WO2022199134A1 - Lightweight organic composite material and preparation method therefor - Google Patents

Lightweight organic composite material and preparation method therefor Download PDF

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Publication number
WO2022199134A1
WO2022199134A1 PCT/CN2021/137301 CN2021137301W WO2022199134A1 WO 2022199134 A1 WO2022199134 A1 WO 2022199134A1 CN 2021137301 W CN2021137301 W CN 2021137301W WO 2022199134 A1 WO2022199134 A1 WO 2022199134A1
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heat
composite material
expandable microspheres
organic composite
elastomer
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PCT/CN2021/137301
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French (fr)
Chinese (zh)
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胡友根
韦剑鸿
许亚东
林志强
赵涛
孙蓉
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中国科学院深圳先进技术研究院
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Publication of WO2022199134A1 publication Critical patent/WO2022199134A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/05—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the invention relates to the field of materials, in particular to a heat-expandable microsphere-based lightweight polymer composite material and a preparation method thereof.
  • Heat-expandable microspheres are polymer microspheres consisting of a thermoplastic polymer shell and an encapsulated liquid alkane gas.
  • the liquid alkane gas inside the microspheres vaporizes or decomposes to increase the internal pressure, and at the same time the thermoplastic polymer shell is softened by heating, so that the microspheres are heated to expand, the diameter increases to several times the original size, and the volume can be increased. Ten times or even a hundred times.
  • the expanded microsphere shell hardens again and the volume is fixed. This is the foaming principle of thermally expanding microspheres.
  • CN 110964376 A uses a small amount of expanded microspheres as a foaming agent, and discloses a water-based foaming ink and its preparation method and application.
  • Bao Jianjun et al (Materials Letters 194 (2017) 234–237) successfully prepared a light-weight epoxy foam sound-absorbing plastic by using 1 ⁇ 3wt% thermally expandable microspheres as a foaming agent.
  • most of the reports on the formation of heat-expandable microspheres mainly focus on the small filling amount of the microspheres, which are only used as foaming agents and not used as the matrix of composite materials.
  • silicon-based low-viscosity fluid materials and viscoelastic polymer materials have a wide range of applications, but due to their high density and weak mechanical strength, they cannot form bulk materials, which limit their applications.
  • the present invention provides a light-weight organic composite material based on heat-expandable microspheres and a preparation method thereof, the purpose of which is to enable the light-weight polymer composite material to use the spherical wall of the heat-expandable microspheres as the matrix of the composite material , and satisfies the composite of polymers or polymer precursors with different viscoelastic properties such as low viscosity fluids, elastomers to thermosetting materials.
  • Polymers of different viscoelastic properties, ranging from viscous fluids, elastomers to thermosets are in the outer voids of the heat-expandable microspheres.
  • the composite material has excellent performance, simple component composition and certain compressibility. The process is simple.
  • an organic composite material based on heat-expandable microspheres includes a continuous phase skeleton formed by interconnecting the spherical walls of the heat-expandable microspheres, and an organic compound filled in the outer gap of the heat-expandable microspheres.
  • Materials; the organic materials are selected from low viscosity fluids, elastomers and thermosetting polymer materials.
  • the low-viscosity fluid is selected from silicone oil, aliphatic hydrocarbons, fatty acids, and fatty alcohols.
  • the elastomer is selected from thermoplastic polyurethane elastomer rubber (TPU), silicone gel, ecoflex ® , polydimethylsiloxane (PDMS), thermoplastic vulcanizate (TPV), thermoplastic polyamide elastic Polyester (TPA), Thermoplastic Copolyester Elastomer (TPC), Styrenic Thermoplastic Elastomer (TPS), Thermoplastic Polyolefin Elastomer (TPO).
  • TPU thermoplastic polyurethane elastomer rubber
  • PDMS polydimethylsiloxane
  • TPV thermoplastic vulcanizate
  • TPA thermoplastic polyamide elastic Polyester
  • TPC Thermoplastic Copolyester Elastomer
  • TPS Styrenic Thermoplastic Elastomer
  • TPO Thermoplastic Polyolefin Elastomer
  • thermosetting material is selected from phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, and polyurethane.
  • the heat-expandable microsphere-based organic composite material is obtained by the following method: mixing heat-expandable microspheres with low-viscosity fluid, elastomer and thermosetting polymer material, or forming low-viscosity fluid, elastomer and The precursors of the thermosetting polymer materials are mixed to obtain a semi-solid or liquid mixture; the mixture is injected into a closed container, and heated to expand the heat-expandable microspheres and the spherical walls of the heat-expandable microspheres are connected to form a continuous phase skeleton.
  • the density of the heat-expandable microsphere-based organic composite material is above 0.04 g/cm 3 ; preferably 0.046 g/cm 3 -0.3 g/cm 3 .
  • the continuous phase skeleton density per unit volume of the heat-expandable microsphere-based organic composite material is above 0.021 g/cm 3 ; preferably 0.021-0.07 g/cm 3 .
  • the mass ratio of the continuous phase skeleton to the organic material filled in the outer gap of the thermally expandable microspheres is 1:0.01-2.5, preferably 1:0.42-1.5.
  • the compression elastic modulus of the heat-expandable microsphere-based organic composite material is 6-30 MPa.
  • the compressive strength of the heat-expandable microsphere-based organic composite material is above 0.22 MPa.
  • the heat-expandable microsphere is a polymer microsphere composed of a thermoplastic polymer shell and a wrapped liquid alkane gas.
  • the heat-expandable microspheres are selected from heat-expandable microspheres with acrylic shell; more preferably, the heat-expandable microspheres are selected from AkzoNobel EXPANCEL TM031DU40, AkzoNobel One of EXPANCEL TM051DU40, AkzoNobel EXPANCEL TM093DU120, AkzoNobel EXPANCEL TM980DU120, Advancell EHM303, Advancell EM403, Japan Matsumoto F-78KD, MSH-550.
  • the organic composite material based on thermally expandable microspheres is a solid material.
  • the heat-expandable microspheres account for the weight fraction: 99.99wt% ⁇ 20wt%; for example, 90wt%, 80wt%, 70wt%, 60wt%, 50wt%, 40wt%, 30wt%, 20wt%.
  • the mass fraction of the low-viscosity fluid, elastomer or thermosetting polymer material in the heat-expandable microsphere-based organic composite material is: 0.01wt%-80wt%, such as 10wt%, 20wt% %, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%.
  • a method for preparing the above-mentioned light-weight organic composite material based on thermally expanding microspheres comprises the following steps:
  • thermosetting polymer material (1) mixing the heat-expandable microspheres with a low-viscosity fluid, an elastomer and a thermosetting polymer material, or with a precursor that forms a low-viscosity fluid, an elastomer and a thermosetting polymer material, to obtain a liquid or semi-solid mixture;
  • the holding time in step 2) is 1-3 hours.
  • the holding temperature in step 2) is 80-180°C.
  • the mass ratio of the combination of thermally expandable microspheres and one or more of low-viscosity fluid, elastomer or thermosetting polymer material is 1:0.01-2.5, preferably 1:0.42 -1.5, eg 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4.
  • the volume of the closed mold cavity in step 2) is selected according to the mass of the heat-expandable microspheres added in step 1), and the volume of the mold cavity is not greater than: the mass of the heat-expandable microspheres is based on The product of the density of the heat-expandable microspheres of the organic composite material of heat-expandable microspheres, wherein the density of the heat-expandable microspheres of the heat-expandable microsphere-based organic composite material is 0.021 g/cm or more, preferably 0.021-0.07 g/cm 3 .
  • the preparation method is a process of changing from a small amount of powder or fluid to a larger volume of bulk material.
  • the size and shape of the closed mold cavity determine the size and shape of the lightweight polymer composite material. Shapes such as spheres, cubes, cylinders, and cones can be prepared without subsequent secondary processing. Blocks or structural parts of shapes and sizes can meet the production and preparation needs of some special structural and special parts.
  • the mixing in step 1) further includes an inhibitor that inhibits the curing of low-viscosity fluids, elastomers, solid polymer materials, or precursors that form low-viscosity fluids, elastomers, and thermosetting polymer materials , preferably, the inhibitor is selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, 3-methyl-1-ethynyl-3-ol, 3, 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol, 2-phenyl-3-butyn-2-ol and other alkynols, 3- Enyne compounds such as methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and 1,3,5,7-tetramethyl-1,3, 5,7-tetravinylcyclotetrasiloxane, benzotriazole
  • the present invention provides a composite embodiment of the lightweight polymer composite material capable of meeting polymers or polymer precursors from low viscosity fluids, elastomers to thermosetting materials, and the like.
  • low viscosity fluids silicone oils, aliphatic hydrocarbons, etc.
  • elastomers TPU, silicone gel, ecoflex, PDMS, TPV, TPA, TPC, TPS, TPO, VHB.
  • Thermosetting materials phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, polyurethane, etc.
  • the liquid epoxy resin can be epoxy resin NPEL-128, epoxy resin BE-188E, epoxy resin E51, epoxy resin YN1828, epoxy resin YN1826, epoxy resin E44, etc.
  • the curing agent can be imidazole, acid anhydride, polythiol, aromatic amine (such as m-xylylenediamine), polyetheramine, aliphatic amine curing agent (such as triethylenediamine, A mixture of one or more of triethylenetetramine, etc.), preferably polyetheramine, m-xylylenediamine, etc.; by weight, weigh the following materials: 100 parts of liquid epoxy resin, curing agent 5-150 parts, preferably 30-70 parts of polyetheramine curing agent, or 7-12 parts of m-xylylenediamine curing agent.
