CN116536021B - Polyurethane adhesive and preparation method thereof - Google Patents
Polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN116536021B CN116536021B CN202310481337.8A CN202310481337A CN116536021B CN 116536021 B CN116536021 B CN 116536021B CN 202310481337 A CN202310481337 A CN 202310481337A CN 116536021 B CN116536021 B CN 116536021B
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- polyol
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- polyurethane
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 80
- 239000000853 adhesive Substances 0.000 title claims abstract description 79
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- 239000004814 polyurethane Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 118
- 150000003077 polyols Chemical class 0.000 claims abstract description 118
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 26
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000012075 bio-oil Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 36
- 239000002808 molecular sieve Substances 0.000 claims description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 26
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 24
- 239000002516 radical scavenger Substances 0.000 claims description 18
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 13
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000004359 castor oil Substances 0.000 claims description 12
- 235000019438 castor oil Nutrition 0.000 claims description 12
- 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 12
- 239000000203 mixture Substances 0.000 claims description 12
- 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 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 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 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 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 3
- 239000013638 trimer Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 17
- 239000000758 substrate Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004261 Ascorbyl stearate Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000012974 tin catalyst Substances 0.000 description 7
- 239000000956 alloy Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000010998 test method 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
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
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a polyurethane adhesive and a preparation method thereof, wherein a component A of the polyurethane adhesive comprises polyether polyol, bio-oil modified polyol, hyperbranched polyol, a catalyst, a first water removing agent and a first filler, and a component B comprises a polyurethane prepolymer, a second water removing agent and a second filler. According to the invention, hyperbranched polyol is introduced into the adhesive system, so that the adhesive strength of the adhesive to the base materials such as aluminum and the like can be greatly improved, and the Young modulus is kept low, so that the adhesive has good flexibility.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a polyurethane adhesive and a preparation method thereof.
Background
Polyurethane adhesives, also called polyurethane adhesives, refer to adhesives containing urethane groups (-NHCOO-) or isocyanate groups (-NCO) in the molecular chain, are an important component in polyurethane resins currently being developed rapidly, have excellent properties, and are widely used in many aspects. Particularly, with the development of new energy automobiles at a high speed in recent years, polyurethane adhesives are also used in automobile battery pack structures, for example, in the process of assembling a power battery, a battery mold and a shell are required to be bonded, and most of power battery shells are made of light and low-cost metal aluminum, so that when polyurethane structural adhesives and polyurethane heat conduction structural adhesives are selected, the polyurethane adhesives are generally required to have higher bonding strength to aluminum materials and alloy metal materials thereof.
However, the polyurethane adhesive has generally poorer bonding effect on metal aluminum, and the epoxy resin adhesive in the prior art has the defects of higher hardness, lower tolerance on high-frequency vibration conditions and the like, and does not meet the use requirement of the existing new energy automobile adhesive. In order to optimize the bonding effect between the polyurethane adhesive and the metal aluminum, the prior art generally needs to bond the aluminum material and the alloy material thereof after surface treatment, for example, polishing the aluminum material and cleaning the surface, but this clearly increases the complexity of the process treatment, which is not beneficial to the improvement of the production efficiency. Therefore, development of a polyurethane adhesive for new energy sources, which has excellent adhesion properties to non-surface-treated aluminum materials and their alloy materials, is a problem to be solved at present.
Disclosure of Invention
The invention aims to solve the problems that the existing polyurethane adhesive has poor adhesion performance with aluminum and other base materials, and the aluminum and other base materials need to be pretreated, so that the process complexity and the cost are increased.
In order to solve the above problems, the present invention provides a polyurethane adhesive comprising: the polyurethane foam comprises a component A and a component B, wherein the component A comprises polyether polyol, bio-oil modified polyol, hyperbranched polyol, a catalyst, a first water scavenger and a first filler, and the component B comprises a polyurethane prepolymer, a second water scavenger and a second filler.
Preferably, the hyperbranched polyol comprises 10-25% by weight of the total polyol, and the total polyol is the sum of the polyether polyol, the bio-oil modified polyol and the hyperbranched polyol.
Preferably, the hyperbranched polyol comprises one or more of hydroxyl-terminated hyperbranched polyesters, brands bolton H2004 and bolton H311, and the hydroxyl-terminated hyperbranched polyester comprises one or more of brands HyPer H101, hyPer H102, hyPer H103 and HyPer H104.
