CN105419714A - Epoxy resin two-component polyurethane adhesive and preparation method thereof - Google Patents
Epoxy resin two-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN105419714A CN105419714A CN201410454889.0A CN201410454889A CN105419714A CN 105419714 A CN105419714 A CN 105419714A CN 201410454889 A CN201410454889 A CN 201410454889A CN 105419714 A CN105419714 A CN 105419714A
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- polyether glycol
- polyurethane adhesive
- isocyanic ester
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 43
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 239000000853 adhesive Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 84
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 42
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 42
- 229920000570 polyether Polymers 0.000 claims description 42
- 150000002148 esters Chemical class 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- -1 polyoxytrimethylene Polymers 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical group C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 7
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 235000019198 oils Nutrition 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 abstract description 24
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 229920001187 thermosetting polymer Polymers 0.000 abstract 1
- 239000013535 sea water Substances 0.000 description 17
- 238000001223 reverse osmosis Methods 0.000 description 13
- 238000010612 desalination reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003116 impacting effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to the technical field of adhesives, especially to an epoxy resin two-component polyurethane adhesive and a preparation method thereof, wherein a component A and a component B are mixed to prepare the epoxy resin two-component polyurethane adhesive, the component A is a hydroxyl-terminated polyurethane prepolymer, and the component B is an isocyanate-based polyurethane prepolymer having an epoxy resin modified terminate. According to the present invention, the epoxy resin complex is introduced to make the adhesive form the interpenetrating network polymer structure, such that the disadvantages of poor hydrolysis resistance, gas bubble generation during the curing process, and the like of the double-component solvent-free polyurethane adhesive are improved, and especially when the material operates in a 800psi high pressure environment, the adhered membrane assembly has the good adhesion property so as to prolong the service life of the membrane assembly.
Description
Technical field
The present invention relates to field of adhesive technology, especially a kind of epoxy resin dual-component polyurethane adhesive and preparation method thereof.
Background technology
The development of membrane technique makes reverse-osmosis membrane element play more and more important effect in brackish water desalination, sea water desaltination and field of municipal sewage treatment.Reverse osmosis membrane assembly is generally spiral wound configuration, semi-permeable membranes, guide layer and graticule mesh film is formed a film in certain sequence bag-shaped, and three limit cast materials of film bag are bonding, and the 4th limit is connected with porous central tube.The process characteristic of reverse osmosis membrane assembly requires that its cast material has ambient temperature curable, high with the good penetrability of film bag, bonding strength, particularly reverse-osmosis membrane element runs in water surrounding, therefore require that cast material still has good bond degree with reverse osmosis membrane assembly in wet condition, namely there is good water resistance.Simultaneously, owing to containing a large amount of salts and other materials in seawater, therefore, seawater desalination reverse osmosis film need run under high pressure (800psi) condition, and this just requires that tackiness agent under high pressure has good bonding strength and water resistance to seawater desalination reverse osmosis membrane module.
The advantages such as double component solvent-free polyurethane adhesive is long with its shelf lives, glued membrane hardness is adjustable, safety and environmental protection become the first-selected product of adhesive film assembly, but traditional polyurethane adhesive exists that bonding strength is not high, chemical proofing is poor, the not shortcoming such as hydrolysis and can not be directly used in bonding seawater desalination reverse osmosis membrane module.
In the prior art, there is a large amount of investigators to start with for this problem, large quantity research has been carried out to tackiness agent.If the patent No. is that CN201110289506.5 " dual-component polyurethane adhesive and preparation method thereof " discloses a kind of polyurethane adhesive be made up of component A and B component, wherein component A is by styrene-grafted polyether glycol, polypropylene glycol PPG400, polypropylene glycol PPG2000 and selective additives (defoamer, catalyzer and water-removal agent); B component by imine modified 4,4 '-'-diphenylmethane diisocyanate and thick MDI (polyphenyl polymethylene isocyanic ester and 4, the mixture of 4 '-'-diphenylmethane diisocyanate); And for example the patent No. is that CN201410163879.1 " a kind of no-solvent polyurethane sizing agent and preparation method thereof " comprises A and B two components, and component A is the isocyanate terminated performed polymer generated by isocyanic ester, small molecules polyether glycol, plant oil modified polyol reaction; B component is the carboxylic polyether glycol generated by small molecules polyether glycol and anhydride reaction, and retardance catalyst preparing forms; Be that NCO:OH=1-1.5 is fully mixed with and obtains by component A and B component according to functional group's mol ratio again.