  • the invention illustrates that the lightweight polymer composite material and the preparation method thereof can be widely used in the fields of material interface properties, material molding, material preparation and the like.
  • the method for preparing a heat-expandable microsphere-based lightweight polymer composite material can prepare a lightweight polymer composite material with a density of 0.046 g/cm 3 -0.3 g/cm 3 .
  • the light-weight polymer composite material based on heat-expandable microspheres has excellent performance and certain compressibility.
  • the invention can also regulate the size and shape of the lightweight polymer composite material, and can prepare shapes such as spheres, cubes, cylinders, cones and the like.
  • the light-weight polymer composite material and the preparation method thereof can control the material properties, for example, the compressive elastic modulus and compressive strength of the composite material can be increased.
  • the lightweight polymer composite material is based on heat-expandable microspheres, and even if the mass fraction of the low-viscosity fluid polymer or polymer precursor is above 67 wt%, the lightweight polymer composite material can maintain good mechanical properties.
  • the preparation method is simple, environmentally friendly, low in energy consumption, high in production efficiency, and has very good application prospects.
  • the present invention has the following beneficial effects:
  • the invention provides a lightweight polymer composite material based on heat-expandable microspheres and a preparation method thereof.
  • the composite material has excellent performance, simple component composition and certain compressibility.
  • the lightweight polymer composite material can satisfy the composite of polymers or polymer precursors with different viscoelastic properties such as low-viscosity fluids, elastomers to thermosetting materials, and the composite of low-viscosity fluids such as silicone oil can be used to change the composite material.
  • Interface properties for the study of properties such as interface loss.
  • Elastomers such as silicone gel, thermosetting materials such as epoxy, etc. are composited with thermally expandable microspheres, and chemical cross-linking reaction occurs inside the composite material and a continuous phase is formed, and the prepared material has excellent comprehensive properties. And the preparation method is simple in process.
  • FIG. 1 is a schematic physical diagram of the preparation process of the embodiment.
  • FIG. 2 is a physical view of the pure thermally expandable microsphere block material in Example 1.
  • Fig. 3 is the compressive stress-strain curve of the embodiment, (a) is the compression curve of the pure heat-expandable microsphere block material of the embodiment 1; (b) is the compression curve of the heat-expandable microsphere and the silicone oil composite block material of the embodiment 2; (c) is the compression curve of the heat-expandable microspheres and the organosilicon gel composite block in Example 3; (d) is the compression curve of the organosilicon gel block.
  • FIG. 4 is a SEM image of the pure thermally expandable microsphere bulk material of Example 1.
  • FIG. 5 is the SEM image of the heat-expandable microsphere and the silicone oil composite block in Example 2.
  • FIG. 6 is an energy spectrum analysis (EDS) diagram of the heat-expandable microspheres and the silicone oil composite block in Example 2.
  • EDS energy spectrum analysis
  • FIG. 7 is a SEM image of the heat-expandable microsphere and the silicone gel composite block in Example 3.
  • FIG. 8 is an energy spectrum analysis (EDS) diagram of the thermally expandable microspheres and the organosilicon gel composite block in Example 3.
  • EDS energy spectrum analysis
  • FIG. 9 is a SEM image of the heat-expandable microsphere and epoxy resin composite block in Example 4.
  • FIG. 10 is a comparison chart of the results of heat-expandable microspheres with different contents in Example 5.
  • FIG. 10 is a comparison chart of the results of heat-expandable microspheres with different contents in Example 5.
  • the heat-expandable microspheres can be selected from AkzoNobel EXPANCEL TM 031DU40, AkzoNobel EXPANCEL TM 051DU40, AkzoNobel EXPANCEL TM 093DU120, AkzoNobel EXPANCEL TM 980DU120, Advancel EHM303, Advancel EM403, Matsumoto F-78KD, MSH- One of the 550.
  • the low viscosity fluid is a fluid with a kinematic viscosity of less than 12500 mm 2 /s at 25°C.
  • it is selected from silicone oil, aliphatic hydrocarbon, etc.; silicone oil types include methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, Methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen-containing silicone oil, hydroxy hydrogen-containing silicone oil, cyano-containing silicone oil, etc., preferably, can be selected from Shin-Etsu KF96-1000cs (25 °C A series of silicone oils such as kinematic viscosity of 1000 mm 2 /s), KF96-3000cs (kinematic viscosity of 3000 mm 2 ).
  • the elastomer is selected from TPU, silicone gel, ecoflex, PDMS, TPV, TPA, TPC, TPS, TPO.
  • the thermosetting material may be selected from one of phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, polyurethane and the like.
  • the liquid epoxy resin can be epoxy resin NPEL-128, epoxy resin BE-188E, epoxy resin E51, epoxy resin YN1828, epoxy resin YN1826, epoxy resin E44, etc.
  • a mixture of one or more of the curing agents; curing agents can be imidazoles, acid anhydrides, polyvalent mercaptans, aromatic amines, polyetheramines, aliphatic amine curing agents (such as triethylenediamine, triethylenetetramine, etc.)
  • curing agents can be imidazoles, acid anhydrides, polyvalent mercaptans, aromatic amines, polyetheramines, aliphatic amine curing agents (such as triethylenediamine, triethylenetetramine, etc.)
  • One or more mixtures in parts by weight, weigh the following materials: 100 parts of liquid epoxy resin, and 5-150 parts of curing agent.
  • the initial compound of the elastomer is added to suppress the curing reaction.
  • Inhibitors can be selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, 3-methyl-1-ethynyl-3-ol, 3, 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol, 2-phenyl-3-butyn-2-ol and other alkynols, 3- Enyne compounds such as methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and 1,3,5,7-tetramethyl-1,3, 5,7-tetravinylcyclotetrasiloxane, benzotriazole, etc., preferably: 1-ethynyl-1-cyclohexanol.
  • the inhibitor content can be from 1/100,000 to 1/1,000.
  • the model is Apreo 2. SEM pictures of the samples taken by the SEM.
  • MAX series high-precision load testing machine (model MAX-1kN-P-2) to test the compression performance of the cube sample (10mm ⁇ 10mm ⁇ 5mm), the test speed is 1mm/min, the compression strain is 90%, The compressive strength of the lightweight polymer composite was measured as the compressive strength at 10% strain.
  • FIG. 2 is a physical view of a pure thermally expandable microsphere block.
  • FIG. 3( a ) is the compression curve of the pure thermally expandable microsphere bulk material of Example 1.
  • FIG. The density of the sample in Example 1 was measured to be 0.055 g/cm 3 , the compressive elastic modulus was 17.3 MPa, and the compressive strength was 0.40 MPa.
  • Figure 4 is the SEM image of the pure thermally expandable microsphere block material, which shows that the thermally expandable microspheres of the powder are extruded from each other by volume expansion at high temperature, and finally form a block material with macroscopic mechanical strength.
  • the heat-expandable microspheres AkzoNobel EXPANCEL TM 031DU40 and dimethyl silicone oil Shin-Etsu KF96H-12500cs were thoroughly mixed to obtain a mixture, and the mass fraction of dimethyl silicone oil was 54wt%. Then take 0.40g of the above mixture, put it into a closed mold cavity (26mm ⁇ 26mm ⁇ 5mm), and then keep it at 95°C for 1.5h, then move it to room temperature, and wait until the mold temperature drops to room temperature, and then re-heat.
  • a light-weight polymer composite based on heat-expandable microspheres can be obtained by opening the mold and sampling.
  • the density of the sample in Example 2 was measured to be 0.12 g/cm 3 , and Fig. 3(b) is the compression curve of Example 2.
  • the compressive elastic modulus was 14 MPa and the compressive strength was 0.34 MPa.
  • the volume fraction of silicone oil compounded in this lightweight polymer composite is about 7 vol%.
  • the silicone oil did not react chemically in the system, but it played a role in regulating the sphere-to-sphere interface of the thermally expanded microspheres and affected the mechanical properties of the composites. It can be seen from the compression curve in Figure 3 that the compression curve of Example 2 is similar to that of pure thermally expandable microspheres, but the mechanical properties are decreased.
  • Figure 5 is the SEM image of the composite material block in Example 2. From the microstructure, it can be seen that the composite material formed by the composite of thermally expandable microspheres and silicone oil is based on thermally expandable microspheres, and the microspheres are still closely combined with the microspheres.
  • Figure 6 is the energy spectrum analysis diagram of the composite material in Example 2.
  • the silicon element (silicon oil contains silicon element, microsphere does not contain silicon element) is distributed at the intersection of the microsphere and the microsphere, that is, the silicone oil exists in the The junction between microspheres and microspheres.
  • silicone oil does not play a role in strength inside the block.
  • silicone oil can usually be used as a lubricant, it will affect the connection between the walls of the thermally expanded microspheres, and cannot form a continuous phase skeleton, and the silicone oil acts as a fluid to reduce the thermal expansion of the microspheres. the interaction between the ball and the ball interface.
  • the method of the present invention can not only form a solid block, but also maintain a certain mechanical strength, and will not appear "loose” because of this; the mechanical strength of the silicone oil is greatly improved, making it possible Available in block form.
