WO2023092286A1 - 聚氨酯相变纳米胶囊、相变聚氨酯灌封胶及其制备方法 - Google Patents

聚氨酯相变纳米胶囊、相变聚氨酯灌封胶及其制备方法 Download PDF

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WO2023092286A1
WO2023092286A1 PCT/CN2021/132473 CN2021132473W WO2023092286A1 WO 2023092286 A1 WO2023092286 A1 WO 2023092286A1 CN 2021132473 W CN2021132473 W CN 2021132473W WO 2023092286 A1 WO2023092286 A1 WO 2023092286A1
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phase
change
polyurethane
nanocapsule
hours
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French (fr)
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宋骏
余志�
饶友
陈建军
黄恒超
缪明松
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广州市白云化工实业有限公司
广东白云科技有限公司
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Priority to PCT/CN2021/132473 priority Critical patent/WO2023092286A1/zh
Publication of WO2023092286A1 publication Critical patent/WO2023092286A1/zh

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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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular

Definitions

  • the invention relates to the field of adhesives, in particular to a polyurethane phase-change nanocapsule, a phase-change polyurethane potting glue and a preparation method thereof.
  • Phase change materials emerged in the 1970s due to the needs of aerospace. It is a material that can store and convert thermal energy by switching between different phases to achieve temperature control. According to the material properties, it can be divided into inorganic phase change materials and organic phase change materials; according to the phase change form, it can be divided into solid-liquid phase change materials, solid-solid phase change materials and solid-vapor phase change materials.
  • phase change materials have the advantages of high energy storage density, good thermal stability and long cycle life, so they have always been a hot spot in the research of phase change materials.
  • phase change polyurethane potting adhesives not only need to have the characteristics of phase change materials with high enthalpy and strong cycle life, but also need to have the characteristics of good leveling, good water resistance, and good insulation. .
  • the demand for thermal conductivity is getting higher and higher. In view of the development trend of the electronics industry, it is of great significance to develop phase-change polyurethane adhesives with high enthalpy and high thermal conductivity.
  • Phase-change microcapsule technology is a hot research field in the field of phase-change materials in recent years.
  • the phase-change materials are melted and dispersed into droplets, and then these droplets are used as nuclei and coated with membrane materials to form particles with a particle size of microns.
  • the high-grade capsule avoids the defect of low cycle life caused by the leakage of phase change materials during the solid-liquid phase transition process.
  • phase change microcapsule suitable for adding to polyurethane glue on the market. There are two reasons for this. One is that most of the phase change materials are at the micron level, and the larger particle size is not conducive to dispersion; The viscosity of the colloid will rise sharply, and the homogeneity of the dispersed colloid will be poor.
  • the present invention provides a kind of phase-change nanocapsule suitable for adding polyurethane glue, thereby realizing the application of phase-change material in phase-change polyurethane potting glue.
  • a polyurethane phase-change nanocapsule which is a nanocapsule formed by coating a phase-change material with an amphiphilic block copolymer, wherein the lipophilic end of the amphiphilic block copolymer is a polyurethane segment, and the hydrophilic end is a Methoxy polyethylene glycol segment.
  • the mass ratio of the polyurethane segment to the methoxypolyethylene glycol segment is 2-3:1.
  • the amphiphilic block copolymer is obtained by reacting polyurethane and methoxypolyethylene glycol, and the polyurethane is obtained by reacting isocyanate and castor oil.
  • the mass ratio of the isocyanate, castor oil and methoxypolyethylene glycol is 1:0.3-0.4:0.4-0.6.
  • the isocyanate is diphenylmethane diisocyanate.
  • the molecular weight of the methoxypolyethylene glycol is 1800-2200.
  • the preparation method of the amphiphilic block copolymer comprises the following steps:
  • the solvent is tetrahydrofuran.
  • the mass ratio of the isocyanate to the solvent is 1:2-3.
  • the phase change material is paraffin and/or stearic acid.
  • the polyurethane phase-change nanocapsules are prepared from the amphiphilic block copolymer and the phase-change material in the presence of a crosslinking agent, and the amphiphilic block copolymer
  • the mass ratio of the feed to the phase change material is 1:0.8-1.2.
  • the crosslinking agent is ethylenediamine.
  • the particle size of the polyurethane phase-change nanocapsules is 100nm-200nm.
  • the loading rate of the phase change material in the polyurethane phase change nanocapsules is not less than 75%.
  • the loading rate of the phase change material in the polyurethane phase change nanocapsules is not less than 80%.
  • the invention also discloses a preparation method of the polyurethane phase-change nanocapsule.
  • a preparation method of polyurethane phase-change nanocapsules comprising the steps of:
  • the organic solvent is ethyl acetate.
  • the concentration of the cross-linking agent in the aqueous solution containing the cross-linking agent is 0.4mmol/mL-0.6mmol/mL.
  • the mass ratio of the amphiphilic block copolymer to the organic solvent is 1:1.8 to 2.2; the mass ratio of the organic solvent to the aqueous solution containing the crosslinking agent is 1:8-12.
  • the present invention also provides a two-component phase-change polyurethane potting compound added with the above-mentioned polyurethane phase-change nanocapsules.
  • a two-component phase-change polyurethane potting adhesive including A component and B component, when used, the mixing mass ratio of A component and B component is 1-5:1,
  • the A component is prepared from raw materials comprising the following components:
  • the B component is prepared from raw materials comprising the following components:
  • the mixing mass ratio of component A and component B is 1-2:1 when used.
  • the mixed viscosity of the two-component phase-change polyurethane potting adhesive before curing is 8000 mPa.s-12000 mPa.s at 25°C.
  • the isocyanate or polymeric isocyanate is selected from one or more of TDI, HDI, polymeric MDI, liquefied MDI and XDI, or selected from TDI, HDI, polymeric MDI, liquefied MDI and XDI
  • An isocyanate-terminated prepolymer prepared by reacting one or more of polyethers, polyesters or vegetable polyols as raw materials.
  • the thermally conductive filler is selected from one or more of silicon crystal powder, spherical alumina, aluminum hydroxide, aluminum nitride, boron nitride and graphene.
  • the first additive is a water removal agent.
  • the water removal agent is monocyclic oxazolidine or bicyclic oxazolidine.
  • the polyol may be one or more of polyether polyol, polyester polyol, and vegetable polyol.
  • the vegetable polyol is castor oil and/or soybean oil modified polyol.
  • the viscosity of the polyol at 25° C. is 400 mPa.s ⁇ 10000 mPa.s.
  • the catalyst is an organotin catalyst and/or a tertiary amine catalyst.
  • the organotin catalyst is stannous octoate and/or dibutyltin dilaurate
  • the tertiary amine catalyst is triethylenediamine and/or triethanolamine
  • the second additive is a leveling agent.
  • the invention also provides a preparation method of the above-mentioned two-component phase-change polyurethane potting glue.
