CN117757406A - Preparation process of two-component polyurethane adhesive - Google Patents
Preparation process of two-component polyurethane adhesive Download PDFInfo
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- CN117757406A CN117757406A CN202311689306.8A CN202311689306A CN117757406A CN 117757406 A CN117757406 A CN 117757406A CN 202311689306 A CN202311689306 A CN 202311689306A CN 117757406 A CN117757406 A CN 117757406A
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- polyurethane adhesive
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical group C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 26
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 22
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 239000013638 trimer Substances 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- -1 diphenylamino phenolphthalein compound Chemical class 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 14
- 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 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 125000003827 glycol group Chemical group 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 8
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 1
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZMUWFFOQTDNMOB-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid;sodium Chemical compound [Na].OCC(C)(CO)C(O)=O ZMUWFFOQTDNMOB-UHFFFAOYSA-N 0.000 description 1
- YPFUJZAAZJXMIP-UHFFFAOYSA-N 3-sulfopropanediol Chemical compound OCC(O)CS(O)(=O)=O YPFUJZAAZJXMIP-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000008430 aromatic amides Chemical group 0.000 description 1
- 238000005266 casting Methods 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
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane, and discloses a preparation process of a double-component polyurethane adhesive, wherein hydroxyl-terminated polyurethane prepolymer obtained by reacting polyalcohol and toluene diisocyanate, and raw materials such as a water-based chain extender, water, a defoaming agent, amino-terminated polyaramid and the like are used as a polyurethane component A; the polyurethane prepolymer of the end isocyanate obtained by the reaction of the polyol and the toluene diisocyanate trimer is taken as a polyurethane B component, and the water-based double-component polyurethane adhesive is obtained by compounding. The end amino contained in the polyaramid can react with the polyurethane prepolymer of the end isocyanate in the curing process, so that the polyaramid containing the phenolphthalein structure is grafted into a polyurethane molecular chain, the tensile property and the hardness of the aqueous polyurethane adhesive are improved, the thermal decomposition temperature of polyurethane is improved, and the polyurethane adhesive has better thermal stability.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a preparation process of a double-component polyurethane adhesive.
Background
The double-component polyurethane adhesive has good adhesive property, and the faster the curing speed is, the wider application in the adhesive aspect of products such as metal, glass, wood and the like; the water-based polyurethane adhesive takes water as a solvent, which is more environment-friendly, but the water-based polyurethane adhesive has the problems of poor water resistance, low strength, poor heat resistance and the like, and the development of the functional polyurethane adhesive is a research hot spot.
The grafting modification of polyurethane by adopting polymers such as amino polysiloxane, hydroxyl-terminated polybutadiene and hydroxyl-terminated nitrile rubber is an effective method for improving the performance of polyurethane; patent CN 112961641B discloses that grafting PVC to polyurethane segments can increase the wettability and compatibility of polyurethane adhesives in materials such as shoe materials, leather, etc., and increase the interfacial force formed between the adhesives and the materials, thereby increasing the peel strength; the polyaramid has excellent heat resistance and strength, can be prepared into high-performance fiber and other functional assistants, and has wide application prospects in the aspects of composite films, adhesives and the like.
Disclosure of Invention
The invention solves the technical problems that: provides a preparation process of a double-component polyurethane adhesive, and solves the problems of poor water resistance, low strength, poor heat resistance and the like of the polyurethane adhesive.