  • the inhibitor added to the B component of the liquid silicone gel (the main components are vinyl silicone oil, catalyst, etc.): 1-ethynyl-1-cyclohexanol, after mixing the two thoroughly, with the liquid silicone
  • the liquid silicone gel was fully mixed with the thermally expandable microspheres AkzoNobel EXPANCEL TM 031DU40 to obtain a mixture, and the mass fraction of the silicone gel was 54 wt %.
  • Example 3 The density of the sample in Example 3 is measured to be 0.12 g/cm 3 .
  • Figure 3(c) is the compression curve of the composite material described in Example 3.
  • the elastic modulus of the material is 10 MPa and the compressive strength is 0.26MPa.
  • the compression curve is similar to the compression curve of the pure microsphere block, not similar to the compression curve of the pure silicone gel block in Fig. 3(d) (Fig. Pure silicone gel blocks made of the same material as the gel). It shows that when the mass fraction of organosilicon gel in the lightweight polymer composite reaches 54wt%, it can still show a compression curve similar to that of pure thermally expanded microspheres.
  • the SEM image in Figure 7 also shows that thermal expansion
  • the microspheres are closely connected with each other, and the silicone gel is distributed at the connection between the spheres. Interfaces and junctions between balls. That is to say, the block material of Example 3 is still based on heat-expandable microspheres, but it is also worth noting that in the above heating process, the A/B components of the liquid silicone gel will undergo cross-linking reaction to form silicone gel. glue. Inside the block, the silica gel plays a role in regulating the interface between the microspheres.
  • the lightweight polymer composite material of the present invention has many advantages such as low density, simple component composition, and excellent compressive mechanical properties, and uses thermally expandable microspheres as the matrix of the composite material, which can meet the requirements of low viscosity fluids.
  • the theoretical density of group a is 0.009 g/cm 3 ; the theoretical density of group b is 0.015 g/cm 3 ; the theoretical density of group c is 0.021 g/cm 3 ; the theoretical density of group d is 0.027 g/cm 3 .
  • the experimental results are shown in Figure 10. Observing the state of group ad, it can be seen that if the amount of heat-expandable microspheres is too small, and the cavity of the sealed mold cannot be filled after expansion, the recombination between the heat-expandable microspheres cannot be realized, and then a tightly connected phase skeleton structure is formed. .

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Abstract

The present invention relates to a lightweight organic composite material and a preparation method therefor. Specifically disclosed is an organic composite material based on thermally expandable microspheres. The organic composite material comprises a continuous phase skeleton formed by interconnection of sphere walls of the thermally expandable microspheres, and an organic material with which outer gaps of the thermally expandable microspheres are filled. The organic material is selected from a low-viscosity fluid, an elastomer, and a thermosetting polymeric material. The organic composite material based on thermally expandable microspheres is obtained by means of the following method: mixing the thermally expandable microspheres with the low-viscosity fluid, the elastomer, and the thermosetting polymeric material, or with precursors forming the low-viscosity fluid, the elastomer, and the thermosetting polymeric material, to obtain a semi-solid or liquid mixture; and injecting the mixture into a closed container and heating same such that the thermally expandable microspheres are expanded and the sphere walls of the thermally expandable microspheres are connected to form the continuous phase skeleton. The material has certain compression performance, and is light in weight, excellent in performance, and wide in application; and the preparation method is simple, convenient, and easy to implement.

Description

一种轻质有机复合材料及其制备方法A kind of lightweight organic composite material and preparation method thereof 技术领域technical field
本发明涉及材料领域，具体涉及一种基于热膨胀微球的轻质聚合物复合材料及其制备方法。The invention relates to the field of materials, in particular to a heat-expandable microsphere-based lightweight polymer composite material and a preparation method thereof.
背景技术Background technique
热膨胀微球是一种由热塑性聚合物外壳和包裹的液态烷烃气体组成的聚合物微球。当加热热膨胀微球时，微球内部的液态烷烃气体汽化或分解使得内部压力增大，同时热塑性聚合物外壳受热软化，使得微球受热膨胀，直径增大到原来的几倍，体积可增大十倍乃至百倍。当温度冷却后，膨胀微球外壳再次变硬，体积固定下来。这即是热膨胀微球的发泡原理。Heat-expandable microspheres are polymer microspheres consisting of a thermoplastic polymer shell and an encapsulated liquid alkane gas. When heating the thermally expanded microspheres, the liquid alkane gas inside the microspheres vaporizes or decomposes to increase the internal pressure, and at the same time the thermoplastic polymer shell is softened by heating, so that the microspheres are heated to expand, the diameter increases to several times the original size, and the volume can be increased. Ten times or even a hundred times. When the temperature cools, the expanded microsphere shell hardens again and the volume is fixed. This is the foaming principle of thermally expanding microspheres.
基于热膨胀微球的发泡原理，CN 110964376 A利用少量膨胀微球作为发泡剂，公开了一种水性发泡油墨及其制备方法和应用。包建军等人(Materials Letters 194(2017)234–237)利用1~3wt%含量的热膨胀微球作为发泡剂成功制备出一种轻质环氧泡沫的吸音塑料。目前大部分关于热膨胀微球成型的报道，大多集中在微球填充量小、只作为发泡剂不做复合材料基体，即很少有以热膨胀微球为基体的聚合物复合材料研究的报道，并且基于热膨胀微球的轻质聚合物复合材料组分组成简单、工艺路线简化的研究也较少。Based on the foaming principle of thermally expanded microspheres, CN 110964376 A uses a small amount of expanded microspheres as a foaming agent, and discloses a water-based foaming ink and its preparation method and application. Bao Jianjun et al (Materials Letters 194 (2017) 234–237) successfully prepared a light-weight epoxy foam sound-absorbing plastic by using 1~3wt% thermally expandable microspheres as a foaming agent. At present, most of the reports on the formation of heat-expandable microspheres mainly focus on the small filling amount of the microspheres, which are only used as foaming agents and not used as the matrix of composite materials. Moreover, there are few studies on the composition of lightweight polymer composites based on thermally expandable microspheres with simple components and simplified process routes.
在现有技术中，硅基低粘度流体材料、粘弹性聚合物材料具有广泛的用途，但是受限于其密度高以及力学强度弱无法形成块材等问题，限制了其一部分的应用。In the prior art, silicon-based low-viscosity fluid materials and viscoelastic polymer materials have a wide range of applications, but due to their high density and weak mechanical strength, they cannot form bulk materials, which limit their applications.
技术问题technical problem
针对现有技术的缺陷，本发明提供一种基于热膨胀微球的轻质有机复合材料及其制备方法，目的在于使所述轻质聚合物复合材料能够以热膨胀微球的球壁作为复合材料基体，并满足低粘度流体、弹性体至热固性材料等不同粘弹性性质的聚合物或聚合物前驱体的复合，聚合物或聚合物前驱体在所述材料内部发生交联反应形成连续相，而低粘度流体、弹性体至热固性材料等不同粘弹性性质的聚合物在热膨胀微球外侧空隙中。所述复合材料性能优良、组分组成简单、并具有一定的压缩性能。工艺简易。In view of the defects of the prior art, the present invention provides a light-weight organic composite material based on heat-expandable microspheres and a preparation method thereof, the purpose of which is to enable the light-weight polymer composite material to use the spherical wall of the heat-expandable microspheres as the matrix of the composite material , and satisfies the composite of polymers or polymer precursors with different viscoelastic properties such as low viscosity fluids, elastomers to thermosetting materials. Polymers of different viscoelastic properties, ranging from viscous fluids, elastomers to thermosets, are in the outer voids of the heat-expandable microspheres. The composite material has excellent performance, simple component composition and certain compressibility. The process is simple.
技术解决方案technical solutions
为使本发明的目的、优点更加清楚，下面将详细描述此发明的技术方案，本发明采用以下技术方案：In order to make the purpose and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below, and the present invention adopts the following technical solutions:
第一方面，提供了一种基于热膨胀微球的有机复合材料，所述有机复合材料中包括由热膨胀微球的球壁相互连接形成的连续相骨架，以及在热膨胀微球外部间隙中填充的有机材料；所述的有机材料选自低粘度流体、弹性体以及热固性聚合物材料。In a first aspect, an organic composite material based on heat-expandable microspheres is provided, the organic composite material includes a continuous phase skeleton formed by interconnecting the spherical walls of the heat-expandable microspheres, and an organic compound filled in the outer gap of the heat-expandable microspheres. Materials; the organic materials are selected from low viscosity fluids, elastomers and thermosetting polymer materials.
在本发明的技术方案中，低粘度流体选自硅油、脂肪烃、脂肪酸、脂肪醇。In the technical solution of the present invention, the low-viscosity fluid is selected from silicone oil, aliphatic hydrocarbons, fatty acids, and fatty alcohols.
在本发明的技术方案中，弹性体选自热塑性聚氨酯弹性体橡胶（TPU）、有机硅凝胶、ecoflex ®、聚二甲基硅氧烷（PDMS）、热塑性硫化橡胶（TPV）、热塑性聚酰胺弹性体（TPA）、热塑性共聚酯弹性体（TPC）、苯乙烯类热塑性弹性体（TPS）、热塑性聚烯烃弹性体（TPO）。 In the technical solution of the present invention, the elastomer is selected from thermoplastic polyurethane elastomer rubber (TPU), silicone gel, ecoflex ® , polydimethylsiloxane (PDMS), thermoplastic vulcanizate (TPV), thermoplastic polyamide elastic Polyester (TPA), Thermoplastic Copolyester Elastomer (TPC), Styrenic Thermoplastic Elastomer (TPS), Thermoplastic Polyolefin Elastomer (TPO).