  • a preparation method of two-component phase-change polyurethane potting glue comprising the steps of:
  • component A stir the isocyanate or polymerized isocyanate, thermally conductive filler, polyurethane phase-change nanocapsules and the first auxiliary agent under vacuum at 20°C to 50°C for 0.5 to 5 hours to obtain the product;
  • Preparation of component B Stir the polyol, catalyst, thermally conductive filler, polyurethane phase-change nanocapsules and the second auxiliary agent under vacuum at 80°C to 120°C for 1 hour to 5 hours to obtain.
  • the vacuum degree of the vacuum stirring is -0.095MPa ⁇ -0.05MPa.
  • the present invention utilizes the amphiphilic block copolymer constructed by the polyurethane chain and the methoxypolyethylene glycol segment to prepare the phase-change polyurethane nanocapsules coated with the phase-change material through the self-assembly method of the polymer, which can be precisely controlled
  • the particle size of the capsule enriches the preparation technology of phase change capsules, overcomes the incompatibility defect of existing phase change microcapsules and polyurethane glue, and improves the application potential of phase change capsules in polyurethane glue.
  • the two-component phase-change polyurethane encapsulant obtained in the present invention has a significant temperature control advantage compared with the traditional polyurethane encapsulant , has excellent enthalpy and thermal conductivity while ensuring low viscosity, and has great application value in important electronic engineering fields, especially in high-end electronic fields that require temperature control.
  • Figure 1 is a TEM image of polyurethane nanocapsules.
  • the "plurality” mentioned in the present invention means two or more.
  • “And/or” describes the association relationship of associated objects, indicating that there may be three types of relationships, for example, A and/or B may indicate: A exists alone, A and B exist simultaneously, and B exists independently.
  • the character “/” generally indicates that the contextual objects are an "or” relationship.
  • the normal temperature involved in the following examples and comparative examples is conventional room temperature, generally within the temperature range of 15°C to 35°C.
  • the viscosity of the castor oil in the following examples and comparative examples is 400mPa.s ⁇ 600mPa.s; the viscosity of the present invention is the test viscosity at 25°C.
  • Embodiment 1 the preparation of polyurethane phase-change nanocapsules (A)
  • Step 1 Add 100 parts of Wanhua Chemical MDI-100 MDI and 35 parts of castor oil into 250 parts of tetrahydrofuran, heat and reflux at 80° C. for 6 hours with azeotropic stirring. Afterwards, 50 parts of methoxypolyethylene glycol (molecular weight: 2000) was added, and heated under reflux at 70°C for azeotropic stirring for 6 hours. Afterwards, the reaction solution was purified by neutral alumina chromatography column (mobile phase was tetrahydrofuran), and then rotary evaporated to obtain a light yellow solid.
  • Step 2 Weigh 50 parts of the light yellow solid prepared in step 1 and 50 parts of paraffin into 100 parts of ethyl acetate, mix and stir at 80° C. for 4 hours. The temperature was lowered to 25° C., and then 1,000 parts of deionized water containing ethylenediamine (the concentration of ethylenediamine was 0.5 mmol/mL) was quickly added under strong mechanical stirring (1200 rpm).
  • the product before vacuum drying was dispersed and sampled and stained with phosphotungstic acid solution for transmission electron microscope (TEM) characterization (as shown in Figure 1). It can be found that the particle size of the prepared polyurethane phase change nanocapsules is concentrated between 100-200nm between.
  • TEM transmission electron microscope
  • Embodiment 2 the preparation of polyurethane phase-change nanocapsules (B)
  • Step 1 Exactly the same as Step 1 in Example 1.
  • Step 2 Weigh 50 parts of the light yellow solid prepared in Step 1 and 50 parts of stearic acid, add them to 100 parts of ethyl acetate, mix and stir at 80° C. for 4 hours. The temperature was lowered to 25° C., and then 1,000 parts of deionized water containing ethylenediamine (the concentration of ethylenediamine was 0.5 mmol/mL) was quickly added under strong mechanical stirring (1200 rpm).
  • the product before vacuum drying was dispersed and sampled and stained with phosphotungstic acid solution for transmission electron microscope (TEM) characterization. It can be found that the particle size of the prepared polyurethane phase-change nanocapsules is consistent with that of Example 1, concentrated between 100-200nm.
  • TEM transmission electron microscope
  • Step 1 Add 100 parts of MDI and 35 parts of castor oil into 250 parts of tetrahydrofuran, heat and reflux at 80° C. for 6 hours with azeotropic stirring. Afterwards, 50 parts of polyethylene glycol was added, and heated under reflux at 70°C for azeotropic stirring for 6 hours. Afterwards, the reaction solution was purified by neutral alumina chromatography column (mobile phase was tetrahydrofuran), and then rotary evaporated to obtain a light yellow solid.
  • Step 2 Weigh 50 parts of the light yellow solid prepared in step 1 and 50 parts of paraffin into 100 parts of ethyl acetate, mix and stir at 80° C. for 4 hours. Then, 1000 parts of deionized water containing ethylenediamine (the concentration of ethylenediamine is 0.5mmol/mL) was quickly added under the condition of strong mechanical stirring (rotating speed 1200rpm). After stirring for half an hour, the mixed solution becomes milky white, and the viscosity of the system increases; continue to stir for 1 hour, filter, and clean the gained solid with deionized water and dry it in vacuum at room temperature for 12 hours to obtain a white powder, i.e. polyurethane phase-change nanocapsules ( C).
  • ethylenediamine the concentration of ethylenediamine is 0.5mmol/mL
  • the product before vacuum drying was dispersed and sampled and stained with phosphotungstic acid solution for transmission electron microscope (TEM) characterization. It can be found that the particle size of the prepared polyurethane phase change nanocapsules is concentrated between 100-200nm.
  • TEM transmission electron microscope
  • the formation principle and process of the polyurethane phase-change nanocapsules of embodiment 1 and embodiment 2 are as follows: the block copolymer composed of polyurethane chain and methoxypolyethylene glycol chain prepared in step 1 can be formed at the interface of the oil-in-water emulsion system Nanocapsules are formed by self-assembly.
  • the block copolymer itself is an amphiphilic polymer, the polyurethane segment is in the oil phase, and the methoxypolyethylene glycol chain is in the water phase, so it can be used as a surfactant to stabilize the emulsion.
  • the emulsion can form nano-droplets under high-speed mechanical stirring, and the droplet interface is a polymer film formed by the self-assembly of block copolymers, while the inside of the droplet is an oil phase containing a large amount of phase-change materials.
  • the ethylenediamine crosslinking agent in the water phase can quickly react with the NCO of the polyurethane chain to crosslink and lock the capsule structure, thereby forming stable polyurethane phase change nanocapsules loaded with phase change materials and with a high loading rate.
  • what the present invention adopts is the methoxypolyethylene glycol that only contains a hydroxyl group, makes two NCO groups of MDI only react with a hydroxyl group of methoxypolyethylene glycol, and another NCO group is in subsequent steps In 2, react with the cross-linking agent ethylenediamine to form polyurea bonds, which can form the nanocapsule wall more firmly, thereby forming stable nanocapsules, and further improving the loading rate of the phase change material in the polyurethane phase change nanocapsules.