Preferably, the catalyst comprises one or more of an organotin catalyst.
Preferably, the first water scavenger comprises a 4A molecular sieve and the second water scavenger comprises a 4A molecular sieve.
Preferably, the first filler comprises alumina and aluminum hydroxide, and the second filler comprises alumina and aluminum hydroxide.
Preferably, the bio-oil modified polyol comprises a castor oil modified polyol.
Preferably, the polyurethane prepolymer comprises an oligomer containing isocyanate groups obtained by reacting one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, and polymeric diphenylmethane diisocyanate with a polyol comprising one or more of polyether polyol, polyester polyol, and polycaprolactone polyol.
Preferably, the component A comprises the following components in parts by weight: 31-66 parts of polyether polyol, 70-75 parts of bio-oil modified polyol, 7-42 parts of hyperbranched polyol, 0.1-0.2 part of catalyst, 1-5 parts of first water scavenger and 750-900 parts of first filler;
the component B comprises the following components in parts by weight: 45-65 parts of hexamethylene diisocyanate prepolymer, 84-120 parts of 4,4' -diphenylmethane diisocyanate prepolymer, 1-5 parts of second water scavenger and 650-900 parts of second filler.
Compared with the prior art, the polyurethane adhesive has the advantages that:
according to the invention, by adding the hyperbranched polyol with high functional groups, more and more firm carbamate linkages are formed by utilizing the chemical bonding action between the functional groups such as hydroxyl groups and amino groups at the tail ends of the hyperbranched polyol and the isocyanate and the hydroxyl groups on the surface of the metal substrate, so that the bonding strength to the substrate is increased; in addition, the urethane generated by the reaction between the A, B components of the polyurethane adhesive has strong polarity, and the urethane groups with high content can form more van der Waals force and hydrogen bond combination with the hydroxyl groups on the surface of the metal substrate, so that the bonding strength of the adhesive to the substrates such as aluminum, steel and the like is improved, and the shearing strength of the polyurethane adhesive to the aluminum and the alloy materials thereof is more than 9MPa. Meanwhile, because the special structure of the hyperbranched polyol contains a large amount of cavity volume in the molecular structure, and can absorb energy when being stressed, the addition of the hyperbranched polyol can improve the crosslinking density of a cured product, but can still keep the material to have a lower modulus, and the Young modulus of the polyurethane adhesive is lower than 500MPa.
The invention also provides a preparation method of the polyurethane adhesive, which is used for preparing the polyurethane adhesive, and comprises the following steps:
uniformly mixing polyether polyol, bio-oil modified polyol, hyperbranched polyol and a catalyst, heating to 110-120 ℃, stirring and dehydrating for 2-3 hours under vacuum condition, cooling, adding a first water removing agent and a first filler, and stirring in vacuum until the mixture is uniform to obtain a component A;
uniformly mixing the polyurethane prepolymer, adding a second water removing agent and a second filler, and stirring in vacuum until the polyurethane prepolymer is uniformly mixed to obtain a component B;
and mixing the component A and the component B to obtain the polyurethane adhesive.
The advantages of the preparation method of the polyurethane adhesive compared with the prior art are the same as those of the polyurethane adhesive compared with the prior art, and are not repeated here.
Drawings
FIG. 1 is a flow chart of a preparation method of a polyurethane adhesive in an embodiment of the invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The polyurethane adhesive of the embodiment of the invention comprises the following components: the polyurethane foam comprises a component A and a component B, wherein the component A comprises polyether polyol, bio-oil modified polyol, hyperbranched polyol, a catalyst, a first water scavenger and a first filler, and the component B comprises a polyurethane prepolymer, a second water scavenger and a second filler.
