CN113736419B - Double-component polyurethane heat-conducting structural adhesive and preparation method thereof - Google Patents

Double-component polyurethane heat-conducting structural adhesive and preparation method thereof Download PDF

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CN113736419B
CN113736419B CN202111214999.6A CN202111214999A CN113736419B CN 113736419 B CN113736419 B CN 113736419B CN 202111214999 A CN202111214999 A CN 202111214999A CN 113736419 B CN113736419 B CN 113736419B
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weight
parts
component
heat
conducting
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CN113736419A (en
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孙辉
钱晓前
周朝栋
邢浩
陶小乐
何永富
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Hangzhou Zhijiang Silicone Chemicals Co Ltd
Hangzhou Zhijiang New Material Co Ltd
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Hangzhou Zhijiang Silicone Chemicals Co Ltd
Hangzhou Zhijiang New Material Co Ltd
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    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • 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

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  • 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 double-component polyurethane heat-conducting structural adhesive which comprises the following components in percentage by volume (0.8-1.2): 1, a component A and a component B; the component A comprises: 10-40 parts by weight of polyether polyol; 1-10 parts by weight of a chain extender; 50-90 parts by weight of a first heat-conducting filler; 0.5-3 parts by weight of a dispersant; 0.1-1 part by weight of a metal catalyst; the component B comprises: 10-35 parts by weight of high-activity polyisocyanate; 1-15 parts by weight of polyether glycol; 1-3 parts by weight of a silane coupling agent; 1-5 parts by weight of low-activity polyisocyanate; 50-90 parts by weight of a second heat-conducting filler. Compared with the prior art, the double-component polyurethane heat-conducting structural adhesive provided by the invention adopts specific content components, realizes better overall interaction, provides lower elastic modulus and better elastic elongation on the basis of meeting the requirements of heat-conducting property and bonding strength, and is particularly suitable for bonding power battery PACK bags.

Description

Double-component polyurethane heat-conducting structural adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of adhesives, in particular to a bi-component polyurethane heat-conducting structural adhesive and a preparation method thereof.
Background
In recent years, the development speed of new energy vehicles is increasing, and various automobile host plants have also provided development targets of new energy vehicles. Under the double stimulation of policy and market, in 2020, new energy vehicles are produced and sold respectively for 136.6 ten thousand and 136.7 ten thousand, and the production rate is increased by 7.5% and 10.9% respectively. The power battery PACK package generally uses aluminum profiles, PET films, PC and the like as main packaging materials, so that the bonding requirement on an adhesive product is higher; meanwhile, as the power battery has serious heat dissipation in the use process, certain heat conducting performance can be provided by adhesive products required at certain specific positions; on the other hand, since the automobile vibrates for a long time during use, it is required that the elastic modulus of the adhesive should not be excessively high. Therefore, the polyurethane is used as a two-component structural adhesive product with both strength and modulus to be applied to the assembly of PACK bags.
Chinese patent with publication number CN109609081A discloses a polyurethane adhesive for bonding power battery PACK structures, and Chinese patent with publication number CN110699033A discloses a two-component polyurethane adhesive and a preparation method and application thereof, but the formula systems have extremely high elastic modulus (usually more than 1000MPa) and cannot meet the working condition of long-time high-frequency vibration of power batteries; chinese patent publication No. CN111303820A discloses a two-component polyurethane structural adhesive for bonding power cells and a preparation method thereof, wherein the elastic modulus (400 MPa-800 MPa) of the product is reduced, but the modulus is still higher, the elastic elongation of the product is lower (about 5%), and the use in more severe environments cannot be met. And none of the above patents have made any special studies on the thermal conductivity.
Disclosure of Invention
In view of the above, the present invention provides a two-component polyurethane thermal conductive structural adhesive and a preparation method thereof, and the two-component polyurethane thermal conductive structural adhesive provided by the present invention provides a lower elastic modulus and a better elastic elongation rate on the basis of satisfying the requirements of thermal conductivity and adhesive strength.