The technical scheme provided by the invention is as follows:
a preparation process of a double-component polyurethane adhesive comprises a component A and a component B;
the component A comprises the following components in parts by weight: 100 parts of polyalcohol, 7-9 parts of toluene diisocyanate, 0.1-0.15 part of dibutyl tin dilaurate, 3-5 parts of glycol chain extender, 4-8 parts of aqueous chain extender, 1-20 parts of amino-terminated polyaramid, 3-7 parts of triethylamine, 0.5-1 part of defoamer and 100-300 parts of water;
the component B comprises the following components in parts by weight: 45-55 parts of polyol and 52-65 parts of toluene diisocyanate trimer;
adding polyalcohol into a reaction bottle, vacuumizing, drying and dehydrating at 100-120 ℃, introducing nitrogen, adding toluene diisocyanate and dibutyltin dilaurate into the reaction bottle at 70-80 ℃, and stirring for reacting for 2-3 hours to obtain hydroxyl-terminated polyurethane prepolymer; cooling, adding a glycol chain extender, a water-based chain extender, water, a defoaming agent and amino-terminated polyaramide, emulsifying uniformly, adding triethylamine, and mixing uniformly to obtain a component A;
adding polyalcohol into a reaction bottle, vacuumizing, drying and dehydrating at 100-120 ℃, introducing nitrogen, adding toluene diisocyanate trimer at 65-75 ℃, stirring and reacting for 2-3 hours to obtain isocyanate-terminated polyurethane prepolymer, and cooling to obtain the component B.
Further, the polyol includes polyether polyol, polyethylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, and polycarbonate diol.
Further, the diol chain extender comprises 1, 4-butanediol, N-methyldiethanolamine.
Further, the aqueous chain extender comprises sodium 2, 2-dimethylolpropionic acid, 1, 2-dihydroxy-3-propanesulfonate.
Further, the preparation process of the amino-terminated polyaramid comprises the following steps:
(1) Adding any solvent of ethyl acetate, toluene, xylene or 1, 4-dioxane into a reaction bottle, wherein the ratio of the solvent to the solvent is 1mol (1.8-2.6) mol (0.12-0.16) mol of phenolphthalein, 4-nitrobenzoic acid and p-toluenesulfonic acid, stirring and reacting for 6-18h at 80-100 ℃, rotary evaporating, dissolving the crude product after washing acetone into ethanol, adding a palladium-carbon catalyst, hydrazine hydrate, stirring and refluxing for 3-6h at 65-80 ℃, filtering, rotary evaporating filtrate, washing the acetone, adding the product into a mixed solvent of ethanol and ethyl acetate, and recrystallizing to obtain the diphenylamino phenolphthalein compound.
(2) Adding N-methyl pyrrolidone, 1mol (1.2-1.4) mol (1-1.3) mol (2.1-2.6) mol of diphenylamino phenolphthalein compound, terephthalic acid, triphenyl phosphite and pyridine into a reaction bottle, stirring for reaction, cooling to separate out precipitate, filtering, washing the product with ethanol, and drying to obtain the amino-terminated polyaramid.
Further, the reaction in (2) is carried out at a temperature of 100 to 120℃for 2 to 4 hours.
The invention has the technical effects that:
the invention takes phenolphthalein and 4-nitrobenzoic acid as reaction raw materials, prepares a novel diphenylamino phenolphthalein compound through esterification and reduction reaction, then carries out amidation polymerization reaction with terephthalic acid, and controls the reaction proportion of the two to obtain the amino-terminated polyaramide containing the phenolphthalein structure, wherein the phenolphthalein structure has the advantages of large polarity and high thermal stability.
The invention takes hydroxyl-terminated polyurethane prepolymer obtained by the reaction of polyalcohol and toluene diisocyanate, water-based chain extender, water, defoamer, amino-terminated polyaramide and other raw materials as a polyurethane A component; the polyurethane prepolymer of the end isocyanate obtained by the reaction of the polyol and the toluene diisocyanate trimer is taken as a polyurethane B component, and the water-based double-component polyurethane adhesive is obtained by compounding. The end amino contained in the polyaramid can react with the polyurethane prepolymer of end isocyanate in the curing process, so that the polyaramid containing the phenolphthalein structure is grafted into a polyurethane molecular chain, and the polyaramid containing the phenolphthalein structure has the characteristics of high strength, high thermal decomposition temperature and high water resistance, obviously improves the tensile property and hardness of the aqueous polyurethane adhesive, improves the thermal decomposition temperature of polyurethane, and has better thermal stability.
The polyaramid containing the phenolphthalein structure contains polar phenolphthalein and aromatic amide groups, so that the interaction force and cohesion between polyurethane molecular chains can be improved, and the peel strength and bonding shear strength of polyurethane can be improved.
