CN116265557A - Polyurethane structural adhesive and preparation method thereof - Google Patents
Polyurethane structural adhesive and preparation method thereof Download PDFInfo
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- CN116265557A CN116265557A CN202111544437.8A CN202111544437A CN116265557A CN 116265557 A CN116265557 A CN 116265557A CN 202111544437 A CN202111544437 A CN 202111544437A CN 116265557 A CN116265557 A CN 116265557A
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- component
- tackifier
- structural adhesive
- polyurethane
- conductive filler
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 70
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 70
- 239000000853 adhesive Substances 0.000 title claims abstract description 69
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 47
- 150000003077 polyols Chemical class 0.000 claims abstract description 47
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 41
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000011231 conductive filler Substances 0.000 claims abstract description 31
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 30
- 229920002799 BoPET Polymers 0.000 claims abstract description 29
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 20
- 239000004359 castor oil Substances 0.000 claims abstract description 19
- 235000019438 castor oil Nutrition 0.000 claims abstract description 19
- 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 19
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims 7
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 18
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 18
- -1 polyethylene terephthalate Polymers 0.000 abstract description 6
- 241001391944 Commicarpus scandens Species 0.000 abstract 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 23
- 239000000945 filler Substances 0.000 description 15
- 239000012528 membrane Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C09J175/06—Polyurethanes from polyesters
-
- 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)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides polyurethane structural adhesive which is used for bonding with PET (polyethylene terephthalate) film materials and comprises a first component and a second component; the first component comprises a prepolymer, a first thermally conductive filler, and a first tackifier; the second component comprises a polyester polyol, a second thermally conductive filler, and a second tackifier; the prepolymer consists of isocyanate and polycaprolactone polyol, the isocyanate consists of HDI trimer and modified MDI, the polyester polyol consists of polycaprolactone polyol and modified castor oil, and the volume ratio of the first component to the second component is (0.9-1.1). The polyurethane structural adhesive solves the problem that the polyurethane structural adhesive is easy to break off in the using process after being bonded with the PET film material, and the peeling strength between the polyurethane structural adhesive and the PET film material is larger than 1N/mm. The invention also provides a preparation method of the polyurethane structural adhesive.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to polyurethane structural adhesive and a preparation method thereof.
Background
Polyurethane is short for polyurethane, and the English name is polyurethane, is an emerging organic polymer material, is known as fifth plastic, is widely applied to numerous fields of national economy due to the excellent performance, and relates to light industry, chemical industry, electronics, textile, medical treatment, building materials, automobiles, national defense, aerospace, aviation and the like.
The Chinese patent with publication number of CN112608707A discloses a double-component polyurethane structural adhesive and a preparation method thereof, wherein the double-component polyurethane structural adhesive comprises an A component and a B component, and the preparation raw materials of the A component comprise the following components in parts by weight: 10-30 parts of castor oil polyalcohol; 10-40 parts of phosphorus trichloride modified polyether polyol; 2-10 parts of aromatic polyester polyol; 15-40 parts of first heat conducting filler; 10-30 parts of first flame retardant filler; 0-30 parts of a first auxiliary agent, wherein the preparation raw materials of the component B comprise the following components in parts by weight: 5-30 parts of isocyanate-terminated polyurethane prepolymer; 30-60 parts of polymethylene polyphenyl polyisocyanate; 15-40 parts of a second heat-conducting filler; 10-30 parts of a second flame retardant filler; 0-6 parts of a second auxiliary agent. The flame retardant property of the material is greatly improved, the phosphorus trichloride modified polyether polyol is a special alkyl phosphite stabilizer, and is a phosphorus-containing polyol flame retardant, so that the flame retardant property and the shear strength of the material are remarkably improved, the consumption of flame retardant filler can be reduced by adding the phosphorus trichloride modified polyether polyol into the component A, the proportion of solid components in the component is reduced, the proportion of liquid components is improved, the density of the component is reduced, the aromatic polyester polyol has excellent hydrolysis resistance, heat stability and primary hydroxyl characteristic, the adhesive force of the glue to various metals and plastics is remarkably improved under the high-temperature condition, the high-temperature shear strength of the material is improved, the phosphorus trichloride modified polyether polyol has synergistic effect with the isocyanate-terminated polyurethane prepolymer component in the structural adhesive, and after the component A and the component B are mixed, the phosphorus trichloride modified polyether polyol can promote the crosslinking reaction of the isocyanate-terminated prepolymer in the component A, the crosslinking reaction is improved, the crosslinking density of the crosslinking reaction between the components is improved, the heat-resistant adhesive has excellent heat-conducting property and the high-temperature shear strength, and the high-temperature structural adhesive has remarkable flame retardant property and low-temperature shear strength. However, the adhesion of the bi-component polyurethane structural adhesive to the PET film is poor, the peel strength between the bi-component polyurethane structural adhesive and the PET film is less than 1N/mm, and the bi-component polyurethane structural adhesive has the problem of easy degumming in the use process.