But the dual-component polyurethane adhesive bonding strength of its research, chemical proofing, hydrolysis effect are all comparatively undesirable, for this reason, this researchist, by long-term research and discovery, provides a kind of new approaches to epoxy resin polyurethane adhesive.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides a kind of epoxy resin dual-component polyurethane adhesive, there is the feature of high-adhesive-strength, high resistance to chemicals medicine and high hydrolysis resistance performance.
Simultaneously, the present invention also provides a kind of preparation method of epoxy resin dual-component polyurethane adhesive, accurately appropriate control is carried out by the processing parameter in the preparation method to the component A in tackiness agent and B component, and to the raw material order of addition in A, B component preparation technology, and then ensure that the performance of tackiness agent improves, improve the feature of the bonding strength of tackiness agent, chemical proofing and anti-hydrolytic performance.
Be achieved particular by following technical scheme:
A kind of epoxy resin dual-component polyurethane adhesive, formed by component A and B component mixed preparing, wherein the mass ratio of component A and B component is (4-6): (3-5).
Described component A and the mass ratio of B component are 5:4.
Described component A is hydroxyl-terminated polyurethane performed polymer, and its material component is polyether glycol 60-120 part, isocyanic ester 2-10 part, epoxy curing agent 1-5 part; Described B component is epoxy resin modification terminal isocyanate group base polyurethane prepolymer for use as, and its material component is isocyanic ester 80-120 part, polyether glycol 15-50 part, epoxy resin composite 2-20 part.
Polyether glycol in described component A to be molecular weight be 400 polyoxypropyleneglycol, the polyoxytrimethylene triol of molecular weight 1000, Viscotrol C, hydrogenated castor oil, soybean oil, the mixture of one or more in plam oil;
Described isocyanic ester is the mixture of one or more in vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate, liquefied mdi, TDI tripolymer, HDI biuret, HDI tripolymer;
Described epoxy curing agent is methyl tetrahydrophthalic anhydride (MeTHPA).
Isocyanic ester described in described B component is one or more mixtures in vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate, liquefied mdi, TDI tripolymer, HDI biuret, HDI tripolymer;
Described polyether glycol is polyoxypropyleneglycol, the polyoxytrimethylene triol of molecular weight 1000, Viscotrol C, the soybean oil of molecular weight 400, the mixture of one or more in plam oil;
Described epoxy resin composite is the composition of one or more in 4,5-oxepane-1,2-dicarboxylic acid 2-glycidyl ester, glycidyl ester type two functional group epoxy resin 711, bisphenol A type epoxy resin E-51.
Described component A is hydroxyl-terminated polyurethane performed polymer, and its material component is polyether glycol 90 parts, isocyanic ester 7 parts, epoxy curing agent 3 parts; Described B component is epoxy resin modification terminal isocyanate group base polyurethane prepolymer for use as, and its material component is isocyanic ester 100 parts, polyether glycol 35 parts, epoxy resin composite 18 parts.