Detailed Description
The following provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
Preparing amino-terminated polyaramid:
(1) Adding any solvent of ethyl acetate, toluene, dimethylbenzene and 1, 4-dioxane into a reaction bottle, wherein the ratio of the solvent to the solvent is 1mol (1.8-2.6) mol (0.12-0.16) mol of phenolphthalein, 4-nitrobenzoic acid and p-toluenesulfonic acid, stirring and reacting for 6-18 hours at the temperature of 80-100 ℃, rotary evaporating, dissolving the crude product after washing acetone into ethanol, adding a palladium-carbon catalyst, hydrazine hydrate, stirring and refluxing for 3-6 hours at the temperature of 65-80 ℃, filtering, rotary evaporating filtrate, washing the acetone, adding the product into a mixed solvent of ethanol and ethyl acetate, and recrystallizing to obtain the diphenylamino phenolphthalein compound. The reaction route is as follows:
(2) Adding N-methyl pyrrolidone, 1mol (1.2-1.4) mol (1-1.3) mol (2.1-2.6) mol of diphenylamino phenolphthalein compound, terephthalic acid, triphenyl phosphite and pyridine into a reaction bottle, stirring and reacting for 2-4h at the temperature of 100-120 ℃, cooling to separate out precipitate, filtering, washing the product with ethanol, and drying to obtain the amino-terminated polyaramid. The reaction route is as follows:
the double-component polyurethane adhesive comprises a component A and a component B.
The component A comprises the following components in parts by weight: 100 parts of polyalcohol, 7-9 parts of toluene diisocyanate, 0.1-0.15 part of dibutyl tin dilaurate, 3-5 parts of any one glycol chain extender of 1, 4-butanediol or N-methyldiethanolamine, 4-8 parts of any one water-based chain extender of 2, 2-dimethylolpropionic acid or 1, 2-dihydroxyl-3-sodium propane sulfonate, 1-20 parts of amino-terminated polyaramid, 3-7 parts of triethylamine, 0.5-1 part of defoamer and 100-300 parts of water;
adding polyalcohol into a reaction bottle, vacuumizing, drying and dehydrating at 100-120 ℃, introducing nitrogen, adding toluene diisocyanate and dibutyltin dilaurate into the reaction bottle at 70-80 ℃, and stirring for reacting for 2-3 hours to obtain hydroxyl-terminated polyurethane prepolymer; cooling, adding a glycol chain extender, a water-based chain extender, water, a defoaming agent and amino-terminated polyaramide, emulsifying uniformly, adding triethylamine, and mixing uniformly to obtain a component A;
the component B comprises the following components in parts by weight: 45-55 parts of polyol and 52-65 parts of toluene diisocyanate trimer; adding polyalcohol into a reaction bottle, vacuumizing, drying and dehydrating at 100-120 ℃, introducing nitrogen, adding toluene diisocyanate trimer at 65-75 ℃, stirring and reacting for 2-3 hours to obtain isocyanate-terminated polyurethane prepolymer, and cooling to obtain the component B.
The polyols in the component A and the component B comprise polyether polyol, polyethylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol and polycarbonate diol.
Example 1
(1) 300mL of 1, 4-dioxane, 40mmol of phenolphthalein, 104mmol of 4-nitrobenzoic acid and 6.4 mmol of p-toluenesulfonic acid are added into a reaction bottle, stirring reflux reaction is carried out at 100 ℃ for 6h, rotary evaporation is carried out, the crude product after washing by acetone is dissolved into 400mL of ethanol, 1.4g of palladium-carbon catalyst is added, 12mL of hydrazine hydrate is stirred reflux is carried out at 65 ℃ for 6h, filtration is carried out, rotary evaporation of filtrate is carried out, acetone washing is carried out, and the product is added into a mixed solvent of ethanol and ethyl acetate for recrystallization, thus obtaining the diphenylamino phenolphthalein compound.
(2) 300mL of N-methylpyrrolidone, 60mmol of the diphenylamino phenolphthalein compound, 50mmol of terephthalic acid, 50mmol of triphenyl phosphite and 110mmol of pyridine are added into a reaction bottle, stirred at a temperature of 110 ℃ for reaction for 3 hours, cooled to separate out precipitate, filtered, the product is washed by ethanol, and dried to obtain the amino-terminated polyaramid.