在本发明的技术方案中，热固性材料选自酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂、聚氨酯。In the technical solution of the present invention, the thermosetting material is selected from phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, and polyurethane.
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料通过以下方法获得：将热膨胀微球与低粘度流体、弹性体以及热固性聚合物材料，或与形成低粘度流体、弹性体以及热固性聚合物材料的前驱体进行混合，得到半固体或液体的混料；将混料注入密闭容器中，并加热使热膨胀微球膨胀且热膨胀微球的球壁连接形成连续相骨架。In the technical solution of the present invention, the heat-expandable microsphere-based organic composite material is obtained by the following method: mixing heat-expandable microspheres with low-viscosity fluid, elastomer and thermosetting polymer material, or forming low-viscosity fluid, elastomer and The precursors of the thermosetting polymer materials are mixed to obtain a semi-solid or liquid mixture; the mixture is injected into a closed container, and heated to expand the heat-expandable microspheres and the spherical walls of the heat-expandable microspheres are connected to form a continuous phase skeleton.
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料的密度为0.04g/cm 3以上；优选为0.046 g/cm 3-0.3g/cm 3。 In the technical solution of the present invention, the density of the heat-expandable microsphere-based organic composite material is above 0.04 g/cm 3 ; preferably 0.046 g/cm 3 -0.3 g/cm 3 .
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料的中单位体积内连续相骨架密度为0.021g/cm 3以上；优选为0.021-0.07 g/cm 3。 In the technical solution of the present invention, the continuous phase skeleton density per unit volume of the heat-expandable microsphere-based organic composite material is above 0.021 g/cm 3 ; preferably 0.021-0.07 g/cm 3 .
在本发明的技术方案中，连续相骨架与在热膨胀微球外部间隙中填充的有机材料的质量比为1:0.01-2.5，优选为1:0.42-1.5。In the technical solution of the present invention, the mass ratio of the continuous phase skeleton to the organic material filled in the outer gap of the thermally expandable microspheres is 1:0.01-2.5, preferably 1:0.42-1.5.
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料的压缩的弹性模量为6-30MPa。In the technical solution of the present invention, the compression elastic modulus of the heat-expandable microsphere-based organic composite material is 6-30 MPa.
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料的压缩强度为0.22MPa以上。In the technical solution of the present invention, the compressive strength of the heat-expandable microsphere-based organic composite material is above 0.22 MPa.
在本发明的技术方案中，所述热膨胀微球是一种由热塑性聚合物外壳和包裹的液态烷烃气体组成的聚合物微球。优选地，所述热膨胀微球选自以丙烯酸外壳的热膨胀微球；更优选地，所述热膨胀微球选自AkzoNobel EXPANCEL TM031DU40，AkzoNobel EXPANCEL TM051DU40，AkzoNobel EXPANCEL TM093DU120，AkzoNobel EXPANCEL TM980DU120，Advancell EHM303，Advancell EM403，日本松本F-78KD，MSH-550中的一种。In the technical solution of the present invention, the heat-expandable microsphere is a polymer microsphere composed of a thermoplastic polymer shell and a wrapped liquid alkane gas. Preferably, the heat-expandable microspheres are selected from heat-expandable microspheres with acrylic shell; more preferably, the heat-expandable microspheres are selected from AkzoNobel EXPANCEL TM031DU40, AkzoNobel One of EXPANCEL TM051DU40, AkzoNobel EXPANCEL TM093DU120, AkzoNobel EXPANCEL TM980DU120, Advancell EHM303, Advancell EM403, Japan Matsumoto F-78KD, MSH-550.
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料为固体材料。In the technical solution of the present invention, the organic composite material based on thermally expandable microspheres is a solid material.
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料中热膨胀微球所占重量分数:99.99wt%~20wt%；例如90wt%、80wt%、70wt%、60wt%、50wt%、40wt%、30wt%、20wt%。In the technical scheme of the present invention, in the organic composite material based on heat-expandable microspheres, the heat-expandable microspheres account for the weight fraction: 99.99wt%～20wt%; for example, 90wt%, 80wt%, 70wt%, 60wt%, 50wt%, 40wt%, 30wt%, 20wt%.
在本发明的技术方案中，所述基于热膨胀微球的有机复合材料中所述低粘度流体、弹性体或热固性聚合物材料所占质量分数为:0.01wt%-80wt%，例如10wt%、20wt%、30wt%、40wt%、50wt%、60wt%、70wt%、80wt%。In the technical solution of the present invention, the mass fraction of the low-viscosity fluid, elastomer or thermosetting polymer material in the heat-expandable microsphere-based organic composite material is: 0.01wt%-80wt%, such as 10wt%, 20wt% %, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%.
第二方面，提供了上述基于热膨胀微球的轻质有机复合材料的制备方法，其包括如下步骤：In a second aspect, a method for preparing the above-mentioned light-weight organic composite material based on thermally expanding microspheres is provided, which comprises the following steps:
(1)将热膨胀微球与低粘度流体、弹性体以及热固性聚合物材料，或与形成低粘度流体、弹性体以及热固性聚合物材料的前驱体进行混合，得到液体或半固体的混料；(1) mixing the heat-expandable microspheres with a low-viscosity fluid, an elastomer and a thermosetting polymer material, or with a precursor that forms a low-viscosity fluid, an elastomer and a thermosetting polymer material, to obtain a liquid or semi-solid mixture;
(2)将上述混料，放入封闭的模具腔室中，以热膨胀微球的发泡温度加热，保温膨胀至反应完全，降温后从模具中取出，获得基于热膨胀微球的轻质有机复合材料。(2) the above-mentioned mixture is put into a closed mold cavity, heated with the foaming temperature of the thermally expandable microspheres, thermally expanded until the reaction is complete, and taken out from the mold after cooling to obtain a light-weight organic composite based on the thermally expandable microspheres Material.
在本发明的技术方案中，步骤2）中保温时间为1-3小时。In the technical solution of the present invention, the holding time in step 2) is 1-3 hours.
在本发明的技术方案中，步骤2）中保温温度为80-180℃。In the technical solution of the present invention, the holding temperature in step 2) is 80-180°C.
在本发明的技术方案中，步骤1）中热膨胀微球与低粘度流体、弹性体或热固性聚合物材料中一种或多种的组合的质量比为1:0.01-2.5，优选为1:0.42-1.5，例如1:0.5、1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.1、1:1.2、1:1.3、1:1.4。In the technical solution of the present invention, in step 1), the mass ratio of the combination of thermally expandable microspheres and one or more of low-viscosity fluid, elastomer or thermosetting polymer material is 1:0.01-2.5, preferably 1:0.42 -1.5, eg 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4.
在本发明的技术方案中，步骤2）中封闭的模具腔室的体积根据步骤1）中加入的热膨胀微球的质量选择，所述模具腔室的体积不大于：热膨胀微球的质量与基于热膨胀微球的有机复合材料的中热膨胀微球的密度的乘积，其中基于热膨胀微球的有机复合材料的中热膨胀微球的密度为0.021g/cm 3以上，优选为0.021-0.07 g/cm 3。 In the technical solution of the present invention, the volume of the closed mold cavity in step 2) is selected according to the mass of the heat-expandable microspheres added in step 1), and the volume of the mold cavity is not greater than: the mass of the heat-expandable microspheres is based on The product of the density of the heat-expandable microspheres of the organic composite material of heat-expandable microspheres, wherein the density of the heat-expandable microspheres of the heat-expandable microsphere-based organic composite material is 0.021 g/cm or more, preferably 0.021-0.07 g/cm 3 .
在本发明的技术方案中，所述制备方法是一个由少量粉体或者流体变成较大体积块材的过程。其中封闭的模具腔室的大小和形状决定了轻质聚合物复合材料的大小和形状，可制备出圆球、方体、柱体、锥体等形状，无需后续二次加工，即可得到符合形状和大小的块材或结构件，可满足了某些特殊结构特殊部件的生产制备需求。In the technical solution of the present invention, the preparation method is a process of changing from a small amount of powder or fluid to a larger volume of bulk material. The size and shape of the closed mold cavity determine the size and shape of the lightweight polymer composite material. Shapes such as spheres, cubes, cylinders, and cones can be prepared without subsequent secondary processing. Blocks or structural parts of shapes and sizes can meet the production and preparation needs of some special structural and special parts.
在本发明的技术方案中，步骤1）混料中还包括抑制低粘度流体、弹性体、固性聚合物材料，或形成低粘度流体、弹性体以及热固性聚合物材料的前驱体固化的抑制剂，优选地，抑制剂选自1-乙炔基-1-环己醇、2-甲基-3-丁炔基-2-醇、3-甲基-1-乙炔基-3-醇、3,5-二甲基-1-己炔基-3-醇、3-甲基-1-十二炔-3-醇、2-苯基-3-丁炔-2-醇等炔醇、3-甲基-3-戊烯-1-炔、3,5-二甲基-3-己烯-1-炔等烯炔化合物，以及1,3,5,7-四甲基-1,3,5,7-四乙烯基环四硅氧烷，苯并三唑等。In the technical solution of the present invention, the mixing in step 1) further includes an inhibitor that inhibits the curing of low-viscosity fluids, elastomers, solid polymer materials, or precursors that form low-viscosity fluids, elastomers, and thermosetting polymer materials , preferably, the inhibitor is selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, 3-methyl-1-ethynyl-3-ol, 3, 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol, 2-phenyl-3-butyn-2-ol and other alkynols, 3- Enyne compounds such as methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and 1,3,5,7-tetramethyl-1,3, 5,7-tetravinylcyclotetrasiloxane, benzotriazole, etc.