The preparation method of this epoxy resin dual-component polyurethane adhesive, comprises the following steps:
(1) component A preparation: polyether glycol and isocyanic ester are mixed according to proportioning, order by merging is that isocyanic ester adds in polyether glycol, and added at 7-10min, and employing stirring speed is 50-90r/min carries out stir process, and to adjust temperature be 60 DEG C ~ 80 DEG C, after its reaction 0.5h ~ 2h, obtain mixture; Again epoxy curing agent is joined in mixture, and at temperature is 50 DEG C ~ 80 DEG C Keep agitation 0.5h ~ 1h, then be placed in normal temperature environment, naturally cool to normal temperature, can component A be obtained, stand-by;
(2) B component preparation: isocyanic ester and polyether glycol are mixed according to proportioning mixing, order by merging is that polyether glycol adds in isocyanic ester, and added at 7-10min, and employing stirring speed is 50-90r/min carries out stir process, and to adjust temperature be 50 DEG C ~ 90 DEG C, after its reaction 0.5h ~ 2h, obtain terminal isocyanate group base polyurethane prepolymer for use as; Again epoxy resin composite is joined in terminal isocyanate group base polyurethane prepolymer for use as, and at temperature is 60 DEG C ~ 80 DEG C Keep agitation 0.5h ~ 1h, then be placed in normal temperature environment, naturally cool to normal temperature, can B component be obtained, stand-by;
(3) be mixed with tackiness agent: after prepared by A, B component, carried out independent splendid attire, and in use, then A, B component are mixed at 1-4min according to proportioning, epoxy resin dual-component polyurethane adhesive can be obtained.
Epoxy resin modification described in the invention two component, solvent-free polyurethane adhesive are interpenetrating net polymer structure.Traditional two components, solvent-free polyurethane adhesive hydrolytic resistance are poor, solidification process has bubble to produce.The bonding strength having a direct impact polyurethane adhesive of bubble.And in epoxy resin, containing the epoxide group of the end of hydroxyl, ehter bond and molecular chain or the active of centre, epoxide group solidifies with the form of ring-opening polymerization, and reaction process does not have small molecule by-product to generate; And hydroxyl in epoxy resin can with isocyanate reaction, thus polyurethane adhesive generates the larger three-dimensional net structure of cross-linking density.The cross-linked network structure that this epoxy resin and urethane intert mutually is when being subject to external force (as high pressure etc.) and impacting, and stress dispersion more even, therefore destroys its structure energy that just needs are larger, thus enhance the water resistance of tackiness agent.Therefore the two component of epoxy resin modification, solvent-free polyurethane adhesive are applicable to the sea water desaltination membrane module of bonding high-voltage operation.
The invention reside in and solve the low problem of sea water desaltination membrane module bonding strength that conventional urethane tackiness agent runs condition of high voltage, the epoxy resin modification double component solvent-free polyurethane adhesive of the sea water desaltination membrane module being applicable to condition of high voltage operation is provided.Bonded adhesives mainly in order to provide a kind of seawater desalination reverse osmosis membrane module run under 800psi condition bonding.
Compared with prior art, technique effect of the present invention is embodied in:
1. the seawater membrane module that epoxy resin dual-component polyurethane adhesive of the present invention is bonding, still has good adhesiveproperties when 800psi runs, and namely has good bonding intensity and chemical resistance.
2. effectively eliminate the shortcoming that conventional urethane adhesive solidification process has bubble to produce, namely there is higher anti-hydrolytic performance.
Embodiment
Below in conjunction with concrete embodiment, further restriction is done to technical scheme of the present invention, but claimed scope is not only confined to done description.
Epoxy resin modification double component solvent-free polyurethane system described in the invention, mainly improves the adhesiveproperties of tackiness agent to sea water desaltination membrane module from the following aspects:
The reaction of epoxy group(ing) and isocyanate group:
By the reaction of epoxy group(ing) and terminal isocyanate group base polyurethane prepolymer for use as, tackiness agent presents three-dimensional crosslinked network structure.
Part has neither part nor lot in the epoxy resin of reaction and corresponding solidifying agent and reacts and generate epoxy adhesive.Three-dimensional net structure polyurethane adhesive, a small amount of epoxy adhesive, by blended, make it to form interpenetrating net polymer, thus the mechanical property of tackiness agent, adhesiveproperties and water resistance are improved.