The double-component polyurethane adhesive consists of a component A and a component B:
200g of polycarbonate diol PCDL-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 120 ℃, nitrogen is introduced, 14g of toluene diisocyanate and 0.2g of dibutyltin dilaurate are added into the reaction bottle at 70 ℃, and stirring reaction is carried out for 3 hours, thus obtaining hydroxyl-terminated polyurethane prepolymer; cooling, adding 6g of 1, 4-butanediol, 10g of 2, 2-dimethylolpropionic acid, 300g of water, 1g of defoamer and 2g of amino-terminated polyaramid, emulsifying uniformly, adding 11g of triethylamine, and mixing uniformly to obtain a component A;
the component B comprises the following components in parts by weight: toluene diisocyanate trimer; 95g of polycarbonate diol PCDL-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 120 ℃, nitrogen is introduced, 118g of toluene diisocyanate trimer is added at 75 ℃, stirring reaction is carried out for 2 hours, thus obtaining isocyanate-terminated polyurethane prepolymer, and the component B is obtained after cooling.
Example 2
(1) 200mL of toluene solvent, 40mmol of phenolphthalein, 72mmol of 4-nitrobenzoic acid and 4.8 mmol of p-toluenesulfonic acid are added into a reaction bottle, stirring reflux reaction is carried out for 12h at 100 ℃, rotary evaporation is carried out, the crude product is dissolved into 400mL of ethanol after acetone washing, 1.4g of palladium-carbon catalyst is added, 15mL of hydrazine hydrate is added, stirring reflux is carried out for 4h at 80 ℃, filtration is carried out, rotary evaporation of filtrate is carried out, acetone washing is carried out, and the product is added into a mixed solvent of ethanol and ethyl acetate for recrystallization, thus obtaining the diphenylamino phenolphthalein compound.
(2) 400mL of N-methylpyrrolidone, 64mmol of the diphenylamino phenolphthalein compound, 50mmol of terephthalic acid, 55mmol of triphenyl phosphite and 120mmol of pyridine are added into a reaction bottle, stirred at 120 ℃ for reaction for 3 hours, cooled to separate out precipitate, filtered, the product is washed with ethanol, and dried to obtain the amino-terminated polyaramid.
The double-component polyurethane adhesive consists of a component A and a component B:
adding 200g of polycaprolactone diol PCL-1000 into a reaction bottle, vacuumizing, drying and dehydrating at 110 ℃, introducing nitrogen, adding 16g of toluene diisocyanate and 0.25g of dibutyltin dilaurate into the reaction bottle at 80 ℃, and stirring for reacting for 2 hours to obtain a hydroxyl-terminated polyurethane prepolymer; cooling, adding 8.5g of N-methyldiethanolamine, 12g of 2, 2-dimethylolpropionic acid, 500g of water, 2g of defoamer and 8g of amino-terminated polyaramid, emulsifying uniformly, adding 10g of triethylamine, and mixing uniformly to obtain a component A;
the component B comprises the following components in parts by weight: toluene diisocyanate trimer; 98g of polycaprolactone diol PCL-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 110 ℃, nitrogen is introduced, 130g of toluene diisocyanate trimer is added at 75 ℃, stirring reaction is carried out for 3 hours, and the isocyanate-terminated polyurethane prepolymer is obtained, and cooling is carried out, thus obtaining the component B.
Example 3
(1) 250mL of xylene solvent, 40mmol of phenolphthalein, 96mmol of 4-nitrobenzoic acid and 5.8 mmol of p-toluenesulfonic acid are added into a reaction bottle, stirring is carried out for reaction for 12h at 100 ℃, rotary evaporation is carried out, the crude product is dissolved into 400mL of ethanol after acetone washing, 1.5g of palladium-carbon catalyst is added, 12mL of hydrazine hydrate is added, stirring and refluxing are carried out for 4h at 70 ℃, filtering is carried out, rotary evaporation of filtrate is carried out, acetone washing is carried out, and the product is added into a mixed solvent of ethanol and ethyl acetate for recrystallization, thus obtaining the diphenylamino phenolphthalein compound.
