CN116554823B - Waterproof polyurethane adhesive and preparation method thereof - Google Patents
Waterproof polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN116554823B CN116554823B CN202310832987.2A CN202310832987A CN116554823B CN 116554823 B CN116554823 B CN 116554823B CN 202310832987 A CN202310832987 A CN 202310832987A CN 116554823 B CN116554823 B CN 116554823B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 6
- 229920000151 polyglycol Polymers 0.000 claims abstract description 3
- 239000010695 polyglycol Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003063 flame retardant Substances 0.000 abstract description 9
- 150000002009 diols Chemical class 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3831—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a waterproof polyurethane adhesive and a preparation method thereof, which belong to the technical field of adhesives, wherein the waterproof polyurethane adhesive comprises a component A and a component B, and the component A comprises the following raw materials in parts by weight: 150-200 parts of polyglycol, 10-20 parts of glycol, 0.001-0.002 part of stannous octoate and 1-2 parts of trimethylolpropane; the component B comprises the following raw materials in parts by weight: 50-80 parts of polyether glycol, 100-120 parts of 4,4 '-diphenylmethane diisocyanate, 10-15 parts of 4,4' -dicyclohexylmethane diisocyanate and 10-12 parts of antioxidant 1010; according to the invention, fluorine is introduced into the diol from the structure, so that the hydrolysis resistance of polyurethane molecular chains can be improved, the excellent flame retardant property can be given to polyurethane by introducing the intermediate 1 structure, the carbon formation property can be given to the benzene ring structure of triphenylmethane triisocyanate, and the flame retardant effect can be improved by cooperating with the intermediate 1.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a waterproof polyurethane adhesive and a preparation method thereof.
Background
The double-component polyurethane adhesive is mainly composed of a hydroxyl-containing aqueous polyol component (component A) and an isocyanate-containing polyisocyanate component (component B) together. In addition, the system also contains other auxiliary agents with special purposes. The components A and B are packaged separately, the components A and B are mixed uniformly before use, and the hydroxyl groups (-OH) in the polyol and the isocyanate groups (-NCO) in the polyisocyanate are utilized to carry out crosslinking reaction to form carbamate by adjusting the proportion of the components A and B, so that the performances of the polyurethane material in various aspects such as strength, curing time and the like can be changed.
However, because the polyurethane adhesive has ester groups, the polyurethane adhesive has very high water absorption, and can absorb moisture in the air when being exposed to the air; after the polyurethane adhesive absorbs moisture, bubbles are generated during processing, so that the tensile strength and the elongation of the TPU adhesive are reduced, and the tensile strength is reduced by 30% when the moisture absorption amount reaches 0.182%.
Disclosure of Invention
In order to solve the technical problems, the invention provides a waterproof polyurethane adhesive and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the waterproof polyurethane adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 150-200 parts of polyglycol, 10-20 parts of glycol, 0.001-0.002 part of stannous octoate and 1-2 parts of trimethylolpropane;
the component B comprises the following raw materials in parts by weight: 50-80 parts of polyether glycol, 100-120 parts of 4,4 '-diphenylmethane diisocyanate, 10-15 parts of 4,4' -dicyclohexylmethane diisocyanate and 10-12 parts of antioxidant 1010;
further, the dihydric alcohol comprises the following steps:
step S1, adding cyanuric chloride into deionized water, heating to 40-45 ℃, dropwise adding 2, 6-tetramethylpiperidine amine aqueous solution, continuously stirring and reacting for 4 hours after the dropwise adding is completed, dropwise adding 35% hydrochloric acid solution after the reaction is completed, regulating the pH value until the pH value of a system is less than 5, cooling to room temperature, continuously stirring for 20 minutes, filtering and drying to prepare an intermediate 1, and controlling the dosage ratio of cyanuric chloride, 2, 6-tetramethylpiperidine amine and deionized water to be 0.1 mol:0.3 mol:100 mL;