  • the loading ratios of the polyurethane phase-change nanocapsules prepared in Example 1 and Example 2 are equivalent, which corresponds to the consistent particle size of the two.
  • the entrapment rate of the phase change material of Example 1 and Example 2 is obviously much higher, this is due to the nanocapsule (C) in Comparative Example 1 used
  • the cross-linking density will decrease and the speed of the cross-linking reaction will slow down (because the isocyanate group is reduced), thus resulting in the phase-change material carried by the phase-change nanocapsules being easily Loss occurs when the cross-linking reaction occurs, therefore, the entrapment efficiency will be significantly reduced.
  • Embodiment 3 the preparation of phase-change polyurethane encapsulant I
  • Component A Take 100 parts of polymeric MDI produced by Yantai Wanhua as PM-200, 150 parts of spherical alumina heat-conducting powder produced by Baitu High-tech Material Technology Co., Ltd. and modeled as BAK90, and 100 parts prepared in Example 1 Polyurethane phase-change nanocapsules (A) and 1 part of ALT 202 oxazolidine produced by Anxiang Elite Chemical Co., Ltd. were added to the planetary machine, and vacuum stirred at 25°C and a vacuum of -0.09MPa 2 hours.
  • Component B Take 50 parts of castor oil, 50 parts of polyether polyol (viscosity 1000-1500cp) produced by Shandong Bluestar Dongda University (viscosity 1000-1500cp), 0.01 part of dibutyltin dilaurate catalyst, 150 parts of Baitu high-tech material technology The model produced by Co., Ltd.
  • Example 1 is the spherical aluminum oxide heat-conducting powder of BAK90, 100 parts of polyurethane phase-change nanocapsules (A) prepared in Example 1 and 0.5 part of BYK chemical company's production of the model BYK370 leveling agent, add planetary machine , stirred for 2 hours at a vacuum degree of -0.09MPa and a temperature of 100° C., and then lowered to room temperature and stirred for 2 hours.
  • Component A Take 100 parts of PM-200 polymeric MDI produced by Yantai Wanhua, 150 parts of spherical alumina heat-conducting powder produced by Baitu High-tech Material Technology Co., Ltd., and 150 parts of the spherical alumina heat-conducting powder produced in Example 1 Polyurethane phase-change nanocapsules (A) and 1 part of ALT 202 oxazolidine produced by Anxiang Elite Chemical Co., Ltd. were added to the planetary machine, and vacuum stirred at 25°C and a vacuum of -0.09MPa 2 hours.
  • Component B Take 50 parts of castor oil, 50 parts of polyether polyol (viscosity 1000-1500cp) produced by Shandong Bluestar Dongda University (viscosity 1000-1500cp), 0.01 part of dibutyltin dilaurate catalyst, 150 parts of Baitu high-tech material technology The model produced by Co., Ltd.
  • Example 1 is the spherical aluminum oxide heat-conducting powder of BAK90, 150 parts of polyurethane phase-change nanocapsules (A) prepared in Example 1 and 0.5 part of BYK chemical company's production of the model BYK370 leveling agent, add planetary machine , stirred for 2 hours at a vacuum degree of -0.09MPa and a temperature of 100° C., and then lowered to room temperature and stirred for 2 hours.
  • Component A Take 100 parts of polymeric MDI produced by Yantai Wanhua as PM-200, 150 parts of spherical alumina heat-conducting powder produced by Baitu High-tech Material Technology Co., Ltd. and model BAK90, 200 parts prepared in Example 1 Polyurethane phase-change nanocapsules (A) and 1 part of ALT 202 oxazolidine produced by Anxiang Elite Chemical Co., Ltd. were added to the planetary machine, and vacuum stirred at 25°C and a vacuum of -0.09MPa 2 hours.
  • Component B Take 50 parts of castor oil, 50 parts of polyether polyol (viscosity 1000-1500cp) produced by Shandong Bluestar Dongda University (viscosity 1000-1500cp), 0.01 part of dibutyltin dilaurate catalyst, 150 parts of Baitu high-tech material technology The model produced by Co., Ltd.
  • Example 1 is the spherical aluminum oxide heat-conducting powder of BAK90, 200 parts of polyurethane phase-change nanocapsules (A) prepared in Example 1 and 0.5 part of the BYK chemical company's production of the model BYK370 leveling agent, add planetary machine , stirred for 2 hours at a vacuum degree of -0.09MPa and a temperature of 100° C., and then lowered to room temperature and stirred for 2 hours.
  • Component A Take 100 parts of PM-200 polymeric MDI produced by Yantai Wanhua, 150 parts of spherical alumina heat-conducting powder of BAK90 produced by Baitu High-tech Material Technology Co., Ltd., 150 parts prepared in Example 2 Polyurethane phase-change nanocapsules (B) and 1 part of ALT 202 oxazolidine produced by Anxiang Elite Chemical Co., Ltd. were added to a planetary machine, and vacuum stirred at 25°C and a vacuum of -0.09MPa 2 hours.
  • Component B Take 50 parts of castor oil, 50 parts of polyether polyol (viscosity 1000-1500cp) produced by Shandong Bluestar Dongda University (viscosity 1000-1500cp), 0.01 part of dibutyltin dilaurate catalyst, 150 parts of Baitu high-tech material technology The model produced by Co., Ltd.
  • Example 2 is the spherical aluminum oxide heat-conducting powder of BAK90, 150 parts of polyurethane phase-change nanocapsules (B) prepared in Example 2 and 0.5 part of the BYK chemical company's production of the model BYK370 leveling agent, add planetary machine , stirred for 2 hours at a vacuum degree of -0.09MPa and a temperature of 100° C., and then lowered to room temperature and stirred for 2 hours.
  • Component A Take 100 parts of PM-200 polymeric MDI produced by Yantai Wanhua, 150 parts of spherical alumina thermal conductive powder of model BAK90 produced by Baitu High-tech Material Technology Co., Ltd., and 100 parts of Hubei Thermo New Energy
  • the phase-change microcapsules (particle size > 1 ⁇ m) of the model ME-37 produced by Science and Technology Co., Ltd. and 1 part of the oxazolidine of the model ALT 202 produced by Anxiang Elite Chemical Co., Ltd. were added to the planetary machine and heated at 25 ° C , Stirring in vacuum for 2 hours under the condition that the degree of vacuum is -0.09MPa.
  • Component B Take 50 parts of castor oil, 50 parts of polyether polyol (viscosity 1000-1500cp) produced by Shandong Bluestar Dongda University (viscosity 1000-1500cp), 0.01 part of dibutyltin dilaurate catalyst, 150 parts of Baitu high-tech material technology BAK90 spherical alumina heat-conducting powder produced by the company, 100 parts of ME-37 phase-change microcapsules (particle size > 1 ⁇ m) produced by Hubei Thermo New Energy Technology Co., Ltd.
