CN115449331A - Water treatment membrane two-component polyurethane adhesive and preparation method thereof - Google Patents
Water treatment membrane two-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN115449331A CN115449331A CN202211275188.1A CN202211275188A CN115449331A CN 115449331 A CN115449331 A CN 115449331A CN 202211275188 A CN202211275188 A CN 202211275188A CN 115449331 A CN115449331 A CN 115449331A
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- castor oil
- polyurethane adhesive
- treatment membrane
- water treatment
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- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 30
- 239000004814 polyurethane Substances 0.000 title claims abstract description 30
- 239000012528 membrane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000004359 castor oil Substances 0.000 claims abstract description 56
- 235000019438 castor oil Nutrition 0.000 claims abstract description 56
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 56
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 10
- 229920005906 polyester polyol Polymers 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 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 12
- 238000003756 stirring Methods 0.000 claims description 7
- -1 carbodiimide modified 4,4' -diphenylmethane diisocyanate Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 18
- 229920000570 polyether Polymers 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 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 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
-
- 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
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to the technical field of adhesives, and particularly provides a water treatment membrane two-component polyurethane adhesive and a preparation method thereof. The water treatment membrane two-component polyurethane adhesive comprises a component A and a component B, wherein the component A is prepared from 50-70% of diisocyanate and 30-50% of castor oil according to 100% of weight; the component B is prepared by 60-80% of castor oil, 20-40% of four-functionality chain extender, 0.01-1% of catalyst, 0.5-2% of adhesion promoter and 0.5-2% of defoaming agent according to 100% of weight; the weight ratio of the component A to the component B is 1. The water treatment membrane two-component polyurethane adhesive is used for bonding a water treatment membrane, and has the characteristics of high curing speed, high shear strength, good hydrolysis resistance, less dissolved substances and the like.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a water treatment membrane two-component polyurethane adhesive and a preparation method thereof.
Background
When the water treatment membrane is applied to water treatment equipment, an adhesive is required to be used for bonding, the curing rate is required to be high, the bonding strength is high, the hardness is moderate, better performance can still be maintained after various deterioration condition tests, few dissolved matters exist and the like.
In the prior art, the polyurethane adhesive is adopted as the adhesive of the water treatment membrane, has better effect, but still needs to be improved continuously.
Disclosure of Invention
The inventor finds that the technical problems of incomplete reaction and easy dissolution of the small molecular chain extender exist in the prior art when the small molecular chain extender is adopted, which is probably because in the mixing reaction process of the components A and B, along with the gradual increase of the molecular weight of polyurethane, a small part of small molecular chain extender which does not participate in the reaction is wrapped and shielded by macromolecules and can not participate in the chain extension reaction continuously; the polyether polyol has a problem of low shear strength due to flexibility of the ether bond.
In order to solve the technical problems, the application provides a water treatment membrane two-component polyurethane adhesive and a preparation method thereof.
The technical scheme is as follows:
a water treatment membrane two-component polyurethane adhesive comprises a component A and a component B;
the component A is prepared from 50-70% of diisocyanate and 30-50% of castor oil according to 100% of weight;
the component B is prepared from 60-80% of castor oil, 20-40% of four-functionality chain extender, 0.01-1% of catalyst, 0.5-2% of adhesion promoter and 0.5-2% of defoaming agent by weight of 100%;
the weight ratio of the component A to the component B is 1.
Preferably, the diisocyanate is selected from the group consisting of 4,4' -diphenylmethane diisocyanate and derivatives thereof.
More preferably, the diisocyanate is selected from carbodiimide-modified 4,4' -diphenylmethane diisocyanate.
Preferably, the castor oil is refined castor oil.
More preferably, the refined castor oil contains 0.5-2% of water removal agent by weight percentage.
Preferably, the tetrafunctional chain extender is selected from the group consisting of tetra-hydroxyl terminated polyester polyols.
More preferably, the hydroxyl number of the tetra-hydroxyl terminated polyester polyol is not less than 90mg KOH/g.
Preferably, the catalyst is selected from organotin catalysts.
Preferably, the adhesion promoter is selected from epoxy silane coupling agents.
The preparation method of the water treatment membrane two-component polyurethane adhesive comprises the following steps of adding diisocyanate into a reactor under the atmosphere of inert gas, heating to 60-80 ℃, adding the castor oil in batches, and continuing to react for 1-5 hours after the addition is finished to obtain the component A;
adding the castor oil, the tetrafunctional chain extender, the catalyst, the defoaming agent and the adhesion promoter into a reactor, heating to 70-85 ℃, stirring for 1-3 hours, and vacuumizing and defoaming to obtain the component B;
the component A and the component B are uniformly mixed according to the weight ratio of 1.