in the step S1, cyanuric chloride reacts with 2, 6-tetramethyl piperidine amine to prepare an intermediate 1, wherein the reaction process is as follows:
s2, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen to discharge air, heating to 80 ℃, stirring at constant speed, adding triphenylmethane triisocyanate and dibutyltin dilaurate, carrying out heat preservation reflux reaction for 3 hours, cooling to room temperature after the reaction is finished, adding diethanolamine, continuing to react for 20 minutes, adding an intermediate 1, continuing stirring and reacting for 1 hour, and carrying out rotary evaporation to remove the acetone after the reaction is finished to obtain dihydric alcohol, wherein the dosage ratio of hexafluoro-n-butanol, triphenylmethane triisocyanate, diethanolamine and acetone is controlled to be 0.1 mol:0.1 mol:150 mL, the dosage of dibutyltin dilaurate is 3-5% of the weight of the triphenylmethane triisocyanate, and the molar ratio of the intermediate 1 to the triphenylmethane triisocyanate is 1:1;
in the step S2, hexafluoro-n-butanol reacts with one isocyanate group on triphenylmethane triisocyanate under the action of dibutyltin dilaurate catalyst to generate an intermediate a, then one isocyanate group on the intermediate a reacts with diethanolamine to generate an intermediate b, then an intermediate 1 is added, and the rest isocyanate groups on the intermediate b react with secondary amine on the intermediate 1 to prepare dihydric alcohol, wherein the reaction process for generating the intermediate b is as follows:
according to the structure, the fluorine element is introduced into the synthesized dihydric alcohol, so that the hydrolysis resistance in a synthesized polyurethane molecular chain can be improved, the introduced intermediate 1 structure can endow polyurethane with excellent flame retardant property, in addition, the triphenylmethane triisocyanate is used as a raw material, and the benzene ring structure can endow the polyurethane with carbon forming property, and the intermediate 1 is cooperated to improve the flame retardant effect.
Further, in the step S1, the 2, 6-tetramethyl piperidine amine aqueous solution is prepared by mixing 2, 6-tetramethyl piperidine amine and deionized water according to the dosage ratio of 0.3 mol:50 mL.
Further, the weight ratio of the component A to the component B is 1:1.5.
A preparation method of a waterproof polyurethane adhesive comprises the following steps:
the first step, stirring the raw materials in the component A for 30min at the temperature of 45 ℃ and the rotating speed of 300-500r/min to obtain the component A;
secondly, stirring the antioxidant 1010 and the 4,4 '-dicyclohexylmethane diisocyanate for 10min at the temperature of 45 ℃ and the rotating speed of 300-500r/min, adding polyether glycol, heating to 75 ℃, reacting for 1h at the temperature of the heat preservation, adding the 4,4' -diphenylmethane diisocyanate, and continuously reacting for 1h to obtain a component B;
and thirdly, uniformly mixing the component A and the component B according to the weight ratio of 1:1.5 when in use, and preparing the water-resistant polyurethane adhesive.
The invention has the beneficial effects that:
the water-resistant polyurethane adhesive is prepared by mixing the component A and the component B when the water-resistant polyurethane adhesive is used, dihydric alcohol in the component A is synthesized by the intermediate 1 and the intermediate B, fluorine is introduced into the dihydric alcohol synthesized by the water-resistant polyurethane adhesive, the hydrolysis resistance in a synthesized polyurethane molecular chain can be improved, the introduced intermediate 1 structure can endow polyurethane with excellent flame retardant property, in addition, triphenylmethane triisocyanate is selected as a raw material, the benzene ring structure of the water-resistant polyurethane adhesive can endow the water-resistant polyurethane adhesive with carbon forming property, and the water-resistant polyurethane adhesive is cooperated with the intermediate 1 to improve the flame retardant effect, so that the technical problem that the polyurethane adhesive is not water-resistant is solved, the excellent flame retardant property is endowed, and the application range of the polyurethane adhesive is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments 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.