Because the adhesion performance between the existing polyurethane adhesive and aluminum alloy materials without surface treatment is poor, pretreatment is usually required for the aluminum and aluminum alloy materials, thereby increasing the complexity and cost of the process. Therefore, the material components of the polyurethane adhesive are improved and optimized, and the adhesive strength between the polyurethane adhesive and the aluminum and other base materials is improved by optimizing the components of the polyurethane adhesive, and the shearing strength of the polyurethane adhesive of the embodiment to the aluminum and the aluminum alloy materials is higher than 9MPa through tests; meanwhile, the polyurethane adhesive of the embodiment can also keep lower elastic modulus, keep good flexibility and improve tolerance under high-frequency vibration conditions, and the Young modulus of the polyurethane adhesive of the embodiment is lower than 500MPa through tests. The specific mechanism analysis is as follows:
the embodiment is a bi-component polyurethane adhesive, which comprises A, B components, belongs to a reactive adhesive, and is configured according to a certain proportion before use, and the two components are mixed for crosslinking reaction so as to realize curing adhesion. Wherein the component A is a main agent, the component B is a curing agent, and the component B is a polyurethane prepolymer containing isocyanate groups. In the embodiment, the hyperbranched polyol with high functional groups is added into the component A, and compared with the conventional polyol, the terminal end of the hyperbranched polyol has more functional groups such as hydroxyl groups, amino groups and the like, so that in the whole polyurethane adhesive system, the terminal hydroxyl groups, amino groups and the like of the hyperbranched polyol of the component A, the isocyanate groups of the component B and the hydroxyl groups on the surface of the metal substrate can be subjected to chemical reaction to form more and firmer urethane bonding, and the bonding strength to the substrate is improved due to the chemical bonding. The reason why more and more stable urethane is formed is mainly that, on the one hand, the terminal hydroxyl group, amine group and the like of the hyperbranched polyol can be chemically bonded to the hydroxyl group on the surface of the substrate to form urethane, and on the other hand, the terminal hydroxyl group, amine group and the like of the hyperbranched polyol can be chemically bonded to the isocyanate group in the B component of the adhesive to form urethane, that is, the chemical bonding between the A, B components of the polyurethane adhesive. Therefore, in this embodiment, by adding the hyperbranched polyol with a high functional group into the adhesive system, more and more firm urethane bonds can be formed, thereby increasing the bonding strength to the substrate. In addition, even though the terminal hydroxyl groups, amine groups and other groups of the hyperbranched polyol are not bonded with the hydroxyl groups on the surface of the substrate, the urethane generated by the reaction between the A, B components of the polyurethane adhesive has strong polarity, so that the high-content urethane groups generated by the reaction can also form more van der Waals force and hydrogen bond combination with the hydroxyl groups on the surface of the metal substrate, thereby enhancing the bonding strength of the adhesive to the substrates such as aluminum, steel and the like.
In addition, in the polyurethane adhesive system of this embodiment, the added hyperbranched polyol can increase the crosslinking density of the cured product, and in general, the higher the crosslinking density is, the higher the modulus is, but because the specific structure of the hyperbranched polyol contains a large amount of hole volumes in the molecular structure and can absorb energy when being stressed, the addition of the hyperbranched polyol in this embodiment can increase the crosslinking density of the cured product, but can still keep the lower modulus of the material, so that the polyurethane adhesive has good flexibility, and the power battery can be subjected to severe vibration in the use process, therefore, the polyurethane adhesive has low modulus and good flexibility, and can play an important role.
In some embodiments, the hyperbranched polyol comprises from 10 to 25 weight percent of the total polyol, the total polyol being the sum of the polyether polyol, the bio-oil modified polyol, and the hyperbranched polyol.
The content of the hyperbranched polyol is optimized, and the duty ratio of the hyperbranched polyol is set in the range, so that the polyurethane adhesive has stronger bonding performance and can keep lower Young modulus.
In some embodiments, the hyperbranched polyol comprises one or more of hydroxyl-terminated hyperbranched polyesters, brands bolton H2004 and bolton H311, including one or more of brands HyPer H101, hyPer H102, hyPer H103, and HyPer H104.
The polyether polyol comprises polyether glycol, polyether triol and the like.
The catalyst includes one or more of organotin catalysts such as dibutyltin dilaurate, stannous octoate, and the like.
The first water scavenger comprises a 4A molecular sieve and the second water scavenger comprises a 4A molecular sieve. The pore diameter of the 4A molecular sieve is 4A, so that any molecules with the diameter smaller than 4A can be adsorbed, and the molecular sieve is mainly used for adsorbing water in a polyurethane system, has the effects of removing water and removing bubbles, and avoids the influence of bubbles on the bonding performance in the curing process of the adhesive.
The first filler comprises alumina and aluminum hydroxide, and the second filler comprises alumina and aluminum hydroxide.
The biological oil modified polyol comprises castor oil modified polyol, and can also be modified by other biological oils such as rapeseed oil, sunflower oil and the like.
In some embodiments, the polyurethane prepolymer comprises an oligomer containing isocyanate groups derived from the reaction of one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, and polymeric diphenylmethane diisocyanate with a polyol comprising one or more of polyether polyol, polyester polyol, and polycaprolactone polyol.