Embodiment 1
A preparation method for epoxy resin dual-component polyurethane adhesive, comprises the following steps:
(1) component A preparation: by 60kg polyether glycol and the mixing of 2kg isocyanic ester, order by merging is that isocyanic ester adds in polyether glycol, and added at 7min, and employing stirring speed is 50r/min carries out stir process, and to adjust temperature be 60 DEG C, after its reaction 0.5h, obtain mixture; Again 1kg epoxy curing agent is joined in mixture, and at temperature is 50 DEG C Keep agitation 0.5h, then be placed in normal temperature environment, naturally cool to normal temperature, can component A be obtained, stand-by;
(2) B component preparation: by 80kg isocyanic ester and the mixing of 15kg polyether glycol, order by merging is that polyether glycol adds in isocyanic ester, and added at 7min, and employing stirring speed is 50r/min carries out stir process, and to adjust temperature be 50 DEG C, after its reaction 0.5h, obtain terminal isocyanate group base polyurethane prepolymer for use as; Again 2kg epoxy resin composite is joined in terminal isocyanate group base polyurethane prepolymer for use as, and at temperature is 60 DEG C Keep agitation 0.5h, then be placed in normal temperature environment, naturally cool to normal temperature, can B component be obtained, stand-by;
(3) be mixed with tackiness agent: after prepared by A, B component, carried out independent splendid attire, and in use, then be that 4:3 mixes at 1min by A, B component according to weight ratio, epoxy resin dual-component polyurethane adhesive can be obtained.
Polyether glycol in described component A to be molecular weight be 400 polyoxypropyleneglycol;
Described isocyanic ester is vulcabond;
Described epoxy curing agent is methyl tetrahydrophthalic anhydride (MeTHPA).
Isocyanic ester described in described B component is HDI biuret;
Described polyether glycol is plam oil;
Described epoxy resin composite is 4,5-oxepane-1, the composition of 2-dicarboxylic acid 2-glycidyl ester, glycidyl ester type two functional group epoxy resin 711, bisphenol A type epoxy resin E-51, the mixture that the proportioning being 1:1:1 according to mass ratio mixes.
Embodiment 2
A preparation method for epoxy resin dual-component polyurethane adhesive, comprises the following steps:
(1) component A preparation: by 120kg polyether glycol and the mixing of 10kg isocyanic ester, order by merging is that isocyanic ester adds in polyether glycol, and added at 10min, and employing stirring speed is 90r/min carries out stir process, and to adjust temperature be 80 DEG C, after its reaction 2h, obtain mixture; Again 5kg epoxy curing agent is joined in mixture, and at temperature is 80 DEG C Keep agitation 1h, then be placed in normal temperature environment, naturally cool to normal temperature, can component A be obtained, stand-by;
(2) B component preparation: by 120kg isocyanic ester and the mixing of 50kg polyether glycol, order by merging is that polyether glycol adds in isocyanic ester, and added at 10min, and employing stirring speed is 90r/min carries out stir process, and to adjust temperature be 90 DEG C, after its reaction 2h, obtain terminal isocyanate group base polyurethane prepolymer for use as; Again 20kg epoxy resin composite is joined in terminal isocyanate group base polyurethane prepolymer for use as, and at temperature is 80 DEG C Keep agitation 1h, then be placed in normal temperature environment, naturally cool to normal temperature, can B component be obtained, stand-by;
(3) be mixed with tackiness agent: after prepared by A, B component, carried out independent splendid attire, and in use, then be that 6:5 mixes at 4min by A, B component according to weight ratio, epoxy resin dual-component polyurethane adhesive can be obtained.
Polyether glycol in described component A is molecular weight is the polyoxytrimethylene triol of 1000, the equal proportion mixture of Viscotrol C;
Described isocyanic ester is tolylene diisocyanate TDI tripolymer, HDI biuret, the trimerical equal proportion mixture of HDI;
Described epoxy curing agent is methyl tetrahydrophthalic anhydride (MeTHPA).
Isocyanic ester described in described B component is tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate equal proportion mixture;
Described polyether glycol is the polyoxytrimethylene triol of molecular weight 1000;
Described epoxy resin composite is 4,5-oxepane-1,2-dicarboxylic acid 2-glycidyl ester.