  • the type BYK370 leveling agent is added to the planetary machine, stirred for 2 hours under the condition of vacuum degree of -0.09MPa and temperature of 100°C, and then lowered to room temperature and stirred for 2 hours.
  • Component A Take 100 parts of PM-200 polymeric MDI produced by Yantai Wanhua, 150 parts of spherical alumina thermal conductive powder of model BAK90 produced by Baitu High-tech Material Technology Co., Ltd., and 200 parts of Hubei Thermo New Energy
  • the phase-change microcapsules (particle size > 1 ⁇ m) of the model ME-37 produced by Science and Technology Co., Ltd. and 1 part of the oxazolidine of the model ALT 202 produced by Anxiang Elite Chemical Co., Ltd. were added to the planetary machine and heated at 25 ° C , Stirring for 2 hours under the condition that the degree of vacuum is -0.09MPa.
  • Component B Take 50 parts of castor oil, 50 parts of polyether polyol (viscosity 1000-1500cp) produced by Shandong Bluestar Dongda University (viscosity 1000-1500cp), 0.01 part of dibutyltin dilaurate catalyst, 150 parts of Baitu high-tech material technology BAK90 spherical alumina heat-conducting powder produced by the company, 200 parts of ME-37 phase-change microcapsules (particle size > 1 ⁇ m) produced by Hubei Thermo New Energy Technology Co., Ltd.
  • the type BYK370 leveling agent is added to the planetary machine, stirred for 2 hours under the condition of vacuum degree of -0.09MPa and temperature of 100°C, and then lowered to room temperature and stirred for 2 hours.
  • Component A take 100 parts of polymeric MDI produced by Yantai Wanhua as PM-200, 150 parts of spherical alumina heat-conducting powder produced by Baitu High-tech Material Technology Co., Ltd., and 150 parts of comparative example 1 Polyurethane phase-change nanocapsules (C) and 1 part of ALT 202 oxazolidine produced by Anxiang Elite Chemical Co., Ltd. were added to a planetary machine, and stirred in vacuum at 25°C and a vacuum of -0.09MPa for 2 hours .
  • Component B Take 50 parts of castor oil, 50 parts of polyether polyol (viscosity 1000-1500cp) produced by Shandong Bluestar Dongda University (viscosity 1000-1500cp), 0.01 part of dibutyltin dilaurate catalyst, 150 parts of Baitu high-tech material technology The model produced by Co., Ltd.
  • spherical aluminum oxide heat-conducting powder of BAK90 150 parts of polyurethane phase-change nanocapsules (C) prepared in comparative example 1 and 0.5 part of the BYK chemical company's production model are the leveling agent of BYK370, add planetary machine, Stir for 2 hours under the condition of vacuum degree of -0.09MPa and temperature of 100°C, then drop to room temperature and stir for 2 hours.
  • Hardness test method GB/T 2411-2008 Plastics and hard rubber use a durometer to measure the indentation hardness (Shore hardness).
  • Thermal conductivity test method ASTM D5470-2017 Standard test method for heat transfer characteristics of thermally conductive insulating materials.
  • Melting enthalpy test method use a differential scanning calorimeter (DSC) to test within the temperature range of 10°C to 65°C, and set the heating rate to 0.1K/min.
  • DSC differential scanning calorimeter