Example 1
The waterproof polyurethane adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 150 parts of polycaprolactone diol, 10 parts of dihydric alcohol, 0.001 part of stannous octoate and 1 part of trimethylolpropane;
the component B comprises the following raw materials in parts by weight: 50 parts of polyether glycol (green N220), 100 parts of 4,4 '-diphenylmethane diisocyanate, 10 parts of 4,4' -dicyclohexylmethane diisocyanate and 10 parts of antioxidant 1010;
the waterproof polyurethane adhesive is prepared by the following steps:
the first step, stirring the raw materials in the component A for 30min at the temperature of 45 ℃ and the rotating speed of 300r/min to obtain the component A;
and secondly, stirring the antioxidant 1010 and the 4,4 '-dicyclohexylmethane diisocyanate for 10min at the temperature of 45 ℃ and the rotating speed of 300r/min, adding polyether glycol, heating to 75 ℃, preserving heat and reacting for 1h, adding the 4,4' -diphenylmethane diisocyanate, and continuing to react for 1h to obtain the component B.
And thirdly, mixing the component A and the component B according to the weight ratio of 1:1.5 when in use.
The dihydric alcohol comprises the following steps:
step S1, adding cyanuric chloride into deionized water, heating to 40 ℃, dropwise adding 2, 6-tetramethylpiperidine amine aqueous solution, continuously stirring and reacting for 4 hours after the dropwise adding is completed, dropwise adding 35% hydrochloric acid solution after the reaction is completed, regulating the pH value until the pH value of a system is less than 5, cooling to room temperature, continuously stirring for 20 minutes, filtering and drying to prepare an intermediate 1, and controlling the dosage ratio of cyanuric chloride, 2, 6-tetramethylpiperidine amine and deionized water to be 0.1 mol:0.3 mol:100 mL;
s2, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen to discharge air, heating to 80 ℃, stirring at constant speed, adding triphenylmethane triisocyanate and dibutyltin dilaurate, carrying out heat preservation reflux reaction for 3 hours, cooling to room temperature after the reaction is finished, adding diethanolamine, continuing to react for 20 minutes, adding an intermediate 1, continuing stirring and reacting for 1 hour, and carrying out rotary evaporation to remove the acetone after the reaction is finished to obtain dihydric alcohol, wherein the dosage ratio of hexafluoro-n-butanol, triphenylmethane triisocyanate, diethanolamine and acetone is controlled to be 0.1 mol:0.1 mol:150 mL, the dosage of dibutyltin dilaurate is 3% of the weight of the triphenylmethane triisocyanate, and the molar ratio of the intermediate 1 to the triphenylmethane triisocyanate is 1:1;
the 2, 6-tetramethyl piperidine amine aqueous solution in the step S1 is prepared by mixing 2, 6-tetramethyl piperidine amine and deionized water according to the dosage ratio of 0.3 mol:50 mL.
Example 2
The waterproof polyurethane adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 180 parts of polycaprolactone diol, 15 parts of dihydric alcohol, 0.001 part of stannous octoate and 1.5 parts of trimethylolpropane;
the component B comprises the following raw materials in parts by weight: 70 parts of polyether glycol (green N220), 110 parts of 4,4 '-diphenylmethane diisocyanate, 12 parts of 4,4' -dicyclohexylmethane diisocyanate and 10 parts of antioxidant 1010;
the waterproof polyurethane adhesive is prepared by the following steps:
the first step, stirring the raw materials in the component A for 30min at the temperature of 45 ℃ and the rotating speed of 400r/min to obtain the component A;
and secondly, stirring the antioxidant 1010 and the 4,4 '-dicyclohexylmethane diisocyanate for 10min at the temperature of 45 ℃ and the rotating speed of 400r/min, adding polyether glycol, heating to 75 ℃, preserving heat and reacting for 1h, adding the 4,4' -diphenylmethane diisocyanate, and continuing to react for 1h to obtain the component B.
And thirdly, mixing the component A and the component B according to the weight ratio of 1:1.5 when in use.
