diol with fluorine chain and the trimethylolpropane into a vacuum drying oven, and carrying out dehydration drying treatment at 90 ℃ for 4 h for later use;
(4) Under the nitrogen atmosphere, 70g of polycarbonate diol with the molecular weight of 2500, 20g of hindered phenol diol with fluorine chains, 5g of trimethylolpropane and 22g of diphenylmethane diisocyanate which are treated in the step (3) are added into a reaction kettle and stirred and reacted for 3 hours at the temperature of 85 ℃ to obtain a polycarbonate type polyurethane prepolymer;
(5) 5g of dibutyltin dilaurate and 20g of ethyl acetate were added to 100g of the polycarbonate polyurethane prepolymer prepared in the step (4) under a nitrogen atmosphere, and stirred at room temperature for 30min to obtain an anti-aging polyurethane adhesive.
Comparative example 1: a preparation method of polyurethane adhesive comprises the following specific preparation steps:
(1) Adding 7.5g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 4.1g of trimethylolpropane into 30g of dichloromethane, stirring and dissolving, adding 6.4g of dicyclohexylcarbodiimide and 0.8g of 4-dimethylaminopyridine, stirring and reacting for 13h at room temperature, washing and distilling under reduced pressure after the reaction is finished to obtain hindered phenol dihydric alcohol;
(2) Respectively placing polycarbonate diol with the molecular weight of 2000, hindered phenol diol and trimethylolpropane into a vacuum drying oven, and dehydrating and drying at 90 ℃ for 4 h for later use;
(3) Under the nitrogen atmosphere, 60g of polycarbonate diol with the molecular weight of 2000, 7.3g of hindered phenol diol, 4g of trimethylolpropane and 18g of diphenylmethane diisocyanate which are treated in the step (2) are added into a reaction kettle and stirred and reacted for 2 hours at 80 ℃ to obtain polycarbonate polyurethane prepolymer;
(4) Adding 3.5g of dibutyltin dilaurate and 17.5g of ethyl acetate into 90g of the polycarbonate type polyurethane prepolymer prepared in the step (3) under the nitrogen atmosphere, and stirring for 22min at room temperature to obtain a polyurethane adhesive;
the main difference between comparative example 1 and example 2 is that: the hindered phenol diol is used for replacing the fluorine-containing chain.
Comparative example 2: a preparation method of polyurethane adhesive comprises the following specific preparation steps:
(1) Adding 4.5g of tromethamine and 4.6g of triethylamine into 18g of dichloromethane, uniformly mixing, adding 17g of perfluorooctanoyl chloride at 3 ℃, stirring for reaction for 15 hours, washing and distilling under reduced pressure after the reaction is finished to obtain the tromethamine containing fluorine chains;
(2) Adding 7.5g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 16.5g of tromethamine containing fluorine chains into 30g of dichloromethane, stirring and dissolving, adding 6.4g of dicyclohexylcarbodiimide and 0.8g of 4-dimethylaminopyridine, stirring and reacting at room temperature for 13 hours, washing and distilling under reduced pressure after the reaction is finished to obtain hindered phenol dihydric alcohol containing fluorine chains;
(3) Respectively placing polyether glycol PPG210 with molecular weight of 2000, hindered phenol glycol with fluorine chain and trimethylolpropane into a vacuum drying oven, and dehydrating and drying at 90 ℃ for 4 h for later use;
(4) Under the nitrogen atmosphere, 60g of polyether glycol PPG210 with the molecular weight of 2000, 15g of hindered phenol glycol with fluorine chains, 4g of trimethylolpropane and 18g of diphenylmethane diisocyanate which are treated in the step (3) are added into a reaction kettle and stirred at 80 ℃ for 2 hours to obtain polyurethane prepolymer;
(5) Adding 3.5g of dibutyltin dilaurate and 17.5g of ethyl acetate into 90g of the polyurethane prepolymer prepared in the step (4) under the nitrogen atmosphere, and stirring for 22min at room temperature to obtain a polyurethane adhesive;
the main difference between comparative example 2 and example 2 is that: a polyether glycol PPG210 having a molecular weight of 2000 was used instead of a polycarbonate glycol having a molecular weight of 2000.
Comparative example 3: a preparation method of polyurethane adhesive comprises the following specific preparation steps:
(1) Adding 7.5g of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 4.1g of trimethylolpropane into 30g of dichloromethane, stirring and dissolving, adding 6.4g of dicyclohexylcarbodiimide and 0.8g of 4-dimethylaminopyridine, stirring and reacting for 13h at room temperature, washing and distilling under reduced pressure after the reaction is finished to obtain hindered phenol dihydric alcohol;
(2) Respectively placing polyether glycol PPG210 with molecular weight of 2000, hindered phenol glycol and trimethylolpropane into a vacuum drying oven, and dehydrating and drying at 90 ℃ for 4 h for later use;
(3) Under the nitrogen atmosphere, 60g of polyether glycol PPG210 with the molecular weight of 2000, 7.3g of hindered phenol glycol, 4g of trimethylolpropane and 18g of diphenylmethane diisocyanate which are treated in the step (2) are added into a reaction kettle and stirred and reacted for 2 hours at 80 ℃ to obtain polyurethane prepolymer;
(4) Adding 3.5g of dibutyltin dilaurate and 17.5g of ethyl acetate into 90g of the polyurethane prepolymer prepared in the step (3) under the nitrogen atmosphere, and stirring for 22min at room temperature to obtain a polyurethane adhesive;
the main difference between comparative example 3 and example 2 is that: a hindered phenol diol was used instead of a hindered phenol diol having a fluorine-containing chain, and a polyether diol PPG210 having a molecular weight of 2000 was used instead of a polycarbonate diol having a molecular weight of 2000.