(2) 400mL of N-methylpyrrolidone, 64mmol of the diphenylamino phenolphthalein compound, 50mmol of terephthalic acid, 50mmol of triphenyl phosphite and 120mmol of pyridine are added into a reaction bottle, stirred at the temperature of 120 ℃ for reaction for 2 hours, cooled to separate out precipitate, filtered, the product is washed by ethanol, and dried to obtain the amino-terminated polyaramid.
The double-component polyurethane adhesive consists of a component A and a component B:
adding 200g of polytetrahydrofuran ether glycol PTMEG-1000 into a reaction bottle, vacuumizing, drying and dehydrating at 110 ℃, introducing nitrogen, adding 18g of toluene diisocyanate and 0.3g of dibutyltin dilaurate into the reaction bottle at 75 ℃, and stirring for reacting for 2 hours to obtain a hydroxyl-terminated polyurethane prepolymer; cooling, adding 7.2g of 1, 4-butanediol, 16g of 1, 2-dihydroxy-3-propane sodium sulfonate, 500g of water, 1g of defoamer and 14g of amino-terminated polyaramid, emulsifying uniformly, adding 14g of triethylamine, and mixing uniformly to obtain a component A;
the component B comprises the following components in parts by weight: toluene diisocyanate trimer; 105g of polytetrahydrofuran ether glycol PTMEG-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 110 ℃, nitrogen is introduced, 104g of toluene diisocyanate trimer is added at 70 ℃, stirring reaction is carried out for 3 hours, thus obtaining isocyanate-terminated polyurethane prepolymer, and the component B is obtained after cooling.
Example 4
(1) 300mL of ethyl acetate solvent, 40mmol of phenolphthalein, 96mmol of 4-nitrobenzoic acid and 6.4 mmol of p-toluenesulfonic acid are added into a reaction bottle, stirring reflux reaction is carried out for 18h at 80 ℃, rotary evaporation is carried out, the crude product is dissolved into 400mL of ethanol after acetone washing, 1.4g of palladium-carbon catalyst is added, 15mL of hydrazine hydrate is added, stirring reflux is carried out for 3h at 70 ℃, filtration is carried out, rotary evaporation of filtrate is carried out, acetone washing is carried out, and the product is added into a mixed solvent of ethanol and ethyl acetate for recrystallization, thus obtaining the diphenylamino phenolphthalein compound.
(2) 500mL of N-methylpyrrolidone, 70mmol of the diphenylamino phenolphthalein compound, 50mmol of terephthalic acid, 60mmol of triphenyl phosphite and 130mmol of pyridine are added into a reaction bottle, stirred at a temperature of 100 ℃ for reaction for 4 hours, cooled to separate out precipitate, filtered, the product is washed with ethanol, and dried to obtain the amino-terminated polyaramid.
The double-component polyurethane adhesive consists of a component A and a component B:
200g of polyethylene glycol-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 100 ℃, nitrogen is introduced, 15.6g of toluene diisocyanate and 0.26g of dibutyltin dilaurate are added into the reaction bottle at 75 ℃, and stirring reaction is carried out for 2 hours, thus obtaining hydroxyl-terminated polyurethane prepolymer; cooling, adding 7.2g of 1, 4-butanediol, 12g of 2, 2-dimethylolpropionic acid, 400g of water, 1.5g of defoamer and 20g of amino-terminated polyaramid, emulsifying uniformly, adding 14g of triethylamine, and mixing uniformly to obtain a component A;
the component B comprises the following components in parts by weight: toluene diisocyanate trimer; 90g of polyethylene glycol-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 100 ℃, nitrogen is introduced, 104g of toluene diisocyanate trimer is added at 75 ℃, stirring reaction is carried out for 2 hours, thus obtaining isocyanate-terminated polyurethane prepolymer, and the component B is obtained after cooling.