The invention provides a double-component polyurethane heat-conducting structural adhesive which comprises the following components in percentage by volume (0.8-1.2): 1, a component A and a component B;
the component A comprises:
10-40 parts by weight of polyether polyol;
1-10 parts by weight of a chain extender;
50-90 parts by weight of a first heat-conducting filler;
0.5-3 parts by weight of a dispersant;
0.1-1 part by weight of a metal catalyst;
the component B comprises:
10-35 parts by weight of high-activity polyisocyanate;
1-15 parts by weight of polyether glycol;
1-3 parts by weight of a silane coupling agent;
1-5 parts by weight of low-activity polyisocyanate;
50-90 parts by weight of a second heat-conducting filler.
Preferably, the polyether polyol has a functionality of 2-4 and an average molecular weight of 300-18000.
Preferably, the chain extender is selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-propanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 2, 4-pentanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 2-methyl-1, 5-pentanediol, 3-methyl-1, one or more of 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 2-octanediol, 3, 6-octanediol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 7-dimethyl-3, 6-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
Preferably, the first thermally conductive filler is selected from one or more of aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, and magnesium hydroxide.
Preferably, the metal catalyst is selected from one or more of an organotin-based catalyst, an organobismuth-based catalyst, an organozinc-based catalyst, and an organozirconium-based catalyst.
Preferably, the high-activity polyisocyanate is selected from one or more of diphenylmethane diisocyanate, polymeric MDI and derivatives thereof;
the low-activity polyisocyanate is selected from one or more of cyclohexane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene-1, 5-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, xylylene diisocyanate, tetramethyl m-xylylene diisocyanate and derivatives thereof.
Preferably, the polyether glycol has an average molecular weight of 400-12000.
Preferably, the silane coupling agent is selected from one or more of an epoxy silane coupling agent, an amino silane coupling agent, a mercapto silane coupling agent, a styryl silane coupling agent, an isobutylene silane coupling agent, an acryl silane coupling agent and an isocyanate silane coupling agent.
Preferably, the component B further comprises:
0.5-3 parts of an auxiliary agent;
the auxiliary agent is selected from one or more of a dispersing agent, a stabilizing agent, an antioxidant and a wetting agent.
The invention also provides a preparation method of the double-component polyurethane heat-conducting structural adhesive, which comprises the following steps:
a) heating polyether polyol, a chain extender, a first heat-conducting filler and a dispersing agent to 110-130 ℃ under stirring, vacuumizing to below-90 KPa, dehydrating for 1.5-2.5 h, then cooling to below 50 ℃, adding a metal catalyst, vacuumizing to below-90 KPa, and continuously stirring for 0.2-1 h to obtain a component A;
b) heating high-activity polyisocyanate, polyether glycol and second heat-conducting filler to 50-70 ℃ under stirring for reacting for 1.5-2.5 h, then cooling to below 50 ℃, adding low-activity polyisocyanate and silane coupling agent, vacuumizing to below-90 KPa, and continuously stirring for 0.2-1 h to obtain a component B;
c) the component A and the component B are mixed according to the volume ratio (0.8-1.2): 1, uniformly mixing to obtain the double-component polyurethane heat-conducting structural adhesive.
The invention provides a double-component polyurethane heat-conducting structural adhesive which comprises the following components in percentage by volume (0.8-1.2): 1, a component A and a component B; the component A comprises: 10-40 parts by weight of polyether polyol; 1-10 parts by weight of a chain extender; 50-90 parts by weight of a first heat-conducting filler; 0.5-3 parts by weight of a dispersant; 0.1-1 part by weight of a metal catalyst; the component B comprises: 10-35 parts by weight of high-activity polyisocyanate; 1-15 parts by weight of polyether glycol; 1-3 parts by weight of a silane coupling agent; 1-5 parts by weight of low-activity polyisocyanate; 50-90 parts by weight of a second heat-conducting filler. Compared with the prior art, the double-component polyurethane heat-conducting structural adhesive provided by the invention adopts specific content components, realizes better overall interaction, provides lower elastic modulus and better elastic elongation on the basis of meeting the requirements of heat-conducting property and bonding strength, and is particularly suitable for bonding power battery PACK bags. Experimental results show that the thermal conductivity coefficient of the double-component polyurethane thermal conductive structural adhesive is 0.9-2.3W/m.K, the tensile shear strength is 9.8-11.4 MPa (23 ℃,7d), the tensile shear strength is 10.7-12.5 MPa (85 ℃, 85%), the tensile shear strength is 12.8-14.6 MPa (cold and hot impact), the tensile strength is 7.6-10.8 MPa (23 ℃,7d), the elongation at break is 8-68%, and the elastic modulus is 79-230 MPa (23 ℃,7 d).