In summary, the present application has the following beneficial effects:
1. this application adopts castor oil and diisocyanate preparation A component, and castor oil is the branched chain structure, contains 3 ester bonds in 1 castor oil molecular structure moreover, and because the molecular weight of castor oil is great, ester bond density is lower, and the density of ester bond is also lower in the A component that obtains, has better hydrolysis resistance when improving cohesive strength, shear strength.
2. In the application, the tetra-hydroxyl polyester polyol of the component B is a macromolecular chain extender, the molecular weight of castor oil is larger, the problem that a small molecular chain extender is easy to dissolve out does not exist, the molecular weight of the tetra-hydroxyl polyester polyol is larger, the wrapping and shielding opportunities are less than that of the small molecular chain extender, and the tetra-hydroxyl polyester polyol is more likely to participate in chain extension reaction; meanwhile, the hydrolytic property and high cohesive strength of the polyester are comprehensively considered, the consumption of the polyester polyol with hydroxyl groups at four ends is less, the influence on the hydrolytic resistance of the cured adhesive is less, and the strength of the polyester polyol is higher, so that the high-strength adhesive is favorably obtained.
3. The adhesive provided by the application obtains comprehensive balance on hydrolysis resistance, micromolecule dissolution, cohesive strength, shear strength and other properties, and has better comprehensive properties.
4. In the application, the diisocyanate is preferably carbodiimide modified 4,4' -diphenylmethane diisocyanate, so that hydrolysis of a polyester chain segment can be inhibited, and hydrolysis resistance of the adhesive is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
The application provides a water treatment membrane two-component polyurethane adhesive on one hand, which comprises a component A and a component B;
the component A is prepared from 50-70% of diisocyanate and 30-50% of castor oil according to 100% by weight;
the component B is prepared by 60-80% of castor oil, 20-40% of four-functionality chain extender, 0.01-1% of catalyst, 0.5-2% of adhesion promoter and 0.5-2% of defoaming agent according to 100% of weight;
the weight ratio of the component A to the component B is 1. Further, the weight ratio of the component A to the component B is 1.
In the present application, further, the diisocyanate is selected from the group consisting of 4,4' -diphenylmethane diisocyanate and derivatives thereof. Further, the diisocyanate is selected from carbodiimide-modified 4,4' -diphenylmethane diisocyanate. The inventor finds that the carbodiimide modified 4,4' -diphenylmethane diisocyanate has a good shielding effect on a polyester chain segment of polyurethane, improves the hydrolysis resistance of the polyester chain segment, and further improves the hydrolysis resistance of the adhesive. Carbodiimide-modified 4,4' -diphenylmethane diisocyanate is available directly from the market, for example, from the Vanhua chemical group, inc.
In this application, further, the castor oil is refined castor oil. Furthermore, the refined castor oil contains 0.5 to 2 weight percent of water removal agent.
The structure of castor oil is shown in the following formula (1),
the castor oil contains triglyceride of higher fatty acid as main component, and the ester bond has low density in the whole molecular structure, so that the polyurethane adhesive has high cohesive strength and shear strength and good hydrolysis resistance, and the cohesive strength and hydrolysis resistance are comprehensively balanced.
Further herein, the tetrafunctional chain extender is selected from the group consisting of tetra-hydroxyl terminated polyester polyols. The tetra-hydroxyl polyester polyol is adopted as a chain extender, and due to the fact that the molecular weight of the chain extender is large, compared with the chain extender which adopts small molecular polyol in the prior art, such as ethylene glycol and 1, 4-butanediol, the chain extender is difficult to dissolve out. Furthermore, the hydroxyl value of the hydroxyl terminated polyester polyol is not lower than 90mg KOH/g, so that the molecular weight of the hydroxyl terminated polyester polyol is controlled not to be higher, and the influence of low activity of the hydroxyl terminated polyester polyol on the function of the hydroxyl terminated polyester polyol as a chain extender is avoided.
In the application, the chain extender with four functional degrees is adopted, so that the crosslinking density of the cured polyurethane adhesive can be improved, the shear strength is improved, the high functional degree is favorable for improving the reaction speed, the problem of insufficient activity of terminal hydroxyl groups caused by large molecular weight is solved, and the surface drying time and the actual drying time can be shortened. The water treatment membrane two-component polyurethane adhesive is tested according to the method of GB/T7123-2002, the surface drying time is not more than 25min, and the actual drying time is not more than 20h.
In the present application, further, the catalyst is selected from organotin catalysts. The organotin catalyst used is dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, etc.