本发明提供了所述轻质聚合物复合材料能够满足低粘度流体、弹性体至热固性材料等的聚合物或聚合物前驱体的复合实施案例。优选地，低粘度的流体:硅油，脂肪烃等；弹性体:TPU、有机硅凝胶、ecoflex、PDMS、TPV、TPA、TPC、TPS、TPO、VHB。热固性材料:酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂、聚氨酯等。以环氧树脂为例，所述液体环氧树脂可为环氧树脂NPEL-128、环氧树脂BE-188E、环氧树脂E51、环氧树脂YN1828、环氧树脂YN1826、环氧树脂E44等等中的一种或多种的混合物；固化剂可为咪唑类、酸酐类、多元硫醇、芳香胺(如间苯二甲胺)、聚醚胺、脂肪胺固化剂(如三乙烯二胺、三乙烯四胺等）中的一种或多种的混合物，优选地聚醚胺、间苯二甲胺等；按重量份计，称取以下各种物料：液体环氧树脂100份、固化剂5-150份，优选地聚醚胺固化剂30-70份，或者间苯二甲胺固化剂份7-12份。本发明说明了该轻质聚合物复合材料及其制备方法在材料界面性质、材料成型、材料制备等领域可具有广泛的应用。The present invention provides a composite embodiment of the lightweight polymer composite material capable of meeting polymers or polymer precursors from low viscosity fluids, elastomers to thermosetting materials, and the like. Preferably, low viscosity fluids: silicone oils, aliphatic hydrocarbons, etc.; elastomers: TPU, silicone gel, ecoflex, PDMS, TPV, TPA, TPC, TPS, TPO, VHB. Thermosetting materials: phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, polyurethane, etc. Taking epoxy resin as an example, the liquid epoxy resin can be epoxy resin NPEL-128, epoxy resin BE-188E, epoxy resin E51, epoxy resin YN1828, epoxy resin YN1826, epoxy resin E44, etc. A mixture of one or more of; the curing agent can be imidazole, acid anhydride, polythiol, aromatic amine (such as m-xylylenediamine), polyetheramine, aliphatic amine curing agent (such as triethylenediamine, A mixture of one or more of triethylenetetramine, etc.), preferably polyetheramine, m-xylylenediamine, etc.; by weight, weigh the following materials: 100 parts of liquid epoxy resin, curing agent 5-150 parts, preferably 30-70 parts of polyetheramine curing agent, or 7-12 parts of m-xylylenediamine curing agent. The invention illustrates that the lightweight polymer composite material and the preparation method thereof can be widely used in the fields of material interface properties, material molding, material preparation and the like.
所述的一种基于热膨胀微球的轻质聚合物复合材料的制备方法，可制备出密度为0.046 g/cm 3-0.3g/cm 3轻质聚合物复合材料。 The method for preparing a heat-expandable microsphere-based lightweight polymer composite material can prepare a lightweight polymer composite material with a density of 0.046 g/cm 3 -0.3 g/cm 3 .
所述的一种基于热膨胀微球的轻质聚合物复合材料性能优良、具有一定压缩性能的。The light-weight polymer composite material based on heat-expandable microspheres has excellent performance and certain compressibility.
本发明还可调控轻质聚合物复合材料的大小和形状，可制备出圆球、方体、柱体、锥体等形状。The invention can also regulate the size and shape of the lightweight polymer composite material, and can prepare shapes such as spheres, cubes, cylinders, cones and the like.
所述轻质聚合物复合材料，及其制备方法在材料性能方面具有调控作用，比如可以增加复合材料的压缩弹性模量和压缩强度等。The light-weight polymer composite material and the preparation method thereof can control the material properties, for example, the compressive elastic modulus and compressive strength of the composite material can be increased.
所述轻质聚合物复合材料以热膨胀微球为基体，即使低粘度流体聚合物或聚合物前驱体质量分数在67wt%以上，所述轻质聚合物复合材料也能保持较好的力学性能。The lightweight polymer composite material is based on heat-expandable microspheres, and even if the mass fraction of the low-viscosity fluid polymer or polymer precursor is above 67 wt%, the lightweight polymer composite material can maintain good mechanical properties.
制备方法简便、环保、能耗低，生产效率高，具有非常良好的应用前景。The preparation method is simple, environmentally friendly, low in energy consumption, high in production efficiency, and has very good application prospects.
有益效果beneficial effect
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供了一种基于热膨胀微球的轻质聚合物复合材料及其制备方法，所述复合材料性能优良、组分组成简单、并具有一定的压缩性能。所述轻质聚合物复合材料能够满足低粘度流体、弹性体至热固性材料等不同粘弹性性质的聚合物或聚合物前驱体的复合，如硅油等低粘度流体的复合可以用于改变复合材料的界面性质，用于界面损耗等性能的研究。如有机硅凝胶等弹性体、环氧等热固性材料等与热膨胀微球复合，并在所述复合材料内部发生化学交联反应以及形成连续相，制备所得材料具有优良的综合性能。并且所述制备方法工艺简易。The invention provides a lightweight polymer composite material based on heat-expandable microspheres and a preparation method thereof. The composite material has excellent performance, simple component composition and certain compressibility. The lightweight polymer composite material can satisfy the composite of polymers or polymer precursors with different viscoelastic properties such as low-viscosity fluids, elastomers to thermosetting materials, and the composite of low-viscosity fluids such as silicone oil can be used to change the composite material. Interface properties, for the study of properties such as interface loss. Elastomers such as silicone gel, thermosetting materials such as epoxy, etc. are composited with thermally expandable microspheres, and chemical cross-linking reaction occurs inside the composite material and a continuous phase is formed, and the prepared material has excellent comprehensive properties. And the preparation method is simple in process.
附图说明Description of drawings
图1为实施例的制备过程示意实物图。FIG. 1 is a schematic physical diagram of the preparation process of the embodiment.
图2为实施例1纯热膨胀微球块材的实物图。FIG. 2 is a physical view of the pure thermally expandable microsphere block material in Example 1. FIG.
图3为实施例的压缩应力应变曲线，(a)为实施例1纯热膨胀微球块材的压缩曲线；(b)为实施例2热膨胀微球与硅油复合块材的压缩曲线；(c)为实施例3热膨胀微球与有机硅凝胶复合块材的压缩曲线；(d)为有机硅凝胶块材的压缩曲线。Fig. 3 is the compressive stress-strain curve of the embodiment, (a) is the compression curve of the pure heat-expandable microsphere block material of the embodiment 1; (b) is the compression curve of the heat-expandable microsphere and the silicone oil composite block material of the embodiment 2; (c) is the compression curve of the heat-expandable microspheres and the organosilicon gel composite block in Example 3; (d) is the compression curve of the organosilicon gel block.
图4为实施例1纯热膨胀微球块材的SEM图。FIG. 4 is a SEM image of the pure thermally expandable microsphere bulk material of Example 1. FIG.
图5为实施例2热膨胀微球与硅油复合块材的SEM图。FIG. 5 is the SEM image of the heat-expandable microsphere and the silicone oil composite block in Example 2. FIG.
图6为实施例2热膨胀微球与硅油复合块材的能谱分析(EDS)图。FIG. 6 is an energy spectrum analysis (EDS) diagram of the heat-expandable microspheres and the silicone oil composite block in Example 2. FIG.
图7为实施例3热膨胀微球与有机硅凝胶复合块材的SEM图。FIG. 7 is a SEM image of the heat-expandable microsphere and the silicone gel composite block in Example 3. FIG.
图8为实施例3热膨胀微球与有机硅凝胶复合块材的能谱分析(EDS)图。FIG. 8 is an energy spectrum analysis (EDS) diagram of the thermally expandable microspheres and the organosilicon gel composite block in Example 3. FIG.
图9为实施例4热膨胀微球与环氧树脂复合块材的SEM图。FIG. 9 is a SEM image of the heat-expandable microsphere and epoxy resin composite block in Example 4. FIG.
图10为实施例5不同含量的热膨胀微球结果对比图。FIG. 10 is a comparison chart of the results of heat-expandable microspheres with different contents in Example 5. FIG.
本发明的实施方式Embodiments of the present invention
为了使本发明的上述目的、特征和优点能够更加明显易懂，下面对本发明的具体实施方式做详细的说明，但不能理解为对本发明的可实施范围的限定。In order to make the above objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention will be described in detail below, but should not be construed as limiting the scope of the present invention.
在本发明的一些具体实施例中，热膨胀微球可选自AkzoNobel EXPANCEL TM031DU40，AkzoNobel EXPANCEL TM051DU40，AkzoNobel EXPANCEL TM093DU120，AkzoNobel EXPANCEL TM980DU120，Advancell EHM303，Advancell EM403，日本松本F-78KD，MSH-550中的一种。 In some specific embodiments of the present invention, the heat-expandable microspheres can be selected from AkzoNobel EXPANCEL TM 031DU40, AkzoNobel EXPANCEL TM 051DU40, AkzoNobel EXPANCEL TM 093DU120, AkzoNobel EXPANCEL TM 980DU120, Advancel EHM303, Advancel EM403, Matsumoto F-78KD, MSH- One of the 550.