In a preferred example, the polyurethane prepolymer is a hexamethylene diisocyanate prepolymer obtained by reacting monomeric hexamethylene diisocyanate with a polyol using Desmodur E305 (Desmodur E305); alternatively, desmodur CD-C, which is a prepolymer of 4,4 '-diphenylmethane diisocyanate derived from the reaction of 4,4' -diphenylmethane diisocyanate with a polyol, is used as Desmodur E305 and Desmodur CD-C, both of which are commercially available.
In some embodiments, the component a comprises, in parts by weight: 31-66 parts of polyether polyol, 70-75 parts of bio-oil modified polyol, 7-42 parts of hyperbranched polyol, 0.1-0.2 part of catalyst, 1-5 parts of first water scavenger and 750-900 parts of first filler;
the component B comprises the following components in parts by weight: 45-65 parts of hexamethylene diisocyanate prepolymer, 84-120 parts of 4,4' -diphenylmethane diisocyanate prepolymer, 1-5 parts of second water scavenger and 650-900 parts of second filler.
The embodiment of the invention also provides a preparation method of the polyurethane adhesive, which is shown in fig. 1 and comprises the following steps:
uniformly mixing polyether polyol, bio-oil modified polyol, hyperbranched polyol and a catalyst, heating to 110-120 ℃, stirring and dehydrating for 2-3 hours under vacuum condition, cooling, adding a first water removing agent and a first filler, and stirring in vacuum until the mixture is uniform to obtain a component A;
uniformly mixing the polyurethane prepolymer, adding a second water removing agent and a second filler, and stirring in vacuum until the polyurethane prepolymer is uniformly mixed to obtain a component B;
and mixing the component A and the component B to obtain the polyurethane adhesive.
The invention is further illustrated by the following specific examples.
Example 1
And (3) preparing a component A: 52 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical company Limited), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va.) and 21 parts of hyperbranched polyol (Boltorn H2004, perston) and 0.1 part of organic tin catalyst (T12, heng Guang Jiu Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing for standby.
And (2) preparing a component B: according to the weight parts, 54 parts of polyurethane prepolymer, namely, all E305 and 91 parts of all CD-C of the Deshi mould are stirred and mixed, 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing and sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
Example 2
And (3) preparing a component A: 52 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical company Limited), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va.) and 21 parts of hyperbranched polyol (Boltorn H311, perston) and 0.1 part of organic tin catalyst (T12, heng Guang Jiu Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing for standby.
And (2) preparing a component B: according to the weight parts, 45 parts of polyurethane prepolymer, namely, all E305 of a Deshi mould and 100 parts of Deshi mould, namely, all CD-C are stirred and mixed, 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing, and is sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
Example 3
And (3) preparing a component A: 52 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical Co., ltd.), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va. Taurus) and 21 parts of hyperbranched polyol (HyperH 101, wuhan hyperbranched technology Co., ltd.) and 0.1 part of organotin catalyst (T12, heng Guangdong Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of alumina and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing.
And (2) preparing a component B: according to the weight parts, 65 parts of polyurethane prepolymer, namely, all E305 and 120 parts of all CD-C of the Deshi mould are stirred and mixed, 1 part of 4A molecular sieve, 450 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing, and is sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
Example 4
And (3) preparing a component A: 58 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical company Limited), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va.) and 15 parts of hyperbranched polyol (Boltorn H2004, perston) and 0.1 part of organic tin catalyst (T12, heng Guang Jiu Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing for standby.
And (2) preparing a component B: according to the weight parts, 54 parts of polyurethane prepolymer, namely, all E305 and 95 parts of all CD-C of the Deshi mould are stirred and mixed, 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing, and is sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
Example 5
And (3) preparing a component A: 39 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical company Limited), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va.) and 34 parts of hyperbranched polyol (Boltorn H311, perston) and 0.1 part of organic tin catalyst (T12, heng Guang Jiu Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing for standby.
And (2) preparing a component B: according to the weight parts, 54 parts of polyurethane prepolymer, namely, all E305 and 97 parts of all CD-C of the Deshi mould are stirred and mixed, 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing, and is sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
In order to verify that the adhesive property of the polyurethane adhesive can be improved by adding the hyperbranched polyol with high functional groups, and the lower modulus is kept, the following comparative examples are also provided.