In addition, the preparation method provided by the invention has the advantages of easily available raw materials, simple operation, mild conditions and excellent industrial application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a double-component polyurethane heat-conducting structural adhesive which comprises the following components in percentage by volume (0.8-1.2): 1, a component A and a component B;
the component A comprises:
10-40 parts by weight of polyether polyol;
1-10 parts by weight of a chain extender;
50-90 parts by weight of a first heat-conducting filler;
0.5-3 parts by weight of a dispersant;
0.1-1 part by weight of a metal catalyst;
the component B comprises:
10-35 parts by weight of high-activity polyisocyanate;
1-15 parts by weight of polyether glycol;
1-3 parts by weight of a silane coupling agent;
1-5 parts by weight of low-activity polyisocyanate;
50-90 parts by weight of a second heat-conducting filler.
In the invention, the double-component polyurethane heat-conducting structural adhesive comprises the following components in volume ratio of (0.8-1.2): 1, preferably, the component A and the component B are prepared from the following components in a volume ratio of (0.8-1.2): 1, more preferably a component and a component B, more preferably a component consisting of, by volume, 1: 1, component A and component B.
In the present invention, the a component includes:
10-40 parts by weight of polyether polyol;
1-10 parts by weight of a chain extender;
50-90 parts by weight of a first heat-conducting filler;
0.5-3 parts by weight of a dispersant;
0.1-1 part by weight of a metal catalyst;
preferably:
15-33 parts of polyether polyol;
3-7 parts of a chain extender;
55-80 parts by weight of a first heat-conducting filler;
0.5-2.5 parts by weight of a dispersant;
0.1-0.5 parts by weight of a metal catalyst;
more preferably:
26-33 parts of polyether polyol;
4-7 parts by weight of a chain extender;
55-65 parts by weight of a first heat-conducting filler;
1.5-2.5 parts by weight of a dispersant;
0.1 part by weight of a metal catalyst.
In the invention, the functionality of the polyether polyol is preferably 2-4, and the average molecular weight is preferably 300-18000. The source of the polyether polyol is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used; in a preferred embodiment of the invention, the polyether polyol is castor oil (modified castor oil).
In the present invention, the chain extender is preferably selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-propanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 2, 4-pentanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 2-octanediol, 3, 6-octanediol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 7-dimethyl-3, 6-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol, more preferably one or more of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 2-ethyl-1, 3-hexanediol and diethylene glycol, most preferably 2-ethyl-1, 3-hexanediol. The source of the chain extender is not particularly limited in the present invention, and the above-mentioned linear aliphatic diols (e.g., ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol), branched aliphatic diols (e.g., 1, 2-propanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 2, 4-pentanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, etc.), which are well known to those skilled in the art, can be used, Commercially available products of 1, 3-hexanediol, 1, 4-hexanediol, 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 2-octanediol, 3, 6-octanediol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 7-dimethyl-3, 6-octanediol) and other low molecular weight diols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol). In the present invention, the chain extender is a small molecule diol, and the average molecular weight is preferably 300 or less.
In the present invention, the first thermally conductive filler is preferably selected from one or more of alumina, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, and magnesium hydroxide, and more preferably aluminum hydroxide and alumina; in a preferred embodiment of the present invention, the first heat conductive filler is aluminum hydroxide and aluminum oxide, and the mass ratio of the aluminum hydroxide to the aluminum oxide is preferably 1: (0.5 to 3), more preferably 1: (0.8 to 1). The source of the first thermally conductive filler is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The heat-conducting filler with the specific components can balance the construction performance (viscosity) and the density of the product to a certain extent.
In the invention, the dispersant is preferably fumed silica; commercially available products known to those skilled in the art may be used.