The dihydric alcohol comprises the following steps:
step S1, adding cyanuric chloride into deionized water, heating to 45 ℃, dropwise adding 2, 6-tetramethylpiperidine amine aqueous solution, continuously stirring and reacting for 4 hours after the dropwise adding is completed, dropwise adding 35% hydrochloric acid solution after the reaction is completed, regulating the pH value until the pH value of a system is less than 5, cooling to room temperature, continuously stirring for 20 minutes, filtering and drying to prepare an intermediate 1, and controlling the dosage ratio of cyanuric chloride, 2, 6-tetramethylpiperidine amine and deionized water to be 0.1 mol:0.3 mol:100 mL;
s2, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen to discharge air, heating to 80 ℃, stirring at constant speed, adding triphenylmethane triisocyanate and dibutyltin dilaurate, carrying out heat preservation reflux reaction for 3 hours, cooling to room temperature after the reaction is finished, adding diethanolamine, continuing to react for 20 minutes, adding an intermediate 1, continuing stirring and reacting for 1 hour, and carrying out rotary evaporation to remove the acetone after the reaction is finished to obtain dihydric alcohol, wherein the dosage ratio of hexafluoro-n-butanol, triphenylmethane triisocyanate, diethanolamine and acetone is controlled to be 0.1 mol:0.1 mol:150 mL, the dosage of dibutyltin dilaurate is 4% of the weight of the triphenylmethane triisocyanate, and the molar ratio of the intermediate 1 to the triphenylmethane triisocyanate is 1:1;
the 2, 6-tetramethyl piperidine amine aqueous solution in the step S1 is prepared by mixing 2, 6-tetramethyl piperidine amine and deionized water according to the dosage ratio of 0.3 mol:50 mL.
Example 3
The waterproof polyurethane adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 200 parts of polycaprolactone diol, 20 parts of dihydric alcohol, 0.002 part of stannous octoate and 2 parts of trimethylolpropane;
the component B comprises the following raw materials in parts by weight: 80 parts of polyether glycol (green N220), 120 parts of 4,4 '-diphenylmethane diisocyanate, 15 parts of 4,4' -dicyclohexylmethane diisocyanate and 12 parts of antioxidant 1010;
the waterproof polyurethane adhesive is prepared by the following steps:
the first step, stirring the raw materials in the component A for 30min at the temperature of 45 ℃ and the rotating speed of 500r/min to obtain the component A;
and secondly, stirring the antioxidant 1010 and the 4,4 '-dicyclohexylmethane diisocyanate for 10min at the temperature of 45 ℃ and the rotating speed of 500r/min, adding polyether glycol, heating to 75 ℃, preserving heat for reaction for 1h, adding the 4,4' -diphenylmethane diisocyanate, and continuing to react for 1h to obtain the component B.
And thirdly, mixing the component A and the component B according to the weight ratio of 1:1.5 when in use.
The dihydric alcohol comprises the following steps:
step S1, adding cyanuric chloride into deionized water, heating to 45 ℃, dropwise adding 2, 6-tetramethylpiperidine amine aqueous solution, continuously stirring and reacting for 4 hours after the dropwise adding is completed, dropwise adding 35% hydrochloric acid solution after the reaction is completed, regulating the pH value until the pH value of a system is less than 5, cooling to room temperature, continuously stirring for 20 minutes, filtering and drying to prepare an intermediate 1, and controlling the dosage ratio of cyanuric chloride, 2, 6-tetramethylpiperidine amine and deionized water to be 0.1 mol:0.3 mol:100 mL;
s2, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen to discharge air, heating to 80 ℃, stirring at constant speed, adding triphenylmethane triisocyanate and dibutyltin dilaurate, carrying out heat preservation reflux reaction for 3 hours, cooling to room temperature after the reaction is finished, adding diethanolamine, continuing to react for 20 minutes, adding an intermediate 1, continuing stirring and reacting for 1 hour, and carrying out rotary evaporation to remove the acetone after the reaction is finished to obtain dihydric alcohol, wherein the dosage ratio of hexafluoro-n-butanol, triphenylmethane triisocyanate, diethanolamine and acetone is controlled to be 0.1 mol:0.1 mol:150 mL, the dosage of dibutyltin dilaurate is 5% of the weight of the triphenylmethane triisocyanate, and the molar ratio of the intermediate 1 to the triphenylmethane triisocyanate is 1:1;
the 2, 6-tetramethyl piperidine amine aqueous solution in the step S1 is prepared by mixing 2, 6-tetramethyl piperidine amine and deionized water according to the dosage ratio of 0.3 mol:50 mL.
Comparative example 1
This comparative example is compared to example 1, using 1, 4-butanediol instead of glycol.
Comparative example 2
This comparative example 2 is a polyurethane adhesive produced by basf.