Comparative example 1
And (3) preparing a component A: 52 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical Co., ltd.), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va. Taurus) and 21 parts of high-molecular polyether glycol (PPG 2000, shanghai high-bridge petrochemical Co., ltd.) and 0.1 part of organotin catalyst (T12, heng Guangda Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing.
And (2) preparing a component B: according to the weight parts, 54 parts of polyurethane prepolymer, namely, all E305 and 91 parts of all CD-C of the Deshi mould are stirred and mixed, 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing and sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
Comparative example 2
And (3) preparing a component A: 52 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical Co., ltd.), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va.) and 21 parts of high-molecular-weight polycarbonate glycol (PH 200, UBE) and 0.1 part of organic tin catalyst (T12, heng Guang Da Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing for standby.
And (2) preparing a component B: according to the weight parts, 54 parts of polyurethane prepolymer, namely, all E305 and 91 parts of all CD-C of the Deshi mould are stirred and mixed, 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing and sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
To illustrate that the proportion of hyperbranched polyol added according to the invention has a higher bond strength in the range of 10-25% and maintains a lower modulus, the invention also provides the following comparative examples.
Comparative example 3
And (3) preparing a component A: 66 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical company Limited), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va.) and 7 parts of hyperbranched polyol (Boltorn H2004, perston) and 0.1 part of organic tin catalyst (T12, heng Guang Jiu Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing for standby.
And (2) preparing a component B: according to the weight parts, 58 parts of polyurethane prepolymer, namely, all E305 and 95 parts of all CD-C of the Deshi mould are stirred and mixed, 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing, and is sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
Comparative example 4
And (3) preparing a component A: 31 parts of low-viscosity polyether glycol (PPG 400, shanghai high-bridge petrochemical company Limited), 70 parts of hydrophobic castor oil modified polyol (Polycin M-365, va.) and 42 parts of hyperbranched polyol (Boltorn H2004, perston) and 0.1 part of organic tin catalyst (T12, heng Guang Jiu Co., ltd.) are mixed together by weight, heated to 110 ℃, stirred and dehydrated for 2 hours under vacuum, cooled, added with 1 part of 4A molecular sieve, 550 parts of aluminum oxide and 200 parts of aluminum hydroxide, and stirred for 2 hours under vacuum for uniform mixing for standby.
And (2) preparing a component B: 50 parts of polyurethane prepolymer, namely, deshi die E305 and 84 parts of Deshi die CD-C are stirred and mixed, 1 part of 4A molecular sieve, 600 parts of aluminum oxide and 200 parts of aluminum hydroxide are added, and the mixture is stirred and mixed for 2 hours in vacuum for uniform mixing and sealed for standby.
And mixing the prepared component A and the prepared component B to obtain the polyurethane adhesive.
The main components and weights of the A and B components of examples 1 to 5 and comparative examples 3 and 4 are shown in tables 1 and 2, and the polyurethane adhesives prepared in examples 1 to 5 and comparative examples 1 to 4 were tested, and the substrates bonded with the polyurethane adhesives were subjected to destructive tests such as peeling or shearing, and the test results are shown in Table 3.
The test method or standard is as follows: shear strength tests were performed on 3 series aluminum substrates and 6 series aluminum substrates according to standard GB/T7124. Young's modulus test experiments were performed according to standard GB/TGB/T1040.