In the present invention, the metal catalyst is preferably selected from one or more of organotin-based catalysts (such as dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide, octyltin oxide, dibutyltin bis (dodecylthio), dibutyltin diacetate), organobismuth-based catalysts (such as bismuth acetate, bismuth isooctanoate, bismuth neodecanoate, bismuth naphthenate, bismuth laurate, bismuth oleate), organozinc-based catalysts (such as zinc isooctanoate, zinc neodecanoate, zinc laurate) and organozirconium-based catalysts (such as zirconium isooctanoate), more preferably organobismuth-based catalysts. The source of the metal catalyst is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the B component includes:
10-35 parts by weight of high-activity polyisocyanate;
1-15 parts by weight of polyether glycol;
1-3 parts by weight of a silane coupling agent;
1-5 parts by weight of low-activity polyisocyanate;
50-90 parts by weight of a second heat-conducting filler;
preferably:
15-32 parts by weight of high-activity polyisocyanate;
5-10 parts of polyether glycol;
2 parts by weight of a silane coupling agent;
2-4 parts by weight of low-activity polyisocyanate;
55-80 parts by weight of a second heat-conducting filler;
more preferably:
24-32 parts by weight of high-activity polyisocyanate;
8-10 parts of polyether glycol;
2 parts by weight of a silane coupling agent;
3 parts by weight of low-activity polyisocyanate;
55-65 parts by weight of a second heat-conducting filler.
In the present invention, the highly reactive polyisocyanate is preferably selected from one or more of diphenylmethane diisocyanate (MDI), polymeric MDI and derivatives thereof (e.g., biuret groups, isocyanurate groups, urethane groups, uretdione groups, carbodiimide groups, allophanate group-modified MDI), and more preferably polymeric MDI. The source of the highly reactive polyisocyanate in the present invention is not particularly limited, and commercially available ones well known to those skilled in the art may be used.
In the invention, the average molecular weight of the polyether glycol is preferably 400-12000, and more preferably 1000-4000. The source of the polyether glycol is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. According to the invention, the polyether diol is introduced into the isocyanate component (B component), so that the elastic modulus and the elongation at break of the two-component polyurethane structural adhesive product can be adjusted to a certain extent, and the product has a wider application range.
In the present invention, the silane coupling agent is preferably selected from the group consisting of epoxysilane coupling agents (e.g., beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane), aminosilane coupling agents (e.g., bis- [ gamma- (trimethoxysilyl) propyl ] amine, N-phenyl-gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, N-butyl-gamma-aminopropyltrimethoxysilane, N-butyl-gamma-aminopropyltriethoxysilane, N-ethyl-gamma-aminopropyltrimethoxysilane, N-ethylgamma-aminopropyltrimethoxysilane, N-propyltrimethoxysilane, N-ethylglycidyloxyethylglycidyloxyethyldodecyltrimethoxysilane, N-propyltrimethoxysilane, N-ethylglycidyloxyethyldodecyltrimethoxysilane, N-ethylglycidyloxyethylglycidyloxyethylglycidyloxyethyldodecyltrimethoxysilane, N-ethyldodecyltriethoxysilane, N-ethyldodecyltrimethoxysilane, and the like, N-ethyl-gamma-aminopropyltriethoxysilane), a mercaptosilane coupling agent (e.g., gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane), a styrylsilane coupling agent (e.g., p-isobutyltrimethoxysilane), an isobutylene silane coupling agent (e.g., gamma-isobutylallylmethyldimethoxysilane, gamma-isobutylpropyltriethoxysilane), a propenyl silane coupling agent (e.g., gamma-propenylpropyltrimethoxysilane), and an isocyanatosilane coupling agent (e.g., gamma-isocyanatopropyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane), more preferably an aminosilane coupling agent; in a preferred embodiment of the invention, the silane coupling agent is an aminosilane coupling agent, in particular bis- [ gamma- (trimethoxysilyl) propyl ] amine. The source of the silane coupling agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The specific silane coupling agent is introduced into the isocyanate component (B component), so that the adhesive property with the base material can be improved to a certain extent on the premise of not reducing the mechanical property of the adhesive.