The properties of the polyurethane adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 were examined, and the results are shown in Table 1 below:
viscosity: GB/T4851-84;
initial adhesion: according to GB/T2791-1995 test, the adhesive is smeared between PVC/PVC film composite films, and the T-peeling strength is tested after drying;
water resistance: placing the mixture into water at 50 ℃ for 24 hours, and observing;
flame retardant properties: samples were prepared according to the standard ANSI/UL 94-1985 and flame retardant ratings were tested according to the UL94 vertical burn test standard.
TABLE 1 results of Performance test of examples 1-3 and comparative examples 1-2
From Table 1 above, it can be seen that the polyurethane adhesives prepared in examples 1-3 of the present invention have excellent water resistance and flame retardance.
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 (5)
1. A waterproof polyurethane adhesive comprises a component A and a component B, and is characterized in that: the component A comprises the following raw materials in parts by weight: 150-200 parts of polyglycol, 10-20 parts of glycol, 0.001-0.002 part of stannous octoate and 1-2 parts of trimethylolpropane;
the component B comprises the following raw materials in parts by weight: 50-80 parts of polyether glycol, 100-120 parts of 4,4 '-diphenylmethane diisocyanate, 10-15 parts of 4,4' -dicyclohexylmethane diisocyanate and 10-12 parts of antioxidant 1010;
the dihydric alcohol comprises the following steps:
step S1, adding cyanuric chloride into deionized water, heating to 40-45 ℃, dropwise adding 2, 6-tetramethylpiperidine amine aqueous solution, continuously stirring and reacting for 4 hours after the dropwise adding is completed, dropwise adding 35% hydrochloric acid solution after the reaction is completed, regulating the pH value until the pH value of a system is less than 5, cooling to room temperature, continuously stirring for 20 minutes, filtering and drying to obtain an intermediate 1;
s2, adding hexafluoro-n-butanol into a three-neck flask filled with acetone, introducing nitrogen, exhausting air, heating to 80 ℃, uniformly stirring, adding triphenylmethane triisocyanate and dibutyltin dilaurate, carrying out heat preservation reflux reaction for 3h, cooling to room temperature after the reaction is finished, adding diethanolamine, continuing to react for 20min, adding the intermediate 1, continuing to stir and react for 1h, and carrying out rotary evaporation to remove the acetone after the reaction is finished to obtain dihydric alcohol.
2. The water-resistant polyurethane adhesive according to claim 1, wherein the dosage ratio of cyanuric chloride, 2, 6-tetramethylpiperidine amine and deionized water is controlled to be 0.1 mol:0.3 mol:100 mL in the step S1, the dosage ratio of hexafluoro-n-butanol, triphenylmethane triisocyanate, diethanolamine and acetone is controlled to be 0.1 mol:0.1 mol:150 mL in the step S2, and the dosage of dibutyltin dilaurate is controlled to be 3-5% of the weight of the triphenylmethane triisocyanate, and the molar ratio of the intermediate 1 to the triphenylmethane triisocyanate is 1:1.
3. The water-resistant polyurethane adhesive according to claim 1, wherein the 2, 6-tetramethyl piperidine amine aqueous solution in the step S1 is prepared by mixing 2, 6-tetramethyl piperidine amine and deionized water according to the dosage ratio of 0.3 mol:50 mL.
4. The water-resistant polyurethane adhesive according to claim 1, wherein the weight ratio of the component A to the component B is 1:1.5.
5. A method of preparing the water resistant polyurethane adhesive of claim 1, comprising the steps of:
the first step, stirring the raw materials in the component A for 30min at the temperature of 45 ℃ and the rotating speed of 300-500r/min to obtain the component A;
secondly, stirring the antioxidant 1010 and the 4,4 '-dicyclohexylmethane diisocyanate for 10min at the temperature of 45 ℃ and the rotating speed of 300-500r/min, adding polyether glycol, heating to 75 ℃, reacting for 1h at the temperature of the heat preservation, adding the 4,4' -diphenylmethane diisocyanate, and continuously reacting for 1h to obtain a component B;
and thirdly, uniformly mixing the component A and the component B according to the weight ratio of 1:1.5 when in use, and preparing the water-resistant polyurethane adhesive.
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