In the present application, further, the adhesion promoter is selected from epoxy silane coupling agents. As the epoxy silane coupling agent, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane and the like are generally used.
In the present application, the defoaming agent is not particularly limited, and dimethyl silicone oil defoaming agent, polyether defoaming agent, acrylate defoaming agent, mineral oil defoaming agent, and the like can be used.
In another aspect, the present application provides a method for preparing a two-component polyurethane adhesive for a water treatment membrane according to any of the above embodiments, comprising the steps of,
adding diisocyanate into a reactor under the atmosphere of inert gas, heating to 60-80 ℃, adding castor oil in batches, and continuing to react for 1-5 hours after the castor oil is added to obtain a component A; the castor oil is added in batches, so that the phenomenon that the performance of the component A is deteriorated due to too fast reaction of the castor oil and diisocyanate can be avoided, the castor oil can be added for 2 to 4 times according to needs, the time interval of each addition is 0.5 to 1 hour, and the weight of the castor oil added for each time can be the same or different.
Adding castor oil, a tetrafunctional chain extender, a catalyst, a defoaming agent and an adhesion promoter into a reactor, heating to 70-85 ℃, stirring for 1-3 hours, and vacuumizing and defoaming to obtain a component B;
when the component A and the component B are used, the components are uniformly mixed according to the weight ratio of 1. Further, the component A and the component B are uniformly mixed according to the weight ratio of 1.
The two-component polyurethane adhesive for water treatment membrane and the preparation method thereof will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
Adding 55 parts of 4,4' -diphenylmethane diisocyanate into a reactor under the atmosphere of nitrogen, heating to 75 ℃, adding 45 parts of refined castor oil (the castor oil contains 1wt% of water removal agent) in three batches with equal weight, wherein the addition time interval of the refined castor oil in the batches is 1 hour, and continuously reacting for 3 hours after the addition is finished to obtain a component A;
adding 72 parts of refined castor oil, 26 parts of hydroxyl-terminated polyester polyol (hydroxyl value is 100 mgKOH/g), 0.05 part of dibutyltin dilaurate, 1 part of polyether defoamer and 0.95 part of gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane into a reactor, heating to 73 ℃, stirring for 1.5 hours, and vacuumizing and defoaming to obtain a component B;
when in use, the component A and the component B are mixed according to the weight ratio of 1.
Example 2
In example 1,4 '-diphenylmethane diisocyanate was replaced with an equal part by weight of carbodiimide-modified 4,4' -diphenylmethane diisocyanate, and the rest of the procedure was kept unchanged.
Example 3
Adding 65 parts of 4,4' -diphenylmethane diisocyanate into a reactor under the atmosphere of nitrogen, heating to 70 ℃, adding 35 parts of refined castor oil (the castor oil contains 1.2wt% of water removal agent) in three batches with equal weight, wherein the batch adding time interval of the refined castor oil is 0.7 hour, and continuously reacting for 3.5 hours after the addition is finished to obtain a component A;
adding 70 parts of refined castor oil, 28 parts of hydroxyl-terminated polyester polyol (hydroxyl value is 120 mgKOH/g), 0.1 part of dibutyltin dilaurate, 0.9 part of polyether defoaming agent and 1 part of gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane into a reactor, heating to 75 ℃, stirring for 2.5 hours, and vacuumizing and defoaming to obtain a component B;
when in use, the component A and the component B are mixed according to the weight ratio of 1.
Example 4
In example 3,4 '-diphenylmethane diisocyanate was replaced with an equal part by weight of carbodiimide-modified 4,4' -diphenylmethane diisocyanate, and the remaining steps were kept unchanged.
Example 5
Adding 70 parts of carbodiimide modified 4,4' -diphenylmethane diisocyanate into a reactor in a nitrogen atmosphere, heating to 68 ℃, adding 30 parts of refined castor oil (the castor oil contains 1wt% of water removal agent) in three batches by equal weight, wherein the addition time interval of the refined castor oil in the batches is 0.8 hour, and continuously reacting for 3.5 hours after the addition is finished to obtain a component A;
adding 62 parts of refined castor oil, 35.5 parts of hydroxyl-terminated polyester polyol (hydroxyl value is 120 mgKOH/g), 0.1 part of dibutyltin dilaurate, 0.9 part of polyether defoamer and 1.5 parts of gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane into a reactor, heating to 77 ℃, stirring for 2 hours, and vacuumizing for defoaming to obtain a component B;
when in use, the component A and the component B are mixed according to the weight ratio of 1.