Table 1:
table 2:
table 3:
as can be seen from Table 3, the polyols of comparative examples 1 and 2 are compounded by polyether polyol and bio-oil modified polyol or by polyether polyol, polycarbonate polyol and bio-oil modified polyol, and the bonding strength of the polyols is basically lower than 7.33MPa, while the bonding strengths of examples 1 to 5 and comparative examples 3 and 4 using the technique of the present invention are much higher than those of comparative examples 1 and 2, wherein the amount of the hyperbranched polyol in comparative example 3 is too low and lower than 10%, resulting in the strength of lower than 9MPa, and the bonding strengths of examples 1 to 5 are all higher than 9MPa; the comparative example 4 has high flexibility when the consumption of hyperbranched polyol is too high, the proportion is up to 29.4% and exceeds 25% required by the invention, so that the elastic modulus exceeds 500MPa, and the elastic modulus of examples 1-5 is below 500MPa. According to the comparison of examples 1-5 and comparative examples 1-4, it is demonstrated that the introduction of hyperbranched polyol and the limitation of the amount of hyperbranched polyol to be used in the range of 10-25% can greatly improve the adhesive strength of the adhesive to aluminum substrates while also maintaining a lower modulus of the material.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (6)
1. A polyurethane adhesive, comprising: the polyurethane foam comprises a component A and a component B, wherein the component A comprises polyether polyol, bio-oil modified polyol, hyperbranched polyol, a catalyst, a first water scavenger and a first filler, and the component B comprises polyurethane prepolymer, a second water scavenger and a second filler; wherein the hyperbranched polyol comprises one or more of hydroxyl-terminated hyperbranched polyester, and hyperbranched polyester polyols with the brands of bolton H2004 and bolton H311, the hydroxyl-terminated hyperbranched polyester comprises one or more of the brands of HyPer H101, hyPer H102, hyPer H103 and HyPer H104, the first water scavenger comprises a 4A molecular sieve, the first filler comprises alumina and aluminum hydroxide, the second water scavenger comprises a 4A molecular sieve, and the second filler comprises alumina and aluminum hydroxide; wherein the hyperbranched polyol comprises 10-25% by weight of the total polyol, the total polyol comprising the polyether polyol, the bio-oil modified polyol and the hyperbranched polyol.
2. The polyurethane adhesive of claim 1, wherein the catalyst comprises one or more of an organotin catalyst.
3. The polyurethane adhesive of claim 1, wherein the bio-oil modified polyol comprises a castor oil modified polyol.
4. The polyurethane adhesive of claim 1, wherein the polyurethane prepolymer comprises an oligomer containing isocyanate groups obtained by reacting one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, and polymeric diphenylmethane diisocyanate with a polyol comprising one or more of polyether polyol, polyester polyol.
5. The polyurethane adhesive of claim 1, wherein the a component comprises, in parts by weight: 31-66 parts of polyether polyol, 70-75 parts of bio-oil modified polyol, 7-42 parts of hyperbranched polyol, 0.1-0.2 part of catalyst, 1-5 parts of first water scavenger and 750-900 parts of first filler;
the component B comprises the following components in parts by weight: 45-65 parts of hexamethylene diisocyanate prepolymer, 84-120 parts of 4,4' -diphenylmethane diisocyanate prepolymer, 1-5 parts of second water scavenger and 650-900 parts of second filler; wherein the hexamethylene diisocyanate prepolymer is obtained by reacting hexamethylene diisocyanate with polyol; the 4,4 '-diphenylmethane diisocyanate prepolymer is obtained by reacting 4,4' -diphenylmethane diisocyanate with polyol.
6. A method for preparing a polyurethane adhesive according to any one of claims 1 to 5, comprising:
uniformly mixing polyether polyol, bio-oil modified polyol, hyperbranched polyol and a catalyst, heating to 110-120 ℃, stirring and dehydrating for 2-3 hours under vacuum condition, cooling, adding a first water removing agent and a first filler, and stirring in vacuum until the mixture is uniform to obtain a component A;
uniformly mixing the polyurethane prepolymer, adding a second water removing agent and a second filler, and stirring in vacuum until the polyurethane prepolymer is uniformly mixed to obtain a component B;
and mixing the component A and the component B to obtain the polyurethane adhesive.
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| CN110776869A (en) * | 2019-06-21 | 2020-02-11 | 南京威邦新材料有限公司 | High-temperature-resistant high-strength polyurethane structural adhesive and preparation method thereof |
| CN111349417A (en) * | 2020-05-07 | 2020-06-30 | 北京天山新材料技术有限公司 | Polyurethane adhesive composition and polyurethane adhesive |
| CN115926716A (en) * | 2022-12-08 | 2023-04-07 | 湖北回天新材料股份有限公司 | High-thermal-conductivity low-density two-component polyurethane structural adhesive and preparation method thereof |
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| CN110776869A (en) * | 2019-06-21 | 2020-02-11 | 南京威邦新材料有限公司 | High-temperature-resistant high-strength polyurethane structural adhesive and preparation method thereof |
| CN111349417A (en) * | 2020-05-07 | 2020-06-30 | 北京天山新材料技术有限公司 | Polyurethane adhesive composition and polyurethane adhesive |
| CN115926716A (en) * | 2022-12-08 | 2023-04-07 | 湖北回天新材料股份有限公司 | High-thermal-conductivity low-density two-component polyurethane structural adhesive and preparation method thereof |
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