Embodiment 3
A preparation method for epoxy resin dual-component polyurethane adhesive, comprises the following steps:
(1) component A preparation: by 90kg polyether glycol and the mixing of 8kg isocyanic ester, order by merging is that isocyanic ester adds in polyether glycol, and added at 9min, and employing stirring speed is 70r/min carries out stir process, and to adjust temperature be 70 DEG C, after its reaction 1.5h, obtain mixture; Again 3kg epoxy curing agent is joined in mixture, and at temperature is 65 DEG C Keep agitation 1.5h, then be placed in normal temperature environment, naturally cool to normal temperature, can component A be obtained, stand-by;
(2) B component preparation: by 100kg isocyanic ester and the mixing of 35kg polyether glycol, order by merging is that polyether glycol adds in isocyanic ester, and added at 9min, and employing stirring speed is 70r/min carries out stir process, and to adjust temperature be 70 DEG C, after its reaction 1.5h, obtain terminal isocyanate group base polyurethane prepolymer for use as; Again 18kg epoxy resin composite is joined in terminal isocyanate group base polyurethane prepolymer for use as, and at temperature is 70 DEG C Keep agitation 0.9h, then be placed in normal temperature environment, naturally cool to normal temperature, can B component be obtained, stand-by;
(3) be mixed with tackiness agent: after prepared by A, B component, carried out independent splendid attire, and in use, then be that 5:4 mixes at 3min by A, B component according to weight ratio, epoxy resin dual-component polyurethane adhesive can be obtained.
Polyether glycol in described component A to be molecular weight be 400 polyoxypropyleneglycol, the polyoxytrimethylene triol of molecular weight 1000, Viscotrol C, hydrogenated castor oil, soybean oil, plam oil equal proportion mixture;
Described isocyanic ester is HDI tripolymer;
Described epoxy curing agent is methyl tetrahydrophthalic anhydride (MeTHPA).
Isocyanic ester described in described B component is diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate, TDI tripolymer, HDI biuret, HDI tripolymer equal proportion mixture;
Described polyether glycol is plam oil;
Described epoxy resin composite is 4,5-oxepane-1,2-dicarboxylic acid 2-glycidyl ester.
Test example:
Epoxy resin dual-component polyurethane adhesive obtained in Example 1, embodiment 2, embodiment 3 is used for bonding seawater desalination reverse osmosis membrane module, and run 1.5h under assembly being placed in 800psi condition, and the viscosity of A, B component and the tree lace stripping strength of membrane module are detected, its data results is as shown in table 1 below:
Table 1
As can be seen from the table, the bonding seawater desalination reverse osmosis membrane module of embodiment of the present invention epoxy resin polyurethane adhesive is carrying out still maintaining good adhesiveproperties in desalting process, therefore, this tackiness agent is applicable to bonding seawater desalination reverse osmosis membrane module.
In the embodiment of the present invention in preparation method by epoxy resin is incorporated in double component solvent-free polyurethane adhesive, because epoxy resin and urethane have good blended property and dispersiveness, therefore can form the cross-linked network structure mutually run through.This network structure is when being subject to impacting with high pressure, and stress dispersion more even, enable material have the performance of molecule segment Relative sliding, destroy this network architecture just needs larger energy.Therefore, the bonding seawater desalination reverse osmosis membrane module of epoxy resin modification double component solvent-free polyurethane adhesive still maintains good tree lace peeling force in sea water desaltination operational process, thus ensures the normal operation of sea water desaltination membrane module.
It is important to point out at this, above embodiment and test example are only limitted to that the invention will be further elaborated, are not to further restriction of the present invention.
Claims (7)
1. an epoxy resin dual-component polyurethane adhesive, is characterized in that, is formed by component A and B component mixed preparing, and wherein the mass ratio of component A and B component is (4-6): (3-5).
2. epoxy resin dual-component polyurethane adhesive as claimed in claim 1, it is characterized in that, described component A and the mass ratio of B component are 5:4.
3. epoxy resin dual-component polyurethane adhesive as claimed in claim 1, it is characterized in that, described component A is hydroxyl-terminated polyurethane performed polymer, and its material component is polyether glycol 60-120 part, isocyanic ester 2-10 part, epoxy curing agent 1-5 part; Described B component is epoxy resin modification terminal isocyanate group base polyurethane prepolymer for use as, and its material component is isocyanic ester 80-120 part, polyether glycol 15-50 part, epoxy resin composite 2-20 part.