Performance testing
Thermal oxidation performance: the anti-aging polyurethane adhesive bars prepared in the examples and the comparative examples are placed in a dry hot air aging oven at 100 ℃, the bars are uniformly spaced by 5cm, and an aging test is performed for 12 weeks;
wet heat oxidation performance: the anti-aging polyurethane adhesive bars prepared in the examples and the comparative examples are placed in a humid heat aging box with the temperature of 80 ℃ and the relative humidity of 90%, the distance between the bars is kept to be 5cm, and an aging test is carried out for 18 weeks;
tensile strength: the anti-aging polyurethane adhesives prepared in examples and comparative examples were subjected to a tensile test according to GB/T528-2009 at a tensile speed of 500mm/min for 5 times, and the average value was taken, and the test results are shown in Table one.
Data analysis: according to the embodiment 1-3, the anti-aging polyurethane adhesive provided by the invention has small reduction of tensile property after thermal oxidation treatment and wet thermal oxidation treatment, which proves that the anti-aging polyurethane adhesive provided by the invention has excellent anti-aging property.
As can be seen from example 2 and comparative example 1, the introduction of the fluorine chain has a significant improvement on the wet heat aging resistance and mechanical properties of the polyurethane adhesive, and the improvement on the aging resistance is mainly due to the fact that the fluorine chain improves the water resistance of the polyurethane, and a hydrophobic barrier is formed between the polyurethane and moisture; the improvement of the mechanical properties is probably due to the fact that longer fluorine chains can be intertwined in the polyurethane network, the cohesive energy and the crosslinking density of the polyurethane adhesive are improved, and the mechanical properties are further improved.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention (including the claims) is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (10)
1. An anti-aging polyurethane adhesive is characterized by comprising the following raw materials in parts by weight: 80-100 parts of polycarbonate polyurethane prepolymer, 2-5 parts of catalyst and 15-20 parts of organic solvent; the polycarbonate polyurethane prepolymer comprises the following raw materials in parts by weight: 50-70 parts of polycarbonate diol, 10-20 parts of fluorine chain-containing hindered phenol diol, 3-5 parts of triol and 15-22 parts of benzene-containing diisocyanate;
the preparation method of the fluorine chain-containing hindered phenol dihydric alcohol comprises the following steps:
s1: adding tromethamine and triethylamine into dichloromethane, uniformly mixing, adding perfluorooctanoyl chloride at 0-5 ℃, stirring for reaction for 12-18h, washing after the reaction is finished, and distilling under reduced pressure to obtain tromethamine containing fluorine chains;
s2: adding 3, 5-di-tert-butyl-4-hydroxybenzoic acid and tromethamine containing fluorine chain into dichloromethane, stirring and dissolving, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stirring and reacting at room temperature for 10-15h, washing and distilling under reduced pressure after the reaction is finished, and obtaining the hindered phenol dihydric alcohol containing fluorine chain.
2. The anti-aging polyurethane adhesive of claim 1, wherein the catalyst is dibutyltin dilaurate or stannous octoate.
3. The anti-aging polyurethane adhesive of claim 1, wherein the organic solvent is acetone or ethyl acetate.
4. The anti-aging polyurethane adhesive of claim 1, wherein the molecular weight of the polycarbonate diol is 1500-2500.
5. The anti-aging polyurethane adhesive of claim 1, wherein the triol is trimethylolpropane.
6. The anti-aging polyurethane adhesive of claim 1, wherein the benzene-containing diisocyanate is diphenylmethane diisocyanate or toluene diisocyanate.
7. The anti-aging polyurethane adhesive according to claim 1, wherein the weight ratio of tromethamine, triethylamine, dichloromethane and perfluorooctanoyl chloride in the step S1 is 3-6:2.8-6:10-25:11.5-22.5.
8. The anti-aging polyurethane adhesive according to claim 1, wherein the weight ratio of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, fluorine-containing tromethamine, methylene chloride, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in step S2 is 5-10:11-22:20-40:4.2-8.5:0.6-1.
9. A process for preparing an anti-aging polyurethane adhesive according to any one of claims 1 to 8, comprising the steps of:
(1) Respectively placing polycarbonate dihydric alcohol, fluorine chain-containing hindered phenol dihydric alcohol and trihydric alcohol into a vacuum drying oven, and dehydrating and drying at 85-90 ℃ for 3-4 h for later use;
(2) Adding the polycarbonate diol, the fluorine chain-containing hindered phenol diol, the triol and the benzene-containing diisocyanate which are treated in the step (1) into a reaction kettle in a nitrogen atmosphere, and stirring and reacting for 1-3 hours at 75-85 ℃ to obtain a polycarbonate polyurethane prepolymer;
(3) And (3) adding a catalyst and an organic solvent into the polycarbonate polyurethane prepolymer prepared in the step (2) under the nitrogen atmosphere, and stirring for 15-30min at room temperature to obtain the anti-aging polyurethane adhesive.
10. Use of an anti-aging polyurethane adhesive according to any one of claims 1 to 8 for the bonding of engineering plastics and composites thereof.
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