在本发明的一些具体实施例中，低粘度的流体为25℃下运动粘度低于12500 mm 2/s的流体。例如选自硅油，脂肪烃等；硅油种类包括甲基硅油、乙基硅油、苯基硅油、甲基含氢硅油、甲基苯基硅油、甲基氯苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油、甲基羟基硅油、乙基含氢硅油、羟基含氢硅油、含氰硅油等，优选地，可选自Shin-Etsu KF96-1000cs（25℃下运动粘度为1000 mm 2/s），KF96-3000cs（25℃下运动粘度为3000 mm 2/s），KF96H-12500cs等一系列硅油。 In some embodiments of the present invention, the low viscosity fluid is a fluid with a kinematic viscosity of less than 12500 mm 2 /s at 25°C. For example, it is selected from silicone oil, aliphatic hydrocarbon, etc.; silicone oil types include methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, Methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen-containing silicone oil, hydroxy hydrogen-containing silicone oil, cyano-containing silicone oil, etc., preferably, can be selected from Shin-Etsu KF96-1000cs (25 ℃ A series of silicone oils such as kinematic viscosity of 1000 mm 2 /s), KF96-3000cs (kinematic viscosity of 3000 mm 2 /s at 25°C), KF96H-12500cs.
在本发明的一些具体实施例中，弹性体选自TPU、有机硅凝胶、ecoflex、PDMS、TPV、TPA、TPC、TPS、TPO。In some embodiments of the invention, the elastomer is selected from TPU, silicone gel, ecoflex, PDMS, TPV, TPA, TPC, TPS, TPO.
在本发明的一些具体实施例中，热固性材料可选自酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂、聚氨酯等中的一种。以环氧树脂为例，所述液体环氧树脂可为环氧树脂NPEL-128、环氧树脂BE-188E、环氧树脂E51、环氧树脂YN1828、环氧树脂YN1826、环氧树脂E44等等中的一种或多种的混合物；固化剂可为咪唑类、酸酐类、多元硫醇、芳香胺、聚醚胺、脂肪胺固化剂(如三乙烯二胺、三乙烯四胺等）中的一种或多种的混合物；按重量份计，称取以下各种物料：液体环氧树脂100份、固化剂5-150份。In some specific embodiments of the present invention, the thermosetting material may be selected from one of phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, polyurethane and the like. Taking epoxy resin as an example, the liquid epoxy resin can be epoxy resin NPEL-128, epoxy resin BE-188E, epoxy resin E51, epoxy resin YN1828, epoxy resin YN1826, epoxy resin E44, etc. A mixture of one or more of the curing agents; curing agents can be imidazoles, acid anhydrides, polyvalent mercaptans, aromatic amines, polyetheramines, aliphatic amine curing agents (such as triethylenediamine, triethylenetetramine, etc.) One or more mixtures; in parts by weight, weigh the following materials: 100 parts of liquid epoxy resin, and 5-150 parts of curing agent.
在本发明的一些具体实施例中，由于弹性体在高温下固化速度较快，为了适当控制所述轻质聚合物复合材料的固化速度，因此在弹性体初始混料中增加用于抑制固化反应的抑制剂，抑制剂可选用1-乙炔基-1-环己醇、2-甲基-3-丁炔基-2-醇、3-甲基-1-乙炔基-3-醇、3,5-二甲基-1-己炔基-3-醇、3-甲基-1-十二炔-3-醇、2-苯基-3-丁炔-2-醇等炔醇、3-甲基-3-戊烯-1-炔、3,5-二甲基-3-己烯-1-炔等烯炔化合物，以及1,3,5,7-四甲基-1,3,5,7-四乙烯基环四硅氧烷，苯并三唑等，优选地：1-乙炔基-1-环己醇。优选地，抑制剂含量可从十万分之一~千分之一。In some specific embodiments of the present invention, since the curing speed of the elastomer is faster at high temperature, in order to properly control the curing speed of the lightweight polymer composite material, the initial compound of the elastomer is added to suppress the curing reaction. Inhibitors can be selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, 3-methyl-1-ethynyl-3-ol, 3, 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol, 2-phenyl-3-butyn-2-ol and other alkynols, 3- Enyne compounds such as methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and 1,3,5,7-tetramethyl-1,3, 5,7-tetravinylcyclotetrasiloxane, benzotriazole, etc., preferably: 1-ethynyl-1-cyclohexanol. Preferably, the inhibitor content can be from 1/100,000 to 1/1,000.
在本发明的一些具体实施例中，性能测试中：In some specific embodiments of the present invention, in the performance test:
1、称重法测试试样的密度；1. Weighing method to test the density of the sample;
2、采用型号为Apreo 2 的扫描电镜拍摄样品的扫描电镜图片。2. The model is Apreo 2. SEM pictures of the samples taken by the SEM.
3、采用：MAX系列高精度荷重试验机(型号为MAX-1kN-P-2)测试正方体试样(10mm×10mm×5mm)的压缩性能，测试速度为1mm/min，压缩应变为90%，并以10％的应变时的压缩强度来衡量所述轻质聚合物复合材料的压缩强度。3. Use: MAX series high-precision load testing machine (model MAX-1kN-P-2) to test the compression performance of the cube sample (10mm×10mm×5mm), the test speed is 1mm/min, the compression strain is 90%, The compressive strength of the lightweight polymer composite was measured as the compressive strength at 10% strain.
实施例1 热膨胀微球块材的制备Example 1 Preparation of heat-expandable microsphere blocks
将0.188g热膨胀微球AkzoNobel EXPANCEL TM031DU40，放入封闭的模具腔室(26mm×26mm×5mm)中，随后在95℃下，保温1.5h后，移至室温处，待模具温度下降至室温后，再开模取样，即可获得热膨胀微球轻质聚合物复合材料。0.188g heat-expandable microspheres AkzoNobel EXPANCEL TM031DU40, put it into a closed mold cavity (26mm x 26mm x 5mm), and then keep it at 95°C for 1.5h, then move it to room temperature, and after the mold temperature drops to room temperature, open the mold and take samples. A heat-expandable microsphere lightweight polymer composite was obtained.
图2为纯热膨胀微球块材的实物图。图3(a)为实施例1纯热膨胀微球块材的压缩曲线。经测量实施例1的试样密度0.055g/cm 3，压缩的弹性模量为17.3 MPa压缩强度为0.40 MPa。图4是纯热膨胀微球块材的SEM图，说明粉体的热膨胀微球通过在高温下体积膨胀从而微球与微球之间的相互挤压，最终形成宏观上具有力学强度的块材。 Figure 2 is a physical view of a pure thermally expandable microsphere block. FIG. 3( a ) is the compression curve of the pure thermally expandable microsphere bulk material of Example 1. FIG. The density of the sample in Example 1 was measured to be 0.055 g/cm 3 , the compressive elastic modulus was 17.3 MPa, and the compressive strength was 0.40 MPa. Figure 4 is the SEM image of the pure thermally expandable microsphere block material, which shows that the thermally expandable microspheres of the powder are extruded from each other by volume expansion at high temperature, and finally form a block material with macroscopic mechanical strength.
实施例2基于热膨胀微球的有机复合材料的制备Example 2 Preparation of Thermally Expandable Microsphere-Based Organic Composites
将热膨胀微球AkzoNobel EXPANCEL TM031DU40与把二甲基有机硅油Shin-Etsu KF96H-12500cs进行充分混合，得到混料，二甲基有机硅油质量分数为54wt%。再将上述混料取0.40g，放入封闭的模具腔室(26mm×26mm×5mm)中，随后在95℃下，保温1.5h后，移至室温处，待模具温度下降至室温后，再开模取样，即可获得一种基于热膨胀微球的轻质聚合物复合材料。 The heat-expandable microspheres AkzoNobel EXPANCEL TM 031DU40 and dimethyl silicone oil Shin-Etsu KF96H-12500cs were thoroughly mixed to obtain a mixture, and the mass fraction of dimethyl silicone oil was 54wt%. Then take 0.40g of the above mixture, put it into a closed mold cavity (26mm × 26mm × 5mm), and then keep it at 95°C for 1.5h, then move it to room temperature, and wait until the mold temperature drops to room temperature, and then re-heat. A light-weight polymer composite based on heat-expandable microspheres can be obtained by opening the mold and sampling.