  • Colloid tensile test method GB/T 1040.2-2006 Determination of tensile properties of plastics Part 2: Tests for molded and extruded plastics.
  • Example 5 Comparing Example 5 and Example 6, it can be seen that the change of the phase change material contained in the polyurethane phase change nanocapsules from paraffin to stearic acid does not cause obvious changes in various properties.

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Abstract

提供聚氨酯相变纳米胶囊、相变聚氨酯灌封胶及其制备方法，所述聚氨酯相变纳米胶囊为由两亲性嵌段共聚物包覆相变材料形成的纳米胶囊，所述两亲性嵌段共聚物的亲油端为聚氨酯链段，亲水端为甲氧基聚乙二醇链段。通过添加聚氨酯相变纳米胶囊，使双组分相变聚氨酯灌封胶具有控温优势，在保证低粘度的同时具有优异的焓值和导热性能，在电子工程领域，尤其在需要温度控制的电子领域具有应用价值。

Description

聚氨酯相变纳米胶囊、相变聚氨酯灌封胶及其制备方法 技术领域
本发明涉及胶粘剂领域，特别是涉及一种聚氨酯相变纳米胶囊、相变聚氨酯灌封胶及其制备方法。
背景技术
相变材料(PCM)受航天的需求而兴起于上世纪70年代。它是一种可以通过不同相态间转换来实现热能的储存和转换从而实现温度控制的材料。按材料属性可以分为无机相变材料和有机相变材料；按相变形态可分为固-液相变材料、固-固相变材料和固-汽相变材料。
有机相变材料具有储能密度大、热稳定性好和循环寿命长等优点，从而一直是相变材料研究热点。但是与传统的聚氨酯复合相变材料不同，相变聚氨酯灌封胶不但需要具有焓值高、循环寿命强的相变材料特点，还需要具有流平性好，防水性佳，绝缘性好等特点。尤其随着电子产品的发展，对于导热性能的需求越来越高。针对电子行业的发展趋势，开发出具有高焓值，高导热的相变聚氨酯胶具有重要意义。
相变微胶囊技术是近些年相变材料领域研究的热门领域，通常将相变材料融化分散成液滴，然后再将这些液滴作为核，利用膜材料进行包覆形成粒径为微米量级的胶囊，避免了相变材料在固-液相变过程中的渗漏导致循环寿命低的缺陷。但是市面上还未有一款适用于添加到聚氨酯胶的相变微胶囊。究其原因有二，其一在于相变材料多在微米级别，粒径较大不利于分散；其二是现存的相变微胶囊与聚氨酯本体相容性较差，使得添加量一增加即会导致胶体粘度急剧上升，同时分散后的胶体均一性较差。
发明内容
基于此，本发明提供了一种适用于聚氨酯胶添加的相变纳米胶囊，从而实 现了相变材料在相变聚氨酯灌封胶中的应用。
具体的技术方案如下：
一种聚氨酯相变纳米胶囊，其为由两亲性嵌段共聚物包覆相变材料形成的纳米胶囊，所述两亲性嵌段共聚物的亲油端为聚氨酯链段，亲水端为甲氧基聚乙二醇链段。
在其中一些实施例中，所述聚氨酯链段和甲氧基聚乙二醇链段的质量比为2～3:1。
在其中一些实施例中，所述两亲性嵌段共聚物由聚氨酯和甲氧基聚乙二醇反应得到，所述聚氨酯由异氰酸酯和蓖麻油反应得到。
在其中一些实施例中，所述异氰酸酯、蓖麻油和甲氧基聚乙二醇的质量比为1:0.3～0.4:0.4～0.6。
在其中一些实施例中，所述异氰酸酯为二苯基甲烷二异氰酸酯。
在其中一些实施例中，所述甲氧基聚乙二醇的分子量为1800～2200。
在其中一些实施例中，所述两亲性嵌段共聚物的制备方法包括如下步骤：
将所述异氰酸酯和蓖麻油加入到溶剂中，加热回流共沸4小时～8小时，然后加入所述甲氧基聚乙二醇，加热回流共沸4小时～8小时，即得。
在其中一些实施例中，所述溶剂为四氢呋喃。
在其中一些实施例中，所述异氰酸酯和所述溶剂的质量比为1:2～3。
在其中一些实施例中，所述相变材料为石蜡和/或硬脂酸。
在其中一些实施例中，所述聚氨酯相变纳米胶囊由所述两亲性嵌段共聚物和所述相变材料在交联剂的存在下制备而成，所述两亲性嵌段共聚物和所述相变材料的投料质量比为1：0.8～1.2。
在其中一些实施例中，所述交联剂为乙二胺。
在其中一些实施例中，所述聚氨酯相变纳米胶囊的粒径为100nm～200nm。
在其中一些实施例中，所述聚氨酯相变纳米胶囊中相变材料的包载率不小于75％。
在其中一些实施例中，所述聚氨酯相变纳米胶囊中相变材料的包载率不小 于80％。
本发明还公开了上述聚氨酯相变纳米胶囊的制备方法。
具体技术方案如下：
一种聚氨酯相变纳米胶囊的制备方法，包括如下步骤：
将所述两亲性嵌段共聚物和所述相变材料加入到有机溶剂中，在回流温度下混合搅拌2小时～6小时，降温至20℃～35℃，然后在转速为1000rpm～1400rpm的强力搅拌条件下加入含有所述交联剂的水溶液，继续在转速为1000rpm～1400rpm的条件下搅拌1小时～2小时，即得所述聚氨酯相变纳米胶囊。
在其中一些实施例中，所述有机溶剂为乙酸乙酯。
在其中一些实施例中，所述含有所述交联剂的水溶液中所述交联剂的浓度为0.4mmol/mL-0.6mmol/mL。
在其中一些实施例中，所述两亲性嵌段共聚物和所述有机溶剂的质量比为1:1.8～2.2；所述有机溶剂和所述含有所述交联剂的水溶液的质量比为1:8～12。
本发明还提供了一种添加有上述聚氨酯相变纳米胶囊的双组分相变聚氨酯灌封胶。
具体技术方案如下：
一种双组分相变聚氨酯灌封胶，包括A组分和B组分，使用时A组分和B组分的混合质量比为1-5:1，
以重量份计，所述A组分由包含如下组分的原料制备而成：
Figure PCTCN2021132473-appb-000001
以重量份计，所述B组分由包含如下组分的原料制备而成：
Figure PCTCN2021132473-appb-000002
Figure PCTCN2021132473-appb-000003
在其中一些实施例中，使用时A组分和B组分的混合质量比为1-2:1。
在其中一些实施例中，所述双组分相变聚氨酯灌封胶在固化前的混合粘度在25℃的条件下为8000mPa.s～12000mPa.s。
在其中一些实施例中，所述异氰酸酯或者聚合异氰酸酯选自TDI、HDI、聚合MDI、液化MDI和XDI中的一种或多种，或者选自以TDI、HDI、聚合MDI、液化MDI和XDI中的一种或多种与聚醚、聚酯或者植物性多元醇为反应原料制备的异氰酸封端的预聚体。
在其中一些实施例中，所述导热填料选自硅晶粉、球形氧化铝、氢氧化铝、氮化铝、氮化硼和石墨烯中的一种或多种。
在其中一些实施例中，所述第一助剂为除水剂。
在其中一些实施例中，所述除水剂为单环噁唑烷或双环噁唑烷。
在其中一些实施例中，所述多元醇可为聚醚多元醇、聚酯多元醇、植物类多元醇中的一种或多种。
在其中一些实施例中，所述植物类多元醇为蓖麻油和/或大豆油改性多元醇。
在其中一些实施例中，所述多元醇在25℃的粘度为400mPa.s～10000mPa.s。
在其中一些实施例中，所述催化剂为有机锡类催化剂和/或叔胺类催化剂。
在其中一些实施例中，所述有机锡类催化剂为辛酸亚锡和/或二月桂酸二丁基锡，所述叔胺类催化剂为三亚乙基二胺和/或三乙醇胺。