Therefore, there is a need to develop a polyurethane structural adhesive and a preparation method thereof, so as to avoid the above-mentioned problems in the prior art.
Disclosure of Invention
The invention aims to provide polyurethane structural adhesive and a preparation method thereof, which solve the problem that the polyurethane structural adhesive is easy to come apart in the using process after being bonded with PET film, and the peel strength between the polyurethane structural adhesive and the PET film is greater than 1N/mm.
The polyurethane structural adhesive is used for bonding with PET (polyethylene terephthalate) film materials and comprises a first component and a second component;
the first component comprises a prepolymer, a first thermally conductive filler, and a first tackifier;
the second component comprises a polyester polyol, a second thermally conductive filler, and a second tackifier;
the prepolymer consists of isocyanate and polycaprolactone polyol, the isocyanate consists of HDI trimer and modified MDI, the polyester polyol consists of polycaprolactone polyol and modified castor oil, and the volume ratio of the first component to the second component is (0.9-1.1).
The polyurethane structural adhesive has the beneficial effects that: the HDI trimer has small molecular weight and lower polarity, can infiltrate the PET membrane material, has strong mechanical strength, low viscosity and good water resistance of the modified MDI, has low polarity and good toughness of the polycaprolactone polyol, can infiltrate the PET membrane material, and the prepolymer consists of the HDI trimer, the modified MDI and the polycaprolactone polyol, so that the mechanical strength and the water resistance of the prepolymer are better, and the PET membrane material can be infiltrated better; the polyester polyol consists of polycaprolactone polyol and modified castor oil, so that the polyester polyol has good hydrophobicity, strength and toughness and can infiltrate PET film materials; the volume ratio of the first component to the second component is (0.9-1.1), so that the first component and the second component are uniformly mixed and react thoroughly; the polyurethane structural adhesive consists of a prepolymer, a first heat-conducting filler, a first tackifier, polyester polyol, a second heat-conducting filler and a second tackifier, so that the polyurethane structural adhesive has good mechanical strength, water resistance and toughness, and can infiltrate into PET film materials well, the peel strength between the polyurethane structural adhesive and the PET film materials is greater than 1N/mm, and the problem that the polyurethane structural adhesive and the PET film materials are easy to come apart after being bonded in the using process is solved.
Optionally, the modified castor oil has an average molecular weight of 400-800 and an average functionality of 3.
Alternatively, the number average molecular weight of the polycaprolactone polyol in the first component and the polycaprolactone polyol in the second component are both 300-1000.
Optionally, the content of the HDI trimer is 10-20% by mass of the first component, the content of the modified MDI is 18-30%, the content of the polycaprolactone polyol in the first component is 20-30%, the content of the first heat-conducting filler is 35-50%, and the content of the first tackifier is 1-3%.
Optionally, the content of the polycaprolactone polyol in the second component is 10-30%, the content of the modified castor oil is 20-40%, the content of the second heat-conducting filler is 40-60%, and the content of the second tackifier is 1-3% based on the mass percentage of the second component.
Optionally, the first thermally conductive filler includes at least one of aluminum nitride, boron nitride, silicon nitride, aluminum oxide, magnesium oxide, and aluminum hydroxide, and the second thermally conductive filler includes at least one of aluminum nitride, boron nitride, silicon nitride, aluminum oxide, magnesium oxide, and aluminum hydroxide.
Optionally, the first heat conductive filler and the second heat conductive filler are both aluminum hydroxide.
Optionally, the first adhesion promoter and the second adhesion promoter are both fumed silica.
The invention further provides a preparation method of the polyurethane structural adhesive, which comprises the following steps:
mixing using HDI trimer and modified MDI to produce isocyanate;
heating reaction is carried out by using the isocyanate and polycaprolactone polyol to prepare a prepolymer;
mixing using the prepolymer, a first thermally conductive filler, and a first tackifier to produce a first component;
mixing using a polycaprolactone polyol and modified castor oil to produce a polyester polyol;
mixing using the polyester polyol, a second thermally conductive filler, and a second tackifier to produce a second component;
the first component and the second component are used for carrying out mixing reaction to prepare the polyurethane structural adhesive, and the volume ratio of the first component to the second component is (0.9-1.1) to (0.9-1.1).