In the present invention, the low-reactive polyisocyanate is preferably selected from one or more of cyclohexane diisocyanate (CHDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), naphthalene-1, 5-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate (H12MDI), Xylylene Diisocyanate (XDI), tetramethylm-xylylene diisocyanate (TMDI) and derivatives thereof (e.g., biuret bodies, trimers), more preferably among HDI biuret, HDI trimer, TDI biuret, TDI trimer, IPDI biuret, or IPDI trimer, most preferably among HDI trimer, TDI trimer, or IPDI trimer; in a preferred embodiment of the invention, the low reactive polyisocyanate is HDI trimer, in particular N3300, available from Covestro. The source of the low-reactive polyisocyanate is not particularly limited in the present invention, and commercially available low-reactive polyisocyanates as described above, which are well known to those skilled in the art, may be used. The specific low-activity isocyanate is introduced into the isocyanate component (B component), so that the interface adhesive force can be continuously provided in the later stage after the product is cured in the initial stage to a certain extent.
In the present invention, the second heat conductive filler is the same as the first heat conductive filler in the above technical solution, and is not described herein again.
In the present invention, the component B preferably further comprises:
0.5-3 parts of an auxiliary agent;
more preferably:
0.5-2.5 parts by weight of an auxiliary agent;
most preferably:
1.5-2.5 parts by weight of an auxiliary agent.
In the present invention, the auxiliary agent is preferably selected from one or more of a dispersant, a stabilizer, an antioxidant and a wetting agent, and more preferably a dispersant. In the invention, the dispersant is preferably fumed silica; commercially available products known to those skilled in the art may be used.
The double-component polyurethane heat-conducting structural adhesive provided by the invention adopts specific components, realizes better overall interaction, provides lower elastic modulus and better elastic elongation on the basis of meeting the requirements of heat-conducting property and bonding strength, and is particularly suitable for bonding power battery PACK bags.
The invention also provides a preparation method of the double-component polyurethane heat-conducting structural adhesive, which comprises the following steps:
a) heating polyether polyol, a chain extender, a first heat-conducting filler and a dispersing agent to 110-130 ℃ under stirring, vacuumizing to below-90 KPa, dehydrating for 1.5-2.5 h, then cooling to below 50 ℃, adding a metal catalyst, vacuumizing to below-90 KPa, and continuously stirring for 0.2-1 h to obtain a component A;
b) heating high-activity polyisocyanate, polyether glycol and second heat-conducting filler to 50-70 ℃ under stirring for reacting for 1.5-2.5 h, then cooling to below 50 ℃, adding low-activity polyisocyanate and silane coupling agent, vacuumizing to below-90 KPa, and continuously stirring for 0.2-1 h to obtain a component B;
c) the component A and the component B are mixed according to the volume ratio (0.8-1.2): 1, uniformly mixing to obtain a double-component polyurethane heat-conducting structural adhesive;
preferably:
a) heating polyether polyol, a chain extender, a first heat-conducting filler and a dispersing agent to 120 ℃ under stirring, vacuumizing to below-90 KPa, dehydrating for 2 hours, then cooling to below 50 ℃, adding a metal catalyst, vacuumizing to below-90 KPa, and continuously stirring for 0.5 hours to obtain a component A;
b) heating high-activity polyisocyanate, polyether glycol and second heat-conducting filler to 60 ℃ under stirring for reacting for 2 hours, then cooling to below 50 ℃, adding low-activity polyisocyanate and silane coupling agent, vacuumizing to below-90 KPa, and continuously stirring for 0.5 hour to obtain a component B;
c) mixing the component A and the component B according to the volume ratio of 1: 1, uniformly mixing to obtain the double-component polyurethane heat-conducting structural adhesive.
In the present invention, the polyether polyol, the chain extender, the first heat conductive filler, the dispersant, the metal catalyst, the high-activity polyisocyanate, the polyether glycol, the second heat conductive filler, the low-activity polyisocyanate, and the silane coupling agent are the same as those in the above technical solution, and are not described herein again.
The preparation method provided by the invention has the advantages of easily available raw materials, simple operation, mild conditions and excellent industrial application prospect.