在其中一些实施例中，所述第二助剂为流平剂。
本发明还提供了上述双组分相变聚氨酯灌封胶的制备方法。
具体技术方案如下：
一种双组分相变聚氨酯灌封胶的制备方法，包括如下步骤：
制备A组分：将所述异氰酸酯或者聚合异氰酸酯、导热填料、聚氨酯相变纳米胶囊和第一助剂在20℃～50℃真空搅拌0.5小时～5小时，即得；
制备B组分：将所述多元醇、催化剂、导热填料、聚氨酯相变纳米胶囊和 第二助剂在80℃～120℃真空搅拌1小时～5小时，即得。
在其中一些实施例中，所述真空搅拌的真空度为-0.095MPa～-0.05MPa。
本发明利用聚氨酯链和甲氧基聚乙二醇链段构筑的两亲性嵌段共聚物通过聚合物自主装方法制备得到了包覆相变材料的相变聚氨酯纳米胶囊，该方法可以精准控制胶囊粒径，丰富了相变胶囊的制备技术，克服了现有相变微胶囊和聚氨酯胶不相容的缺陷，提高了相变胶囊在聚氨酯胶中的应用潜力。
通过添加本发明的包载相变材料的相变聚氨酯纳米胶囊，使本发明所得的双组分相变聚氨酯灌封胶相较于传统的聚氨酯灌封胶在实用性上具有显著的控温优势，在保证低粘度的同时具有优异的焓值和导热性能，在重要电子工程领域，尤其在需要温度控制的高端电子领域具有巨大的应用价值。
附图说明
图1为聚氨酯纳米胶囊的TEM图。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
除非另有定义，本发明所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不用于限制本发明。
本发明的术语“包括”和“具有”以及它们任何变形，意图在于覆盖不排他的包含。例如包含了一系列步骤的过程、方法、装置、产品或设备没有限定于已列出的步骤或模块，而是可选地还包括没有列出的步骤，或可选地还包括对于这些过程、方法、产品或设备固有的其它步骤。
在本发明中提及的“多个”是指两个或两个以上。“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。字符“/”一般表示前后关联对象是一种“或”的关系。
以下实施例和对比例中所涉及的份数均指质量份数。
以下实施例和对比例中所涉及的常温即常规室温，一般在15℃～35℃的温度范围内。
以下实施例和对比例中的蓖麻油的粘度为400mPa.s～600mPa.s；本发明所述粘度均为25℃条件下的测试粘度。
以下实施例和对比例中所用原料或者试剂均为普通市售产品。
以下为具体实施例。
实施例1：聚氨酯相变纳米胶囊(A)的制备
步骤1：将100份万华化学的型号为MDI-100的MDI和35份蓖麻油加入到250份的四氢呋喃中，在80℃下加热回流共沸搅拌6小时。之后加入50份甲氧基聚乙二醇(分子量为2000)，70℃下加热回流共沸搅拌6小时。之后将反应液通过中性氧化铝层析柱(流动相为四氢呋喃)提纯后旋蒸获得淡黄色固体。
产物红外谱图特征峰如下：3312cm -1为N-H的吸收峰，2876cm -1为聚乙二醇链中-CH 2-的伸缩振动峰，2273cm -1为异氰酸酯基团NCO的不对称伸缩振动峰，1716cm -1为酰胺中C＝O的吸收峰，1540cm -1为酰胺中N-H面内弯曲振动峰和C-N的伸缩峰，1378cm -1为聚乙二醇链中CH 3的对称振动峰，1236cm -1为酰胺的吸收峰，1115cm -1为聚乙二醇链中C-O-C的对称伸缩振动峰。
步骤2：称取50份步骤1中制取的淡黄色固体和50份石蜡加入到100份乙酸乙酯中，在80℃回流混合搅拌4小时。降温至25℃，然后在机械强力搅拌条件下(转速1200rpm)快速加入含有乙二胺的去离子水1000份(乙二胺浓度为0.5mmol/mL)。在转速1200rpm下搅拌半小时后，混合液变成乳白色，体系粘 度增大；继续在转速1200rpm下搅拌1小时，过滤，将所得固体用去离子水清洗后常温真空干燥12小时，可得白色粉末，即聚氨酯相变纳米胶囊(A)。
将真空干燥前的产物进行分散制样并用磷钨酸溶液染色后进行透射电镜(TEM)表征(如图1所示)，可发现制备的聚氨酯相变纳米胶囊的粒径集中在100-200nm之间。
实施例2：聚氨酯相变纳米胶囊(B)的制备
步骤1：与实施例1中的步骤1完全一样。
步骤2：称取50份步骤1中制取的淡黄色固体和50份硬脂酸加入到100份乙酸乙酯中，在80℃回流混合搅拌4小时。降温至25℃，然后在机械强力搅拌条件下(转速1200rpm)快速加入含有乙二胺的去离子水1000份(乙二胺浓度为0.5mmol/mL)。在转速1200rpm下搅拌半小时后，混合液变成乳白色，体系粘度增大；继续在转速1200rpm下搅拌1小时，过滤，将所得固体用去离子水清洗后常温真空干燥12小时，可得白色粉末，即聚氨酯相变纳米胶囊(B)。
将真空干燥前的产物进行分散制样并用磷钨酸溶液染色后进行透射电镜(TEM)表征可发现制备的聚氨酯相变纳米胶囊的粒径和实施例1一致，集中在100-200nm之间。
对比例1聚氨酯相变纳米胶囊(C)的制备
聚氨酯相变纳米胶囊(C)的制备与实施例1的区别在于将其中的甲氧基聚乙二醇替换成相应分子量的聚乙二醇，具体如下：
步骤1：将100份MDI和35份蓖麻油加入到250份的四氢呋喃中，在80℃下加热回流共沸搅拌6小时。之后加入50份聚乙二醇，70℃下加热回流共沸搅拌6小时。之后将反应液通过中性氧化铝层析柱(流动相为四氢呋喃)提纯后旋蒸获得淡黄色固体。
步骤2：称取50份步骤1中制取的淡黄色固体和50份石蜡加入到100份乙酸乙酯中，在80℃回流混合搅拌4小时。然后在机械强力搅拌条件下(转速 1200rpm)快速加入含有乙二胺的去离子水1000份(乙二胺浓度为0.5mmol/mL)。搅拌半小时后，混合液变成乳白色，体系粘度增大；继续搅拌1小时，过滤，将所得固体用去离子水清洗后常温真空干燥12小时，可得白色粉末，即聚氨酯相变纳米胶囊(C)。
将真空干燥前的产物进行分散制样并用磷钨酸溶液染色后进行透射电镜(TEM)表征，可发现制备的聚氨酯相变纳米胶囊的粒径集中在100-200nm之间。
实施例1与实施例2的聚氨酯相变纳米胶囊的形成原理和过程如下：步骤1制备的聚氨酯链与甲氧基聚乙二醇链组成的嵌段共聚物可在水包油的乳液体系界面通过自主装形成纳米胶囊。此嵌段共聚物本身为两亲性聚合物，聚氨酯链段处在油相中，甲氧基聚乙二醇链处于水相中，从而可作为表面活性剂稳定乳液。而乳液在高速机械搅拌下可形成纳米液滴，液滴界面则是嵌段共聚物自组装形成的高分子膜，而液滴内部则是含有大量相变材料的油相。加之水相中的乙二胺交联剂可迅速与聚氨酯链的NCO反应交联锁住胶囊结构，从而形成稳定的包载相变材料的并且包载率高的聚氨酯相变纳米胶囊。另外，本发明采用的是仅含有一个羟基的甲氧基聚乙二醇，使得MDI的两个NCO基团只与甲氧基聚乙二醇的一个羟基反应，另外一个NCO基团在后续步骤2中与交联剂乙二胺反应形成聚脲键，这样可以更加牢固的形成纳米胶囊壁，从而形成稳定的纳米胶囊，进一步提高聚氨酯相变纳米胶囊中相变材料的包载率。
通过计算石蜡或硬脂酸的投料量和干燥后的聚氨酯相变纳米胶囊包载的石蜡或硬脂酸的质量可计算出该聚氨酯相变纳米胶囊的包载率，具体为称取步骤2中制备纳米胶囊前投入淡黄色固体的质量，再称取步骤二制备过程结束后的白色粉末，白色粉末的质量减去淡黄色固体的质量即为该聚氨酯相变纳米胶囊包载石蜡的质量，再除以步骤二中投入石蜡的总质量，即得到该聚氨酯相变纳米胶囊中石蜡的包载率，结果如表1所示。通过对比可知实施例1和实施例2制备的聚氨酯相变纳米胶囊的包载率相当，这与二者的粒径大小一致相对应。而 通过和对比例1制备的纳米胶囊(C)相比较，实施例1和实施例2的相变材料的包载率明显高很多，这是由于对比例1中的纳米胶囊(C)所使用的聚乙二醇分子链上具有两个羟基官能团，在与异氰酸基团反应的过程中会比甲氧基聚乙二醇多消耗一倍量的异氰酸基团，而在后续制备乳液与乙二胺进行交联时的交联密度会减小并且交联反应的速度会减慢(因为异氰酸基团减少了)，从而导致所得相变纳米胶囊包载的相变材料容易在交联反应发生时流失，因此，包载率会明显降低。