The preparation method of the polyurethane structural adhesive has the beneficial effects that: the HDI trimer has small molecular weight and lower polarity, can infiltrate the PET membrane material, has strong mechanical strength, low viscosity and good water resistance of the modified MDI, has low polarity and good toughness of the polycaprolactone polyol, can infiltrate the PET membrane material, and the prepolymer consists of the HDI trimer, the modified MDI and the polycaprolactone polyol, so that the mechanical strength and the water resistance of the prepolymer are better, and the PET membrane material can be infiltrated better; the polyester polyol consists of polycaprolactone polyol and modified castor oil, so that the polyester polyol has good hydrophobicity, strength and toughness and can infiltrate PET film materials; the volume ratio of the first component to the second component is (0.9-1.1), so that the first component and the second component are uniformly mixed and react thoroughly; the polyurethane structural adhesive consists of a prepolymer, a first heat-conducting filler, a first tackifier, polyester polyol, a second heat-conducting filler and a second tackifier, so that the polyurethane structural adhesive has good mechanical strength, water resistance and toughness, and can infiltrate into PET film materials well, the peel strength between the polyurethane structural adhesive and the PET film materials is greater than 1N/mm, and the problem that the polyurethane structural adhesive and the PET film materials are easy to come apart after being bonded in the using process is solved.
Optionally, the temperature of the heating reaction is 70-100 ℃.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used herein, the word "comprising" and the like means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof without precluding other elements or items.
In the embodiment of the invention, the polyurethane structural adhesive is used for bonding with PET (polyethylene terephthalate) film and comprises a first component and a second component;
the first component comprises a prepolymer, a first thermally conductive filler, and a first tackifier;
the second component comprises a polyester polyol, a second thermally conductive filler, and a second tackifier;
the prepolymer consists of isocyanate and polycaprolactone polyol, the isocyanate consists of HDI trimer and modified MDI, the polyester polyol consists of polycaprolactone polyol and modified castor oil, and the volume ratio of the first component to the second component is (0.9-1.1). The HDI trimer has small molecular weight and lower polarity, can infiltrate the PET membrane material, has strong mechanical strength, low viscosity and good water resistance of the modified MDI, has low polarity and good toughness of the polycaprolactone polyol, can infiltrate the PET membrane material, and the prepolymer consists of the HDI trimer, the modified MDI and the polycaprolactone polyol, so that the mechanical strength and the water resistance of the prepolymer are better, and the PET membrane material can be infiltrated better; the polyester polyol consists of polycaprolactone polyol and modified castor oil, so that the polyester polyol has good hydrophobicity, strength and toughness and can infiltrate PET film materials; the volume ratio of the first component to the second component is (0.9-1.1), so that the first component and the second component are uniformly mixed and react thoroughly; the polyurethane structural adhesive consists of a prepolymer, a first heat-conducting filler, a first tackifier, polyester polyol, a second heat-conducting filler and a second tackifier, so that the polyurethane structural adhesive has good mechanical strength, water resistance and toughness, and can infiltrate into PET film materials well, the peel strength between the polyurethane structural adhesive and the PET film materials is greater than 1N/mm, and the problem that the polyurethane structural adhesive and the PET film materials are easy to come apart after being bonded in the using process is solved.
In some embodiments of the present invention, the HDI trimer is produced by trimerization of hexamethylene diisocyanate, wherein HDI is hexamethylene diisocyanate, and the chemical formula is C 8 H 12 N 2 O 2 The CAS number is 822-06-0.
In some embodiments of the present invention, the modified MDI is a carbodiimide-modified MDI, i.e., a liquefied MDI, also known as a monomer-modified MDI, which is a pure MDI into which carbodiimide groups (-n=c=n-) are introduced by self-condensation, and MDI is diphenylmethane-4, 4' -diisocyanate having the chemical formula C 15 H 10 N 2 O 2 CAS number 101-68-8.
In some embodiments of the invention, the modified castor oil has an average molecular weight of 400 to 800 and an average functionality of 3.
In some embodiments of the invention, the number average molecular weight of the polycaprolactone polyol in the first component and the polycaprolactone polyol in the second component are both 300-1000.
In some embodiments of the present invention, the HDI trimer is present in an amount of 10 to 20% by mass of the first component, the modified MDI is present in an amount of 18 to 30% by mass of the first component, the polycaprolactone polyol is present in an amount of 20 to 30% by mass of the first component, the first thermally conductive filler is present in an amount of 35 to 50% by mass of the first component, and the first adhesion promoter is present in an amount of 1 to 3% by mass of the first component.