The invention provides a double-component polyurethane heat-conducting structural adhesive which comprises the following components in percentage by volume (0.8-1.2): 1, a component A and a component B; the component A comprises: 10-40 parts by weight of polyether polyol; 1-10 parts by weight of a chain extender; 50-90 parts by weight of a first heat-conducting filler; 0.5-3 parts by weight of a dispersant; 0.1-1 part by weight of a metal catalyst; the component B comprises: 10-35 parts by weight of high-activity polyisocyanate; 1-15 parts by weight of polyether glycol; 1-3 parts by weight of a silane coupling agent; 1-5 parts by weight of low-activity polyisocyanate; 50-90 parts by weight of a second heat-conducting filler. Compared with the prior art, the double-component polyurethane heat-conducting structural adhesive provided by the invention adopts specific content components, realizes better overall interaction, provides lower elastic modulus and better elastic elongation on the basis of meeting the requirements of heat-conducting property and bonding strength, and is particularly suitable for bonding power battery PACK bags. Experimental results show that the thermal conductivity coefficient of the double-component polyurethane thermal conductive structural adhesive is 0.9-2.3W/m.K, the tensile shear strength is 9.8-11.4 MPa (23 ℃,7d), the tensile shear strength is 10.7-12.5 MPa (85 ℃, 85%), the tensile shear strength is 12.8-14.6 MPa (cold and hot impact), the tensile strength is 7.6-10.8 MPa (23 ℃,7d), the elongation at break is 8-68%, and the elastic modulus is 79-230 MPa (23 ℃,7 d).
In addition, the preparation method provided by the invention has the advantages of easily available raw materials, simple operation, mild conditions and excellent industrial application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available products; wherein polyether polyol A1 is modified castor oil, SOVERMOL 805 available from BASF; chain extender A2 is 2-ethyl-1, 3-hexanediol, Sigma-Aldrich; the aluminum hydroxide is Apyral 20X and is purchased from Nabaltec; the alumina was spherical alumina, DAM-07, available from DENKA; the dispersant was fumed silica, H20, available from Wacker; the metal catalyst is COSCAT 83, purchased from Vertellus; the epoxy silane coupling agent is gamma-glycidyl ether propyl trimethoxy silane, Silquest A-187, available from Momentive; the high active polyisocyanate is polymeric MDI, PM200, available from Vanhua Chemicals; polyether glycol is C-2020 available from Wawa Chemicals; the aminosilane coupling agent was bis- [ gamma- (trimethoxysilyl) propyl ] amine, Dynasilan 1124, available from EVONIK; the low reactive polyisocyanate was N3300, available from Covestro; the plasticizer was diisodecyl phthalate DIDP, available from Exxon Mobil.
The performance test method adopted by the invention is as follows:
tensile strength, elongation at break, elastic modulus: the test is carried out by adopting the method in HG/T4363-;
tensile shear strength: the test was performed by the method in HG/T4363-;
coefficient of thermal conductivity: the test was carried out using the method in ISO 22007-2.
Examples
(1) Heating polyether polyol A1, a chain extender A2, a heat-conducting filler and a dispersing agent to 120 ℃ under stirring, vacuumizing to below-90 KPa, dehydrating for 2 hours, then cooling to below 50 ℃, adding a metal catalyst, vacuumizing to below-90 KPa, and continuously stirring for 0.5 hours to obtain a component A;
(2) heating high-activity polyisocyanate, polyether diol A2, dried heat-conducting filler and dispersing agent to 60 ℃ under stirring for reacting for 2 hours, then cooling to below 50 ℃, adding low-activity polyisocyanate and silane coupling agent, vacuumizing to below-90 KPa, and continuing stirring for 0.5 hour to obtain a component B;
(3) mixing the component A and the component B according to the volume ratio of 1: 1, uniformly mixing to obtain the double-component polyurethane heat-conducting structural adhesive.
The selection and formulation of the components of examples 1-6 and comparative examples 1-3 are shown in Table 1.
TABLE 1 ingredient selection and proportioning data Table for examples 1-6 and comparative examples 1-3
Figure BDA0003310297840000111
Figure BDA0003310297840000121
In the above comparative example, the other raw materials of comparative example 1 were not changed, and the component B was not added with the aminosilane coupling agent and the low-reactive polyisocyanate; comparative example 2 other raw materials were unchanged, component A added with epoxy silane coupling agent, component B added with no amino silane coupling agent and low-activity polyisocyanate; comparative example 3 the other raw materials were unchanged, the component B was not polyether glycol, and a plasticizer was added.