4. epoxy resin dual-component polyurethane adhesive as claimed in claim 3, it is characterized in that, polyether glycol in described component A to be molecular weight be 400 polyoxypropyleneglycol, the polyoxytrimethylene triol of molecular weight 1000, Viscotrol C, hydrogenated castor oil, soybean oil, the mixture of one or more in plam oil; Described isocyanic ester is the mixture of one or more in vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate, liquefied mdi, TDI tripolymer, HDI biuret, HDI tripolymer; Described epoxy curing agent is methyl tetrahydrophthalic anhydride (MeTHPA).
5. epoxy resin dual-component polyurethane adhesive as claimed in claim 3, it is characterized in that, isocyanic ester described in described B component is one or more mixtures in vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate, liquefied mdi, TDI tripolymer, HDI biuret, HDI tripolymer; Described polyether glycol is polyoxypropyleneglycol, the polyoxytrimethylene triol of molecular weight 1000, Viscotrol C, the soybean oil of molecular weight 400, the mixture of one or more in plam oil; Described epoxy resin composite is the composition of one or more in 4,5-oxepane-1,2-dicarboxylic acid 2-glycidyl ester, glycidyl ester type two functional group epoxy resin 711, bisphenol A type epoxy resin E-51.
6. epoxy resin dual-component polyurethane adhesive as claimed in claim 3, it is characterized in that, described component A is hydroxyl-terminated polyurethane performed polymer, and its material component is polyether glycol 90 parts, isocyanic ester 7 parts, epoxy curing agent 3 parts; Described B component is epoxy resin modification terminal isocyanate group base polyurethane prepolymer for use as, and its material component is isocyanic ester 100 parts, polyether glycol 35 parts, epoxy resin composite 18 parts.
7. the preparation method of the epoxy resin dual-component polyurethane adhesive as described in any one of claim 1-6, is characterized in that, comprise the following steps:
(1) component A preparation: polyether glycol and isocyanic ester are mixed according to proportioning, order by merging is that isocyanic ester adds in polyether glycol, and added at 7-10min, and employing stirring speed is 50-90r/min carries out stir process, and to adjust temperature be 60 DEG C ~ 80 DEG C, after its reaction 0.5h ~ 2h, obtain mixture; Again epoxy curing agent is joined in mixture, and at temperature is 50 DEG C ~ 80 DEG C Keep agitation 0.5h ~ 1h, then be placed in normal temperature environment, naturally cool to normal temperature, can component A be obtained, stand-by;
(2) B component preparation: isocyanic ester and polyether glycol are mixed according to proportioning mixing, order by merging is that polyether glycol adds in isocyanic ester, and added at 7-10min, and employing stirring speed is 50-90r/min carries out stir process, and to adjust temperature be 50 DEG C ~ 90 DEG C, after its reaction 0.5h ~ 2h, obtain terminal isocyanate group base polyurethane prepolymer for use as; Again epoxy resin composite is joined in terminal isocyanate group base polyurethane prepolymer for use as, and at temperature is 60 DEG C ~ 80 DEG C Keep agitation 0.5h ~ 1h, then be placed in normal temperature environment, naturally cool to normal temperature, can B component be obtained, stand-by;
(3) be mixed with tackiness agent: after prepared by A, B component, carried out independent splendid attire, and in use, then A, B component are mixed at 1-4min according to proportioning, epoxy resin dual-component polyurethane adhesive can be obtained.
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| CN109554152A (en) * | 2018-10-30 | 2019-04-02 | 山东北方现代化学工业有限公司 | A kind of heat-resisting one-component polyurethane sealant and preparation method thereof |
| CN109851753A (en) * | 2018-11-21 | 2019-06-07 | 上海华峰新材料研发科技有限公司 | The polyurethane and its preparation method and application of epoxy-modified polymer modification |
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| CN111704878B (en) * | 2020-06-18 | 2022-04-22 | 广州市黄埔乐天实业有限公司 | Modified cellulose-based thread sealant and preparation method thereof |
| CN112300711A (en) * | 2020-11-18 | 2021-02-02 | 东莞市新懿电子材料技术有限公司 | Glue special for VCM motor and preparation method thereof |
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