表1
Figure PCTCN2021132473-appb-000004
实施例3：相变聚氨酯灌封胶I的制备
A组分：取100份的烟台万华生产的型号为PM-200的聚合MDI、150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，100份实施例1中制备的聚氨酯相变纳米胶囊(A)和1份安乡艾利特化工有限公司生产的型号为ALT 202的噁唑烷，加入行星机，在25℃、真空度为-0.09MPa的条件下真空搅拌2小时。
B组分：取50份蓖麻油，50份山东蓝星东大生产的型号为DL3000D的聚醚多元醇(粘度1000-1500cp)，0.01份二月桂酸二丁基锡催化剂，150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，100份实施例1中制备的聚氨酯相变纳米胶囊(A)和0.5份毕克化学公司生产的型号为BYK370的流平剂，加入行星机，在真空度为-0.09MPa、温度为100℃的条件下搅拌2小时，然后降至常温搅拌2小时。
实施例4：相变聚氨酯灌封胶II的制备
A组分：取100份的烟台万华生产的型号为PM-200的聚合MDI、150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，150份实施例1中制备的聚氨酯相变纳米胶囊(A)和1份安乡艾利特化工有限公司生产的型号为ALT 202的噁唑烷，加入行星机，在25℃、真空度为-0.09MPa的条件下真空搅拌2小时。
B组分：取50份蓖麻油，50份山东蓝星东大生产的型号为DL3000D的聚醚多元醇(粘度1000-1500cp)，0.01份二月桂酸二丁基锡催化剂，150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，150份实施例1中制备的聚氨酯相变纳米胶囊(A)和0.5份毕克化学公司生产的型号为BYK370的流平剂，加入行星机，在真空度为-0.09MPa、温度为100℃的条件下搅拌2小时，然后降至常温搅拌2小时。
实施例5：相变聚氨酯灌封胶III的制备
A组分：取100份的烟台万华生产的型号为PM-200的聚合MDI、150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，200份实施例1中制备的聚氨酯相变纳米胶囊(A)和1份安乡艾利特化工有限公司生产的型号为ALT 202的噁唑烷，加入行星机，在25℃、真空度为-0.09MPa的条件下真空搅拌2小时。
B组分：取50份蓖麻油，50份山东蓝星东大生产的型号为DL3000D的聚醚多元醇(粘度1000-1500cp)，0.01份二月桂酸二丁基锡催化剂，150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，200份实施例1中制备的聚氨酯相变纳米胶囊(A)和0.5份毕克化学公司生产的型号为BYK370的流平剂，加入行星机，在真空度为-0.09MPa、温度为100℃的条件下搅拌2小时，然后降至常温搅拌2小时。
实施例6：相变聚氨酯灌封胶IV的制备
A组分：取100份的烟台万华生产的型号为PM-200的聚合MDI、150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，150份实施例2中制备的聚氨酯相变纳米胶囊(B)和1份安乡艾利特化工有限公司生产的型号为ALT 202的噁唑烷，加入行星机，在25℃、真空度为-0.09MPa的条件下真空搅拌2小时。
B组分：取50份蓖麻油，50份山东蓝星东大生产的型号为DL3000D的聚醚多元醇(粘度1000-1500cp)，0.01份二月桂酸二丁基锡催化剂，150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，150份实施例2中制备的聚氨酯相变纳米胶囊(B)和0.5份毕克化学公司生产的型号为BYK370的流平剂，加入行星机，在真空度为-0.09MPa、温度为100℃的条件下搅拌2小时，然后降至常温搅拌2小时。
对比例2：相变聚氨酯灌封胶V的制备
A组分：取100份的烟台万华生产的型号为PM-200的聚合MDI、150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，100份湖北赛默新能源科技有限公司生产的型号为ME-37的相变微胶囊(粒径＞1μm)和1份安乡艾利特化工有限公司生产的型号为ALT 202的噁唑烷，加入行星机，在25℃、真空度为-0.09MPa的条件真空搅拌2小时。
B组分：取50份蓖麻油，50份山东蓝星东大生产的型号为DL3000D的聚醚多元醇(粘度1000-1500cp)，0.01份二月桂酸二丁基锡催化剂，150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，100份湖北赛默新能源科技有限公司生产的型号为ME-37的相变微胶囊(粒径＞1μm)和0.5份毕克化学公司生产的型号为BYK370的流平剂，加入行星机，在真空度为-0.09MPa、温度为100℃的条件下搅拌2小时，然后降至常温搅拌2小时。
对比例3：相变聚氨酯灌封胶VI的制备
A组分：取100份的烟台万华生产的型号为PM-200的聚合MDI、150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，200份湖北赛默新能源科技有限公司生产的型号为ME-37的相变微胶囊(粒径＞1μm)和1份安乡艾利特化工有限公司生产的型号为ALT 202的噁唑烷，加入行星机，在25℃、真空度为-0.09MPa的条件搅拌2小时。
B组分：取50份蓖麻油，50份山东蓝星东大生产的型号为DL3000D的聚醚多元醇(粘度1000-1500cp)，0.01份二月桂酸二丁基锡催化剂，150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，200份湖北赛默新能源科技有限公司生产的型号为ME-37的相变微胶囊(粒径＞1μm)和0.5份毕克化学公司生产的型号为BYK370的流平剂，加入行星机，在真空度为-0.09MPa、温度为100℃的条件下搅拌2小时，然后降至常温搅拌2小时。
对比例4相变聚氨酯灌封胶VII的制备
A组分：取100份的烟台万华生产的型号为PM-200的聚合MDI、150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，150份对比例1制备的聚氨酯相变纳米胶囊(C)和1份安乡艾利特化工有限公司生产的型号为ALT 202的噁唑烷，加入行星机，在25℃、真空度为-0.09MPa的条件真空搅拌2小时。