In some embodiments of the present invention, the second component comprises, by mass, 10 to 30% of the polycaprolactone polyol, 20 to 40% of the modified castor oil, 40 to 60% of the second thermally conductive filler, and 1 to 3% of the second tackifier.
In some embodiments of the present invention, the first thermally conductive filler comprises at least one of aluminum nitride, boron nitride, silicon nitride, aluminum oxide, magnesium oxide, and aluminum hydroxide, and the second thermally conductive filler comprises at least one of aluminum nitride, boron nitride, silicon nitride, aluminum oxide, magnesium oxide, and aluminum hydroxide.
In some possible embodiments of the invention, the first thermally conductive filler and the second thermally conductive filler are both aluminum hydroxide.
In some embodiments of the invention, the first tackifier and the second tackifier are both fumed silica.
In an embodiment of the invention, the preparation method of the polyurethane structural adhesive comprises the following steps:
mixing using HDI trimer and modified MDI to produce isocyanate;
heating reaction is carried out by using the isocyanate and polycaprolactone polyol to prepare a prepolymer;
mixing using the prepolymer, a first thermally conductive filler, and a first tackifier to produce a first component;
mixing using a polycaprolactone polyol and modified castor oil to produce a polyester polyol;
mixing using the polyester polyol, a second thermally conductive filler, and a second tackifier to produce a second component;
the first component and the second component are used for carrying out mixing reaction to prepare the polyurethane structural adhesive, and the volume ratio of the first component to the second component is (0.9-1.1) to (0.9-1.1). The HDI trimer has small molecular weight and lower polarity, can infiltrate the PET membrane material, has strong mechanical strength, low viscosity and good water resistance of the modified MDI, has low polarity and good toughness of the polycaprolactone polyol, can infiltrate the PET membrane material, and the prepolymer consists of the HDI trimer, the modified MDI and the polycaprolactone polyol, so that the mechanical strength and the water resistance of the prepolymer are better, and the PET membrane material can be infiltrated better; the polyester polyol consists of polycaprolactone polyol and modified castor oil, so that the polyester polyol has good hydrophobicity, strength and toughness and can infiltrate PET film materials; the volume ratio of the first component to the second component is (0.9-1.1), so that the first component and the second component are uniformly mixed and react thoroughly; the polyurethane structural adhesive consists of a prepolymer, a first heat-conducting filler, a first tackifier, polyester polyol, a second heat-conducting filler and a second tackifier, so that the polyurethane structural adhesive has good mechanical strength, water resistance and toughness, and can infiltrate into PET film materials well, the peel strength between the polyurethane structural adhesive and the PET film materials is greater than 1N/mm, and the problem that the polyurethane structural adhesive and the PET film materials are easy to come apart after being bonded in the using process is solved.
In some possible embodiments of the invention, the temperature of the elevated temperature reaction is 70-100 ℃.
In other possible embodiments of the invention, the isocyanate is weighed and placed in a vessel, the polycaprolactone polyol is added with stirring at 70-100 ℃, and the prepolymer is prepared by introducing dry nitrogen into the vessel and then prepolymerizing until the isocyanate content is 5-20%, and the prepolymerization discharge is stopped.
Examples
Examples 1 to 6
Examples 1-6 of the present invention each provide a polyurethane structural adhesive with specific compositions and contents as shown in Table 1.
TABLE 1 composition and content of polyurethane structural gums in examples 1-6
The preparation method of examples 1-6 is:
mixing using HDI trimer and modified MDI to produce isocyanate;
weighing the isocyanate, placing the isocyanate in a container, adding the polycaprolactone polyol under the condition of 70-100 ℃, stirring, introducing dry nitrogen into the container, and then performing prepolymerization to obtain a prepolymer, and stopping the prepolymerization discharge until the isocyanate content is 5-20%.
Mixing using the prepolymer, a first thermally conductive filler, and a first tackifier to produce a first component;
mixing using a polycaprolactone polyol and modified castor oil to produce a polyester polyol;
mixing using the polyester polyol, a second thermally conductive filler, and a second tackifier to produce a second component;
mixing the first component and the second component to obtain the polyurethane structural adhesive, wherein the volume ratio of the first component to the second component in the embodiment 1 is 1:0.9; the volume ratio of the first component to the second component in example 2 is 1:1; the volume ratio of the first component to the second component in example 3 is 1:1.1; the volume ratio of the first component to the second component in example 4 was 0.9:1; the volume ratio of the first component to the second component in example 5 is 1:1; the volume ratio of the first component to the second component in example 6 was 1.1:1.