Comparative example 1
This comparative example differs from example 1 in that no amino-terminated polyaramid is added to the A-component
The double-component polyurethane adhesive consists of a component A and a component B:
200g of polycarbonate diol PCDL-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 120 ℃, nitrogen is introduced, 14g of toluene diisocyanate and 0.2g of dibutyltin dilaurate are added into the reaction bottle at 70 ℃, and stirring reaction is carried out for 3 hours, thus obtaining hydroxyl-terminated polyurethane prepolymer; cooling, adding 6g of 1, 4-butanediol, 10g of 2, 2-dimethylolpropionic acid, 300g of water and 1g of defoamer, emulsifying uniformly, adding 11g of triethylamine, and mixing uniformly to obtain a component A;
the component B comprises the following components in parts by weight: toluene diisocyanate trimer; 95g of polycarbonate diol PCDL-1000 is added into a reaction bottle, vacuum drying and dehydration are carried out at 120 ℃, nitrogen is introduced, 118g of toluene diisocyanate trimer is added at 75 ℃, stirring reaction is carried out for 2 hours, thus obtaining isocyanate-terminated polyurethane prepolymer, and the component B is obtained after cooling.
And uniformly mixing the component A and the component B, coating on the surface of a steel plate, curing for 5 hours at 60 ℃, curing for 7 days at room temperature, and testing the shear strength according to the method of GB/T7124-2008. Peel strength was measured according to GB/T7122-1996 method.
And (3) uniformly mixing the component A and the component B, pouring the mixture into a mold for casting and molding, curing at 60 ℃ for 5 hours, and curing at room temperature for 7 days to obtain a polyurethane adhesive cured product. Shore hardness was tested according to GB/T531.1-2008. Tensile properties were tested according to the method of GB/T528-2009.
Water absorption test of polyurethane adhesive cured product: weighing a certain massQuantity M 0 The cured product was immersed in water for 48 hours, and then the cured product was taken out, wiped with water, weighed for M, and the water absorption was calculated.
Water absorption= (M-M) 0 )/M 0 ×100％。
The thermal performance of the polyurethane adhesive cured product is tested by adopting a thermogravimetric analyzer, and the temperature is 25-800 ℃ and the nitrogen atmosphere.
| Initial decomposition temperature (. Degree. C.) | Carbon residue (%) | |
| Example 1 | 324.1 | 9.6 |
| Example 2 | 330.5 | 12.1 |
| Example 3 | 333.9 | 14.8 |
| Example 4 | 328.6 | 16.9 |
| Comparative example 1 | 306.8 | 7.1 |
The initial decomposition temperature is the temperature at which the mass loss is 5%. The carbon residue was the mass remaining rate at 800 ℃.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (9)
1. The preparation process of the two-component polyurethane adhesive is characterized in that the two-component polyurethane adhesive comprises a component A and a component B;
the component A comprises the following components in parts by weight: 100 parts of polyalcohol, 7-9 parts of toluene diisocyanate, 0.1-0.15 part of dibutyl tin dilaurate, 3-5 parts of glycol chain extender, 4-8 parts of aqueous chain extender, 1-20 parts of amino-terminated polyaramid, 3-7 parts of triethylamine, 0.5-1 part of defoamer and 100-300 parts of water;
the component B comprises the following components in parts by weight: 45-55 parts of polyol and 52-65 parts of toluene diisocyanate trimer;
the preparation process of the polyurethane adhesive comprises the following steps:
adding polyalcohol into a reaction bottle, vacuumizing, drying, dehydrating, introducing nitrogen, adding toluene diisocyanate and dibutyltin dilaurate into the reaction bottle at 70-80 ℃, and stirring for reaction to obtain hydroxyl-terminated polyurethane prepolymer; cooling, adding a glycol chain extender, a water-based chain extender, water, a defoaming agent and amino-terminated polyaramide, emulsifying uniformly, adding triethylamine, and mixing uniformly to obtain a component A;
adding polyol into a reaction bottle, vacuumizing, drying, dehydrating, introducing nitrogen, adding toluene diisocyanate trimer into the reaction bottle at 65-75 ℃, stirring for reaction to obtain isocyanate-terminated polyurethane prepolymer, and cooling to obtain the component B.
2. The process for preparing a two-component polyurethane adhesive according to claim 1, wherein the polyol comprises polyether polyol, polyethylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, and polycarbonate diol.