经测量实施例2的试样密度0.12g/cm 3，图3(b)为实施例2的压缩曲线，压缩的弹性模量为14MPa，压缩强度为0.34MPa。实际上，该轻质聚合物复合材料中硅油复合的体积分数约为7vol%。硅油在该体系内没有发生化学反应，但对热膨胀微球的球与球的界面起了调控作用，并影响了复合材料的力学性能。在图3中的压缩曲线可知实施例2的压缩曲线与纯热膨胀微球类似，但是力学性能下降，这是由于硅油的存在减小了热膨胀微球界面之间的相互作用，这一点可以从图5的SEM图以及图6的能谱分析图得到佐证。图5是实施例2复合材料块材的SEM图，从微观结构上可以看出热膨胀微球与硅油复合所形成的复合材料是以热膨胀微球为基体，微球与微球之间依旧密切结合，图6为实施例2复合材料的能谱分析图，可以清晰地看到硅元素（硅油含有硅元素，微球不含有硅元素）分布在微球与微球的相交处，即硅油存在于微球与微球之间的交界处。但是硅油在块材内部起不到强度作用，虽然硅油通常可以作为润滑剂使用，会影响热膨胀微球球壁之间的连接，而无法形成连续相骨架，而且硅油为流体起到了降低热膨胀微球的球与球界面之间的相互作用。但是出人预料的是，采用本发明的方法不但可以形成固体块材，而且可以保持一定的力学强度，也不会因此出现“松塌”形象；极大的改善了硅油的力学强度，使其可以以块材的形式使用。 The density of the sample in Example 2 was measured to be 0.12 g/cm 3 , and Fig. 3(b) is the compression curve of Example 2. The compressive elastic modulus was 14 MPa and the compressive strength was 0.34 MPa. In fact, the volume fraction of silicone oil compounded in this lightweight polymer composite is about 7 vol%. The silicone oil did not react chemically in the system, but it played a role in regulating the sphere-to-sphere interface of the thermally expanded microspheres and affected the mechanical properties of the composites. It can be seen from the compression curve in Figure 3 that the compression curve of Example 2 is similar to that of pure thermally expandable microspheres, but the mechanical properties are decreased. This is because the presence of silicone oil reduces the interaction between the interfaces of the thermally expandable microspheres, which can be seen from Fig. The SEM image of 5 and the energy spectrum analysis image of Fig. 6 are corroborated. Figure 5 is the SEM image of the composite material block in Example 2. From the microstructure, it can be seen that the composite material formed by the composite of thermally expandable microspheres and silicone oil is based on thermally expandable microspheres, and the microspheres are still closely combined with the microspheres. , Figure 6 is the energy spectrum analysis diagram of the composite material in Example 2. It can be clearly seen that the silicon element (silicon oil contains silicon element, microsphere does not contain silicon element) is distributed at the intersection of the microsphere and the microsphere, that is, the silicone oil exists in the The junction between microspheres and microspheres. However, silicone oil does not play a role in strength inside the block. Although silicone oil can usually be used as a lubricant, it will affect the connection between the walls of the thermally expanded microspheres, and cannot form a continuous phase skeleton, and the silicone oil acts as a fluid to reduce the thermal expansion of the microspheres. the interaction between the ball and the ball interface. However, unexpectedly, the method of the present invention can not only form a solid block, but also maintain a certain mechanical strength, and will not appear "loose" because of this; the mechanical strength of the silicone oil is greatly improved, making it possible Available in block form.
实施例3基于热膨胀微球的有机复合材料的制备Example 3 Preparation of Thermally Expandable Microsphere-Based Organic Composites
向液态有机硅凝胶的B组分（主要成分为乙烯基硅油、催化剂等）中添加的抑制剂:1-乙炔基-1-环己醇，并将二者充分混合后，与液态有机硅凝胶的A组分（主要成分为含氢硅油等）进行混合，A:B=1:4，抑制剂含量为十万分之五。之后将液态有机硅凝胶与热膨胀微球AkzoNobel EXPANCEL TM031DU40充分混合，得到混料，有机硅凝胶质量分数为54wt%。再将上述混料取0.40g，放入封闭的模具腔室(26mm×26mm×5mm)中，随后在95℃下，保温1.5h后，移至室温处，待模具温度下降至室温后，再开模取样，即可获得一种基于热膨胀微球的轻质聚合物复合材料。需指出的是，在上述加热过程中，液态有机硅凝胶的A/B组分会发生交联反应生成有机硅凝胶。 The inhibitor added to the B component of the liquid silicone gel (the main components are vinyl silicone oil, catalyst, etc.): 1-ethynyl-1-cyclohexanol, after mixing the two thoroughly, with the liquid silicone The A component of the gel (the main component is hydrogen-containing silicone oil, etc.) is mixed, A:B=1:4, and the inhibitor content is 5/100,000. Afterwards, the liquid silicone gel was fully mixed with the thermally expandable microspheres AkzoNobel EXPANCEL TM 031DU40 to obtain a mixture, and the mass fraction of the silicone gel was 54 wt %. Then take 0.40g of the above mixture, put it into a closed mold cavity (26mm × 26mm × 5mm), and then keep it at 95°C for 1.5h, then move it to room temperature, and wait until the mold temperature drops to room temperature, and then re-heat. A light-weight polymer composite based on heat-expandable microspheres can be obtained by opening the mold and sampling. It should be pointed out that during the above heating process, the A/B component of the liquid silicone gel will undergo a cross-linking reaction to form a silicone gel.
经测量实施例3的试样密度0.12g/cm 3，与实施例1相比，图3(c)为实施例3所述复合材料的的压缩曲线，材料弹性模量为10MPa，压缩强度为0.26MPa。并且压缩曲线与纯微球块材的压缩曲线类似，而不是类似于图3(d)纯有机硅凝胶块材的压缩曲线（图3（d）显示的是与本实施例中采用有机硅凝胶相同材料制成的纯有机硅凝胶块材）。说明该轻质聚合物复合材料中有机硅凝胶复合的质量分数达54wt%时，仍然能体现出类似于纯热膨胀微球块材相似的压缩曲线，在图7的SEM图中也表明，热膨胀微球相互之间密切相接，有机硅凝胶分布在球与球之间的连接处，在图8的能谱分析图也表明硅元素(硅凝胶含有硅元素)存在于微球与微球之间的界面和交界处。即说明实施例3的块材依旧以热膨胀微球为基体，但是实际上也值得注意的是，在上述加热过程中，液态有机硅凝胶的A/B组分会发生交联反应生成有机硅凝胶。而在块材内部，硅凝胶对微球与微球之间的界面起到调控作用。 The density of the sample in Example 3 is measured to be 0.12 g/cm 3 . Compared with Example 1, Figure 3(c) is the compression curve of the composite material described in Example 3. The elastic modulus of the material is 10 MPa and the compressive strength is 0.26MPa. And the compression curve is similar to the compression curve of the pure microsphere block, not similar to the compression curve of the pure silicone gel block in Fig. 3(d) (Fig. Pure silicone gel blocks made of the same material as the gel). It shows that when the mass fraction of organosilicon gel in the lightweight polymer composite reaches 54wt%, it can still show a compression curve similar to that of pure thermally expanded microspheres. The SEM image in Figure 7 also shows that thermal expansion The microspheres are closely connected with each other, and the silicone gel is distributed at the connection between the spheres. Interfaces and junctions between balls. That is to say, the block material of Example 3 is still based on heat-expandable microspheres, but it is also worth noting that in the above heating process, the A/B components of the liquid silicone gel will undergo cross-linking reaction to form silicone gel. glue. Inside the block, the silica gel plays a role in regulating the interface between the microspheres.
实施例4基于热膨胀微球的有机复合材料的制备Example 4 Preparation of Thermally Expandable Microsphere-Based Organic Composites
向液态 BE-188E双酚A中添加固化剂（间苯二甲胺），并将二者充分混合后，与热膨胀微球AkzoNobel EXPANCEL TM031DU40进行混合，三者的百分比是BE-188E双酚A:固化剂:热膨胀微球=46:4:50。再将上述混料取0.376g，放入封闭的模具腔室(26mm×26mm×5mm)中，随后在95℃下，保温1.5h后，移至室温处，待模具温度下降至室温后，再开模取样，即可获得一种基于热膨胀微球的轻质聚合物复合材料。需指出的是，在上述加热过程中，双酚A与固化剂发生化学交联反应以及形成连续相——环氧树脂相，从图9的SEM图中，可知该轻质聚合物复合材料依然是以热膨胀微球作为基体，在实施例4的轻质复合材料内部：环氧树脂相存在于微球与微球之间的连接处，大部分的环氧存在于多个微球相接的间隙中。综上所述，本发明所述的轻质聚合物复合材料，具有密度小、组分组成简单、压缩力学性能优良等多种优点，并以热膨胀微球作为复合材料基体，能够满足低粘度流体、弹性体至热固性材料等不同粘弹性性质的聚合物或聚合物前驱体的复合。且制备方法简便、环保、能耗低，生产效率高，具有非常良好的应用前景。Add the curing agent (m-xylylenediamine) to the liquid BE-188E bisphenol A, mix the two thoroughly, and mix with the heat-expandable microspheres AkzoNobel EXPANCEL TM031DU40 is mixed, and the percentage of the three is BE-188E bisphenol A: curing agent: heat-expandable microspheres = 46:4:50. Then take 0.376g of the above mixture, put it into a closed mold cavity (26mm×26mm×5mm), and then keep it at 95°C for 1.5h, then move it to room temperature. A light-weight polymer composite based on heat-expandable microspheres can be obtained by sampling from the mold. It should be pointed out that during the above heating process, bisphenol A and the curing agent undergo a chemical cross-linking reaction and form a continuous phase-epoxy resin phase. From the SEM image of Figure 9, it can be seen that the lightweight polymer composite material is still Using thermally expandable microspheres as the matrix, inside the lightweight composite material of Example 4: the epoxy resin phase exists at the junction between the microspheres and the microspheres, and most of the epoxy exists in the joints of multiple microspheres. in the gap. To sum up, the lightweight polymer composite material of the present invention has many advantages such as low density, simple component composition, and excellent compressive mechanical properties, and uses thermally expandable microspheres as the matrix of the composite material, which can meet the requirements of low viscosity fluids. Composites of polymers or polymer precursors with different viscoelastic properties, such as elastomers to thermosets. And the preparation method is simple, environmentally friendly, low in energy consumption, high in production efficiency, and has a very good application prospect.