Performance evaluation:
the polyurethane structural adhesive provided in the comparative example is manufactured by the Dubang scientific and technological materials Co., ltd, and the product model is PU2117F.
The peel strength between the polyurethane structural adhesives of examples 1 to 6 and comparative examples and the PET film was measured according to the test method in the GB/T2791 standard, and the tensile shear strength of the polyurethane structural adhesives of examples 1 to 6 and comparative examples was measured according to the test method in the ISO 4587 standard.
Table 2 performance parameters of polyurethane structural adhesives
As can be seen from Table 2, the peel strength between the polyurethane structural adhesive and the PET film material in the invention is greater than 1N/mm, the peel strength between the polyurethane structural adhesive and the PET film material in the comparative example is 0.8N/mm, and the peel strength between the polyurethane structural adhesive and the PET film material in the invention is increased, so that the problem that the polyurethane structural adhesive and the PET film material are easy to come apart in the using process is solved; the tensile shear strength of the polyurethane structural adhesive is 7.3-8.0 MPa, and the tensile shear strength of the polyurethane structural adhesive in the comparative example is 7.6MPa, so that the peel strength between the polyurethane structural adhesive and the PET film is increased, the performance of the tensile shear strength is not affected, and the requirements of the market on the tensile shear strength are met.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (10)
1. The polyurethane structural adhesive is characterized by being used for bonding with PET film materials and comprising a first component and a second component;
the first component comprises a prepolymer, a first thermally conductive filler, and a first tackifier;
the second component comprises a polyester polyol, a second thermally conductive filler, and a second tackifier;
the prepolymer consists of isocyanate and polycaprolactone polyol, the isocyanate consists of HDI trimer and modified MDI, the polyester polyol consists of polycaprolactone polyol and modified castor oil, and the volume ratio of the first component to the second component is (0.9-1.1).
2. The polyurethane construction adhesive according to claim 1, wherein the modified castor oil has an average molecular weight of 400 to 800 and an average functionality of 3.
3. The polyurethane construction adhesive according to claim 1, wherein the number average molecular weight of the polycaprolactone polyol in the first component and the polycaprolactone polyol in the second component are both 300-1000.
4. The polyurethane construction adhesive according to claim 1, wherein the content of the HDI trimer is 10 to 20% by mass of the first component, the content of the modified MDI is 18 to 30%, the content of the polycaprolactone polyol in the first component is 20 to 30%, the content of the first heat conductive filler is 35 to 50%, and the content of the first tackifier is 1 to 3%.
5. The polyurethane construction adhesive according to claim 1, wherein the second component comprises, by mass, 10 to 30% of the polycaprolactone polyol, 20 to 40% of the modified castor oil, 40 to 60% of the second heat conductive filler, and 1 to 3% of the second tackifier.
6. The polyurethane structural adhesive of claim 1, wherein the first thermally conductive filler comprises at least one of aluminum nitride, boron nitride, silicon nitride, aluminum oxide, magnesium oxide, and aluminum hydroxide, and the second thermally conductive filler comprises at least one of aluminum nitride, boron nitride, silicon nitride, aluminum oxide, magnesium oxide, and aluminum hydroxide.
7. The polyurethane construction adhesive according to claim 1 or 7, wherein the first and second thermally conductive fillers are both aluminum hydroxide.
8. The polyurethane construction adhesive of claim 1, wherein the first tackifier and the second tackifier are both fumed silica.
9. The preparation method of the polyurethane structural adhesive is characterized by comprising the following steps of:
mixing using HDI trimer and modified MDI to produce isocyanate;
heating reaction is carried out by using the isocyanate and polycaprolactone polyol to prepare a prepolymer;
mixing using the prepolymer, a first thermally conductive filler, and a first tackifier to produce a first component;
mixing using a polycaprolactone polyol and modified castor oil to produce a polyester polyol;
mixing using the polyester polyol, a second thermally conductive filler, and a second tackifier to produce a second component;
the first component and the second component are used for carrying out mixing reaction to prepare the polyurethane structural adhesive, and the volume ratio of the first component to the second component is (0.9-1.1) to (0.9-1.1).
10. The method for preparing a polyurethane construction adhesive according to claim 9, wherein the temperature of the heating reaction is 70-100 ℃.
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| CN118064102A (en) * | 2024-03-04 | 2024-05-24 | 道夫新材料(惠州)有限公司 | Polyurethane thermal conductive structural adhesive and preparation method thereof |
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| CN119081633A (en) * | 2024-10-09 | 2024-12-06 | 铠博新材料(天津)有限公司 | Polyurethane heat conduction structural adhesive |
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