3. The process for preparing a two-component polyurethane adhesive according to claim 1, wherein the diol chain extender comprises 1, 4-butanediol, N-methyldiethanolamine.
4. The process for preparing a two-component polyurethane adhesive according to claim 1, wherein the aqueous chain extender comprises 2, 2-dimethylolpropionic acid, sodium 1, 2-dihydroxy-3-propane sulfonate.
5. The process for preparing the two-component polyurethane adhesive according to claim 1, wherein the process for preparing the amino-terminated polyaramid is as follows:
(1) Adding solvent, phenolphthalein, 4-nitrobenzoic acid and p-toluenesulfonic acid into a reaction bottle, stirring at 80-100 ℃ for reaction for 6-18 hours, rotary evaporating, dissolving the crude product into ethanol after washing by acetone, adding palladium-carbon catalyst and hydrazine hydrate, stirring at 65-80 ℃ for reflux for 3-6 hours, filtering, rotary evaporating filtrate, washing by acetone, adding the product into a mixed solvent of ethanol and ethyl acetate, and recrystallizing to obtain the diphenylamino phenolphthalein compound;
(2) Adding N-methyl pyrrolidone, diphenylamino phenolphthalein compound, terephthalic acid, triphenyl phosphite and pyridine into a reaction bottle, stirring for reaction, cooling to separate out precipitate, filtering, washing the product with ethanol, and drying to obtain the amino-terminated polyaramid.
6. The process for preparing a two-component polyurethane adhesive according to claim 1, wherein the solvent in (1) comprises ethyl acetate, toluene, xylene, 1, 4-dioxane.
7. The preparation process of the two-component polyurethane adhesive according to claim 1, wherein the proportion of phenolphthalein, 4-nitrobenzoic acid and p-toluenesulfonic acid in the component (1) is 1mol (1.8-2.6 mol) and 0.12-0.16 mol.
8. The process for preparing a two-component polyurethane adhesive according to claim 1, wherein the proportion of the diphenylamino phenolphthalein compound, terephthalic acid, triphenyl phosphite and pyridine in (2) is (1.2-1.4) 1mol (1-1.3) 2.1-2.6 mol.
9. The process for preparing a two-component polyurethane adhesive according to claim 1, wherein the reaction in (2) is carried out at a temperature of 100 to 120 ℃ for 2 to 4 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61148222A (en) * | 1984-12-20 | 1986-07-05 | Toyobo Co Ltd | Production of polyurethane resin |
| CN103254451A (en) * | 2013-05-17 | 2013-08-21 | 合肥工业大学 | Preparation method of phenolphthalein allyl amine-type benzoxazine/polyurethane blend resin |
| CN104130410A (en) * | 2014-07-21 | 2014-11-05 | 中国科学院宁波材料技术与工程研究所 | Phenolphthalein copolyimide and preparation method thereof |
| CN116462805A (en) * | 2023-05-29 | 2023-07-21 | 山西利根定信息科技有限公司 | Preparation method and application of water-resistant impact-resistant waterborne polyurethane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61148222A (en) * | 1984-12-20 | 1986-07-05 | Toyobo Co Ltd | Production of polyurethane resin |
| CN103254451A (en) * | 2013-05-17 | 2013-08-21 | 合肥工业大学 | Preparation method of phenolphthalein allyl amine-type benzoxazine/polyurethane blend resin |
| CN104130410A (en) * | 2014-07-21 | 2014-11-05 | 中国科学院宁波材料技术与工程研究所 | Phenolphthalein copolyimide and preparation method thereof |
| CN116462805A (en) * | 2023-05-29 | 2023-07-21 | 山西利根定信息科技有限公司 | Preparation method and application of water-resistant impact-resistant waterborne polyurethane |
Non-Patent Citations (1)
| Title |
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| H. RAJAN ET AL: ""Synthesis and Properties of Segmented Polyurethane Using Phenolphthalein as Chain Extenders"", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 48, no. 12, 30 June 1993 (1993-06-30), pages 2095 - 2099, XP000462332, DOI: 10.1002/app.1993.070481204 * |
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