TABLE 2 Performance data for examples 1-6 and comparative examples 1-3
Figure BDA0003310297840000122
As can be seen from table 2, in comparative examples 1 and 2, the adhesive strength to the substrate was significantly reduced, and in comparative example 3, the elastic modulus was significantly increased and the elongation at break was significantly reduced.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. A double-component polyurethane heat-conducting structural adhesive comprises the following components in percentage by volume (0.8-1.2): 1, a component A and a component B;
the component A comprises:
10-40 parts by weight of polyether polyol;
1-10 parts by weight of a chain extender;
50-90 parts by weight of a first heat-conducting filler;
0.5-3 parts by weight of a dispersant;
0.1-1 part by weight of a metal catalyst;
the component B comprises:
10-35 parts by weight of high-activity polyisocyanate;
1-15 parts by weight of polyether glycol;
1-3 parts by weight of a silane coupling agent;
1-5 parts by weight of low-activity polyisocyanate;
50-90 parts by weight of a second heat-conducting filler;
the high-activity polyisocyanate is selected from one or more of diphenylmethane diisocyanate, polymeric MDI and derivatives thereof;
the silane coupling agent is selected from one or more of epoxy silane coupling agent, amino silane coupling agent, mercapto silane coupling agent, styryl silane coupling agent, isobutylene silane coupling agent, propenyl silane coupling agent and isocyanate silane coupling agent;
the low-activity polyisocyanate is selected from one or more of cyclohexane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene-1, 5-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, xylylene diisocyanate, tetramethyl m-xylylene diisocyanate and derivatives thereof.
2. The two-component polyurethane heat-conducting structural adhesive as claimed in claim 1, wherein the polyether polyol has a functionality of 2-4 and an average molecular weight of 300-18000.
3. The two-component polyurethane heat-conductive structural adhesive according to claim 1, wherein the chain extender is selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-propanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 2, 4-pentanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, One or more of 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 2-octanediol, 3, 6-octanediol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 7-dimethyl-3, 6-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
4. The two-component polyurethane heat-conducting structural adhesive according to claim 1, wherein the first heat-conducting filler is one or more selected from the group consisting of aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide and magnesium hydroxide.
5. The two-component polyurethane heat-conducting structural adhesive as claimed in claim 1, wherein the metal catalyst is one or more selected from an organotin catalyst, an organobismuth catalyst, an organozinc catalyst and an organozirconium catalyst.
6. The two-component polyurethane heat-conducting structural adhesive as claimed in claim 1, wherein the polyether glycol has an average molecular weight of 400-12000.
7. The two-component polyurethane heat-conducting structural adhesive according to any one of claims 1 to 6, wherein the component B further comprises:
0.5-3 parts of an auxiliary agent;
the auxiliary agent is selected from one or more of a dispersing agent, a stabilizing agent, an antioxidant and a wetting agent.
8. A preparation method of the two-component polyurethane heat-conducting structural adhesive as claimed in any one of claims 1 to 6, comprising the following steps:
a) heating polyether polyol, a chain extender, a first heat-conducting filler and a dispersing agent to 110-130 ℃ under stirring, vacuumizing to below-90 KPa, dehydrating for 1.5-2.5 h, then cooling to below 50 ℃, adding a metal catalyst, vacuumizing to below-90 KPa, and continuously stirring for 0.2-1 h to obtain a component A;
b) heating high-activity polyisocyanate, polyether glycol and second heat-conducting filler to 50-70 ℃ under stirring for reacting for 1.5-2.5 h, then cooling to below 50 ℃, adding low-activity polyisocyanate and silane coupling agent, vacuumizing to below-90 KPa, and continuously stirring for 0.2-1 h to obtain a component B;
c) the component A and the component B are mixed according to the volume ratio (0.8-1.2): 1, uniformly mixing to obtain the double-component polyurethane heat-conducting structural adhesive.
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