B组分：取50份蓖麻油，50份山东蓝星东大生产的型号为DL3000D的聚醚多元醇(粘度1000-1500cp)，0.01份二月桂酸二丁基锡催化剂，150份百图高新材料科技有限公司生产的型号为BAK90的球形氧化铝导热粉，150份对比例1制备的聚氨酯相变纳米胶囊(C)和0.5份毕克化学公司生产的型号为BYK370的流平剂，加入行星机，在真空度为-0.09MPa、温度为100℃的条件下搅拌2小时，然后降至常温搅拌2小时。
对实施例3-6以及对比例2-4制备的相变聚氨酯灌封胶进行如下性能测试。除混合粘度测试外，其他性能测试是在25℃，空气湿度50％RH的环境下固化 72小时后测试其性能，具体方法如下：
混合粘度测试方法：GB/T 2794-2013胶粘剂粘度的测定单圆筒旋转黏度计法。
硬度测试的方法：GB/T 2411-2008塑料和硬橡胶使用硬度计测定压痕硬度(邵氏硬度)。
导热系数测试方法：ASTM D5470-2017导热绝缘材料的热传输特性的标准试验方法。
热熔焓值测试方法：使用差式扫描量热仪(DSC)在10℃到65℃温度区间内进行测试，升温速度设置为0.1K/min。
胶体拉伸测试方法：GB/T 1040.2-2006塑料拉伸性能的测定第2部分：模塑和挤塑塑料的试验。
测试结果如下表2所示。
表2
Figure PCTCN2021132473-appb-000005
通过实施例3-5对比可知，包载了石蜡的聚氨酯相变纳米胶囊添加量越多， 固化后的灌封胶热熔焓值越大，同时粘度也会增大，而其硬度和拉伸强度并未出现明显区别，说明聚氨酯相变纳米胶囊的添加量不会对聚氨酯灌封胶的力学性能有很大影响；同时，导热系数并未出现太大变化，这是由于灌封胶的导热性能主要由添加的导热填料起主要作用，聚氨酯相变纳米胶囊的添加量不会对聚氨酯灌封胶的导热性能有很大影响。
对比实施例5和实施例6可知，聚氨酯相变纳米胶囊内包载的相变材料从石蜡变为硬脂酸，并不会引起各性能的明显变化。
通过对比例2和对比例3与实施例的对比可以发现，在其他配方不变的情况下添加等质量的市售相变微胶囊后，聚氨酯灌封胶的混合粘度增加了二十多倍，这是由于普通市售的相变微胶囊与聚氨酯胶体本身相容性不好，加之胶囊粒径为微米级别，远远大于本发明制备的聚氨酯相变纳米胶囊，从而导致聚氨酯灌封胶的混合粘度极高，而且热熔焓值也较低，说明添加该市售相变微胶囊后的聚氨酯灌封胶的相变效果较差。
通过对比例4与实施例4的对比可以发现，虽然对比例4和实施例4中添加的相变纳米胶囊占比一样，但是由于对比例4所用相变纳米胶囊中相变材料的包载率明显比实施例4所用相变纳米胶囊的包载率低(如表1所示)，因此对比例4所制备的灌封胶的热熔焓值明显低于实施例4，其相变效果较差。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种聚氨酯相变纳米胶囊，其特征在于，其为由两亲性嵌段共聚物包覆相变材料形成的纳米胶囊，所述两亲性嵌段共聚物的亲油端为聚氨酯链段，亲水端为甲氧基聚乙二醇链段。
  2. 根据权利要求1所述的聚氨酯相变纳米胶囊，其特征在于，所述聚氨酯链段和甲氧基聚乙二醇链段的质量比为2～3:1。
  3. 根据权利要求1所述的聚氨酯相变纳米胶囊，其特征在于，所述两亲性嵌段共聚物由聚氨酯和甲氧基聚乙二醇反应得到，所述聚氨酯由异氰酸酯和蓖麻油反应得到；
    优选地，所述异氰酸酯、蓖麻油和甲氧基聚乙二醇的质量比为1:0.3～0.4:0.4～0.6；
    优选地，所述异氰酸酯为二苯基甲烷二异氰酸酯；
    优选地，所述甲氧基聚乙二醇的分子量为1800～2200。
  4. 根据权利要求3所述的聚氨酯相变纳米胶囊，其特征在于，所述两亲性嵌段共聚物的制备方法包括如下步骤：
    将所述异氰酸酯和蓖麻油加入到溶剂中，加热回流共沸4小时～8小时，然后加入所述甲氧基聚乙二醇，加热回流共沸4小时～8小时，即得；
    优选地，所述溶剂为四氢呋喃；
    优选地，所述异氰酸酯和所述溶剂的质量比为1:2～3。
  5. 根据权利要求1所述的聚氨酯相变纳米胶囊，其特征在于，所述聚氨酯相变纳米胶囊由所述两亲性嵌段共聚物和所述相变材料在交联剂的存在下制备而成，所述两亲性嵌段共聚物和所述相变材料的投料质量比为1：0.8～1.2；
    优选地，所述交联剂为乙二胺。
  6. 根据权利要求1-5任一项所述的聚氨酯相变纳米胶囊，其特征在于，所述相变材料为石蜡和/或硬脂酸；和/或，
    所述聚氨酯相变纳米胶囊的粒径为100nm～200nm；和/或，
    所述聚氨酯相变纳米胶囊中相变材料的包载率不小于75％；
    优选地，所述聚氨酯相变纳米胶囊中相变材料的包载率不小于80％。
  7. 一种权利要求1-6任一项所述的聚氨酯相变纳米胶囊的制备方法，其特征在于，包括如下步骤：
    将所述两亲性嵌段共聚物和所述相变材料加入到有机溶剂中，在回流温度下混合搅拌2小时～6小时，降温至20℃～35℃，然后在转速为1000rpm～1400rpm的强力搅拌条件下加入含有所述交联剂的水溶液，继续在转速为1000rpm～1400rpm的条件下搅拌1小时～2小时，即得所述聚氨酯相变纳米胶囊；
    优选地，所述有机溶剂为乙酸乙酯；
    优选地，所述含有所述交联剂的水溶液中所述交联剂的浓度为0.4mmol/mL-0.6mmol/mL；
    优选地，所述两亲性嵌段共聚物和所述有机溶剂的质量比为1:1.8～2.2；所述有机溶剂和所述含有所述交联剂的水溶液的质量比为1:8～12。
  8. 一种相变聚氨酯灌封胶，其特征在于，包括A组分和B组分，使用时A组分和B组分的混合质量比为1-5:1，
    以重量份计，所述A组分由包含如下组分的原料制备而成：
    Figure PCTCN2021132473-appb-100001
    以重量份计，所述B组分由包含如下组分的原料制备而成：
    Figure PCTCN2021132473-appb-100002
  9. 根据权利要求8所述的相变聚氨酯灌封胶，其特征在于，使用时A组分和B组分的混合质量比为1-2:1；和/或，
    所述双组分相变聚氨酯灌封胶在固化前的混合粘度在25℃的条件下为8000mPa.s～12000mPa.s；和/或，
    所述异氰酸酯或者聚合异氰酸酯选自TDI、HDI、聚合MDI、液化MDI和XDI中的一种或多种，或者选自以TDI、HDI、聚合MDI、液化MDI和XDI中的一种或多种与聚醚、聚酯或者植物性多元醇为反应原料制备的异氰酸封端的预聚体；和/或，
    所述导热填料选自硅晶粉、球形氧化铝、氢氧化铝、氮化铝、氮化硼和石墨烯中的一种或多种；和/或，
    所述第一助剂为除水剂；和/或，
    所述多元醇可为聚醚多元醇、聚酯多元醇、植物类多元醇中的一种或多种；和/或，
    所述多元醇在25℃的粘度为400mPa.s～10000mPa.s；和/或，
    所述催化剂为有机锡类催化剂和/或叔胺类催化剂，所述有机锡类催化剂为辛酸亚锡和/或二月桂酸二丁基锡，所述叔胺类催化剂为三亚乙基二胺和/或三乙醇胺；和/或，
    所述第二助剂为流平剂。
  10. 一种权利要求8或9所述的相变聚氨酯灌封胶的制备方法，其特征在于，包括如下步骤：
    制备A组分：将所述异氰酸酯或者聚合异氰酸酯、导热填料、聚氨酯相变纳米胶囊和第一助剂在20℃～50℃真空搅拌0.5小时～5小时，即得；
    制备B组分：将所述多元醇、催化剂、导热填料、聚氨酯相变纳米胶囊和第二助剂在80℃～120℃真空搅拌1小时～5小时，即得。
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