Example 6
In example 5, the carbodiimide-modified 4,4' -diphenylmethane diisocyanate was adjusted from 70 parts to 63 parts and the refined castor oil was adjusted from 30 parts to 37 parts in preparation of component A, and the remaining steps were kept unchanged.
Example 7
In example 5, when component B was prepared, the refined castor oil was adjusted from 62 parts to 70 parts and the tetrahydroxy polyester polyol was adjusted from 35.5 parts to 27.5 parts, and the remaining steps were kept unchanged.
Example 8
In example 5, when component B was prepared, the refined castor oil was adjusted from 62 parts to 75 parts and the tetrahydroxy polyester polyol was adjusted from 35.5 parts to 22.5 parts, and the remaining steps were kept unchanged.
Comparative example 1
In example 5, in preparing part A, 30 parts of refined castor oil were replaced with a combination of 20 parts of refined castor oil and 10 parts of polyether glycol (trade name polyether N-210), and the remaining steps were kept unchanged.
Comparative example 2
Adding 70 parts of carbodiimide modified 4,4' -diphenylmethane diisocyanate into a reactor in a nitrogen atmosphere, heating to 68 ℃, adding 30 parts of polyether glycol (trade name polyether N-210) in three batches with equal weight, wherein the time interval of the batch addition of the polyether glycol is 0.8 hour, and continuously reacting for 3.5 hours after the addition is finished to obtain a component A;
adding 62 parts of refined castor oil, 35.5 parts of four-terminal hydroxyl polyether polyol (trade name 403 polyether), 0.1 part of dibutyltin dilaurate, 0.9 part of polyether defoaming agent and 1.5 parts of gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane into a reactor, heating to 77 ℃, stirring for 2 hours, and vacuumizing and defoaming to obtain a component B;
when in use, the component A and the component B are mixed according to the weight ratio of 1.
Comparative example 3
In example 5, the remaining steps were unchanged, except that the tetrahydroxy polyester polyol was replaced with an equal weight part of a tetrahydroxy polyether polyol (trade name 403 polyether) in the preparation of component B.
Comparative example 4
In example 5, 35.5 parts of the hydroxyl terminated polyester polyol was replaced with a combination of 30 parts of hydroxyl terminated polyester polyol and 5.5 parts of 1,4 butanediol to prepare component B, with the remaining steps remaining unchanged.
Comparative example 5
In comparative example 3, 35.5 parts of the hydroxyl terminated polyether polyol were replaced with a combination of 30 parts of hydroxyl terminated polyether polyol and 5.5 parts of 1, 4-butanediol, and the remainder of the procedure was maintained.
Performance testing
Commercially available PVDF curtain hollow fiber membranes were bonded with the adhesive glues of examples 1 to 8 and comparative examples 1 to 5, and left at room temperature for 48 hours after bonding.
And (3) testing the shear strength: testing according to the method of GB/T7124-2008.
Double eighty-five test: and (3) placing the sample to be tested in a test box with the humidity of 85 ℃/85% for 1000 hours, taking out the sample to be tested for drying, placing the sample at room temperature for 24 hours, and calculating the shear strength retention rate after testing according to the shear strength test.
Hydrolysis resistance test: and (3) soaking the sample to be tested in boiling water for 100 hours, taking out and wiping the sample to be tested, standing the sample at room temperature for 24 hours, and calculating the shear strength retention rate after testing according to the shear strength test.
Shear strength retention = (shear strength before test-shear strength after test)/shear strength before test × 100%.
And (3) testing a dissolved substance: accurately weighing 100 +/-0.1 g (to 0.0001 g) of cured bonding glue to be tested, placing the bonding glue to be tested in a quick extractor, adding 1000ml of water, and heating, refluxing and extracting for 4 hours. And after extraction, putting the bonding adhesive to be tested into a thermostat at 85 ℃ to dry to constant weight, cooling, and weighing the weight as Wg, wherein the content of the dissolved substance is = (100-W)/100 multiplied by 100%.
The results are shown in table 1 below.
TABLE 1
Based on the data in Table 1, comparing example 2 with example 1, and example 4 with example 3, it is demonstrated that the shear strength retention after the Bisarv test and the hydrolysis resistance test is increased by using carbodiimide modified 4,4 '-diphenylmethane diisocyanate compared with 4,4' -diphenylmethane diisocyanate, and the hydrolysis resistance of the adhesive is improved.
Comparing example 5 and example 6, the amount of castor oil in the A component is increased, the amount of diisocyanate is decreased, the hard segment content of the polyurethane adhesive is decreased, and the shear strength is decreased.
In comparative example 5, example 7 and example 8, the weight of castor oil in the B component was increased, the weight of polyester polyol was decreased, the shear strength of the adhesive was decreased, but the hydrolysis resistance was improved.
Compared with the comparative examples 1 to 3, the adhesive has the advantages that the polyether content in the adhesive is increased, the shear strength is obviously reduced, and the hydrolysis resistance is improved to a certain extent.
Comparing example 5 with comparative examples 4 and 5, a certain amount of small molecule chain extender is added into the adhesive glue, so that the dissolution is obviously improved.
Therefore, the water treatment membrane two-component polyurethane adhesive has the advantages of balanced shear strength, hydrolysis resistance and the performance of a dissolved substance, the shear strength is not lower than 15MPa, the dissolved substance is lower than 10ppm, and the comprehensive performance is good.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A water treatment membrane two-component polyurethane adhesive is characterized in that: comprises a component A and a component B;
the component A is prepared from 50-70% of diisocyanate and 30-50% of castor oil by weight of 100%;
the component B is prepared from 60-80% of castor oil, 20-40% of four-functionality chain extender, 0.01-1% of catalyst, 0.5-2% of adhesion promoter and 0.5-2% of defoaming agent by weight of 100%;
the weight ratio of the component A to the component B is 1.
2. A water treatment membrane two-component polyurethane adhesive as claimed in claim 1, wherein: the diisocyanate is selected from 4,4' -diphenylmethane diisocyanate and derivatives thereof.
3. The water-treatment membrane two-component polyurethane adhesive according to claim 2, characterized in that: the diisocyanate is selected from carbodiimide modified 4,4' -diphenylmethane diisocyanate.
4. A water treatment membrane two-component polyurethane adhesive as claimed in claim 1, wherein: the castor oil is refined castor oil.
5. A water treatment membrane two-component polyurethane adhesive according to claim 4, characterized in that: the refined castor oil contains 0.5-2% of water removal agent by weight percentage.
6. A water treatment membrane two-component polyurethane adhesive as claimed in claim 1, wherein: the tetrafunctional chain extender is selected from the group consisting of tetra-hydroxyl terminated polyester polyols.
7. The water-treatment membrane two-component polyurethane adhesive according to claim 6, characterized in that: the hydroxyl value of the tetra-hydroxyl polyester polyol is not less than 90mg KOH/g.
8. The water-treatment membrane two-component polyurethane adhesive according to claim 1, characterized in that: the catalyst is selected from organotin catalysts.
9. A water treatment membrane two-component polyurethane adhesive as claimed in claim 1, wherein: the adhesion promoter is selected from epoxy silane coupling agents.
10. A method of preparing a water treatment membrane two-component polyurethane adhesive as claimed in any one of claims 1 to 9, characterized in that: comprises the following steps of (a) carrying out,
adding the diisocyanate into a reactor under the inert gas atmosphere, heating to 60-80 ℃, adding the castor oil in batches, and continuing to react for 1-5 hours after the castor oil is added to obtain the component A;
adding the castor oil, the tetrafunctional chain extender, the catalyst, the defoaming agent and the adhesion promoter into a reactor, heating to 70-85 ℃, stirring for 1-3 hours, and vacuumizing and defoaming to obtain the component B;
the component A and the component B are uniformly mixed according to the weight ratio of 1.5-1 when in use.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117264596A (en) * | 2023-10-10 | 2023-12-22 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
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| CN101717488A (en) * | 2009-12-03 | 2010-06-02 | 上海维凯化学品有限公司 | Epoxy resin modified water-based polyurethane emulsion and preparation method thereof |
| CN107083229A (en) * | 2017-05-12 | 2017-08-22 | 南京威邦新材料有限公司 | A kind of preparation method of membrane for water treatment bi-component polyurethane pouring sealant |
| CN109280528A (en) * | 2018-10-09 | 2019-01-29 | 杭州之江新材料有限公司 | A kind of High-strength double-component polyurethane group angle glue and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101717488A (en) * | 2009-12-03 | 2010-06-02 | 上海维凯化学品有限公司 | Epoxy resin modified water-based polyurethane emulsion and preparation method thereof |
| CN107083229A (en) * | 2017-05-12 | 2017-08-22 | 南京威邦新材料有限公司 | A kind of preparation method of membrane for water treatment bi-component polyurethane pouring sealant |
| CN109280528A (en) * | 2018-10-09 | 2019-01-29 | 杭州之江新材料有限公司 | A kind of High-strength double-component polyurethane group angle glue and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117264596A (en) * | 2023-10-10 | 2023-12-22 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
| CN117264596B (en) * | 2023-10-10 | 2024-05-10 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
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Application publication date: 20221209 |