实施例5 复合材料最低密度检测Example 5 Minimum density detection of composite materials
分别将0.03g（a组）、0.05g（b组）、0.07g（c组）和0.09g（d组）热膨胀微球AkzoNobel EXPANCEL TM031DU40，放入封闭的模具腔室(26mm×26mm×5mm)中，随后在95℃下，保温1.5 h后，移至室温处，待模具温度下降至室温后，再开模取样，观察不同组样品，并计算理论密度。a组的理论密度为0.009g/cm 3；b组的理论密度为0.015g/cm 3；c组的理论密度为0.021g/cm 3；d组的理论密度为0.027g/cm 3。实验结果见图10，观察a-d组的状态可知如果热膨胀微球的用量过少，膨胀后无法填充满密封模具腔体，则无法实现热膨胀微球之间的复合，进而形成紧密的连接相骨架结构。所以在制备以热膨胀微球的球壁连接形成的连续相骨架时，需要调节微球添加量或封闭的模具腔室的体积，使得热膨胀微球的球壁连接形成的连续相骨架单位密度至少为0.021g/cm 3。 Put 0.03g (group a), 0.05g (group b), 0.07g (group c) and 0.09g (group d) of AkzoNobel EXPANCEL TM031DU40 heat-expandable microspheres into a closed mold cavity (26mm×26mm×5mm) Then, at 95 °C, after holding for 1.5 h, it was moved to room temperature. After the mold temperature dropped to room temperature, the mold was opened to take samples, different groups of samples were observed, and the theoretical density was calculated. The theoretical density of group a is 0.009 g/cm 3 ; the theoretical density of group b is 0.015 g/cm 3 ; the theoretical density of group c is 0.021 g/cm 3 ; the theoretical density of group d is 0.027 g/cm 3 . The experimental results are shown in Figure 10. Observing the state of group ad, it can be seen that if the amount of heat-expandable microspheres is too small, and the cavity of the sealed mold cannot be filled after expansion, the recombination between the heat-expandable microspheres cannot be realized, and then a tightly connected phase skeleton structure is formed. . Therefore, when preparing the continuous phase skeleton formed by the connection of the spherical walls of the heat-expandable microspheres, it is necessary to adjust the addition amount of the microspheres or the volume of the closed mold cavity so that the unit density of the continuous phase skeleton formed by the connection of the spherical walls of the heat-expandable microspheres is at least 0.021 g/cm 3 .

Claims (10)

  1. 一种基于热膨胀微球的有机复合材料，其特征在于，所述有机复合材料中包括由热膨胀微球的球壁相互连接形成的连续相骨架，以及在热膨胀微球外部间隙中填充的有机材料；所述的有机材料选自低粘度流体、弹性体以及热固性聚合物材料； An organic composite material based on heat-expandable microspheres, characterized in that the organic composite material comprises a continuous phase skeleton formed by interconnecting spherical walls of the heat-expandable microspheres, and an organic material filled in the outer gap of the heat-expandable microspheres; Described organic material is selected from low viscosity fluid, elastomer and thermosetting polymer material;
    优选地，所述基于热膨胀微球的有机复合材料的中单位体积内连续相骨架密度为0.021g/cm 3以上；优选为0.021-0.07 g/cm 3； Preferably, the continuous phase skeleton density per unit volume of the heat-expandable microsphere-based organic composite material is above 0.021 g/cm 3 ; preferably 0.021-0.07 g/cm 3 ;
    更优选为，所述基于热膨胀微球的有机复合材料中热膨胀微球所占重量分数:99.99wt%~20wt%；More preferably, the heat-expandable microspheres account for the weight fraction in the organic composite material based on the heat-expandable microspheres: 99.99wt%～20wt%;
    更优选地，所述基于热膨胀微球的有机复合材料中所述低粘度流体、弹性体或热固性聚合物材料所占质量分数为:0.01wt%-80wt%。More preferably, the mass fraction of the low-viscosity fluid, elastomer or thermosetting polymer material in the heat-expandable microsphere-based organic composite material is: 0.01wt%-80wt%.
  2. 根据权利要求1所述的有机复合材料，其特征在于，所述热膨胀微球是一种由热塑性聚合物外壳和包裹的液态烷烃气体组成的聚合物微球； The organic composite material according to claim 1, wherein the heat-expandable microsphere is a polymer microsphere consisting of a thermoplastic polymer shell and a wrapped liquid alkane gas;
    优选地，所述热膨胀微球选自以丙烯酸外壳的热膨胀微球；Preferably, the heat-expandable microspheres are selected from heat-expandable microspheres with acrylic shell;
    更优选地，所述热膨胀微球选自AkzoNobel EXPANCEL TM031DU40，AkzoNobel EXPANCEL TM051DU40，AkzoNobel EXPANCEL TM093DU120，AkzoNobel EXPANCEL TM980DU120，Advancell EHM303，Advancell EM403，日本松本F-78KD，MSH-550中的一种。More preferably, the heat-expandable microspheres are selected from AkzoNobel EXPANCEL TM031DU40, AkzoNobel One of EXPANCEL TM051DU40, AkzoNobel EXPANCEL TM093DU120, AkzoNobel EXPANCEL TM980DU120, Advancell EHM303, Advancell EM403, Japan Matsumoto F-78KD, MSH-550.
  3. 根据权利要求1所述的有机复合材料，其特征在于，低粘度流体选自硅油、脂肪烃、脂肪酸、脂肪醇； The organic composite material according to claim 1, wherein the low-viscosity fluid is selected from the group consisting of silicone oil, aliphatic hydrocarbons, fatty acids, and fatty alcohols;
    所述弹性体选自弹性体选自热塑性聚氨酯弹性体橡胶（TPU）、有机硅凝胶、ecoflex ®、聚二甲基硅氧烷（PDMS）、热塑性硫化橡胶（TPV）、热塑性聚酰胺弹性体（TPA）、热塑性共聚酯弹性体（TPC）、苯乙烯类热塑性弹性体（TPS）、热塑性聚烯烃弹性体（TPO）。 The elastomer is selected from elastomers selected from thermoplastic polyurethane elastomer rubber (TPU), silicone gel, ecoflex ® , polydimethylsiloxane (PDMS), thermoplastic vulcanizate (TPV), thermoplastic polyamide elastomer ( TPA), thermoplastic copolyester elastomer (TPC), styrenic thermoplastic elastomer (TPS), thermoplastic polyolefin elastomer (TPO).
    所述热固性材料选自酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂、聚氨酯。The thermosetting material is selected from phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, and polyurethane.
  4. 根据权利要求1所述的有机复合材料，其特征在于，所述基于热膨胀微球的有机复合材料通过以下方法获得：将热膨胀微球与低粘度流体、弹性体以及热固性聚合物材料，或与形成低粘度流体、弹性体以及热固性聚合物材料的前驱体进行混合，得到半固体或液体的混料；将混料注入密闭容器中，并加热使热膨胀微球膨胀且热膨胀微球的球壁连接形成连续相骨架。 The organic composite material according to claim 1, wherein the heat-expandable microsphere-based organic composite material is obtained by combining the heat-expandable microspheres with low-viscosity fluids, elastomers, and thermosetting polymer materials, or with forming Low viscosity fluid, elastomer and precursor of thermosetting polymer material are mixed to obtain a semi-solid or liquid mixture; the mixture is injected into a closed container and heated to expand the thermally expandable microspheres and the spherical walls of the thermally expandable microspheres are connected to form Continuous phase skeleton.
  5. 根据权利要求1所述的有机复合材料，其特征在于，所述基于热膨胀微球的有机复合材料的密度为0.046 g/cm 3-0.3g/cm 3。 The organic composite material according to claim 1, wherein the density of the heat-expandable microsphere-based organic composite material is 0.046 g/cm 3 -0.3 g/cm 3 .
  6. 根据权利要求1所述的有机复合材料，其特征在于，所述基于热膨胀微球的有机复合材料为固体材料。 The organic composite material according to claim 1, wherein the heat-expandable microsphere-based organic composite material is a solid material.
  7. 根据权利要求1-4任一项所述的基于热膨胀微球的有机复合材料的制备方法，其特征在于，其包括如下步骤： The preparation method of the thermally-expandable microsphere-based organic composite material according to any one of claims 1-4, characterized in that, it comprises the steps:
    (1)将热膨胀微球与低粘度流体、弹性体以及热固性聚合物材料中的至少一种材料进行混合，或将热膨胀微球与形成低粘度流体、弹性体以及热固性聚合物材料中的至少一种材料的前驱体进行混合，得到液体或半固体的混料；(1) mixing the heat-expandable microspheres with at least one of low-viscosity fluid, elastomer and thermosetting polymer material, or mixing heat-expandable microspheres with at least one of low-viscosity fluid, elastomer and thermosetting polymer material The precursors of these materials are mixed to obtain a liquid or semi-solid mixture;
    (2)将上述混料，放入封闭的模具腔室中，以热膨胀微球的发泡温度加热，保温膨胀至反应完全，降温后从模具中取出，获得基于热膨胀微球的有机复合材料；(2) above-mentioned mixing is put into a closed mould cavity, heated with the foaming temperature of thermally expandable microspheres, thermally expanded until the reaction is complete, taken out from the mould after cooling, to obtain an organic composite material based on thermally expandable microspheres;
    优选地，热固性聚合物材料前驱体中包括热固性聚合物材料固化固化剂，固化剂选自咪唑类、酸酐类、多元硫醇、芳香胺、聚醚胺、脂肪胺固化剂中的一种或多种的混合物；Preferably, the thermosetting polymer material precursor includes a thermosetting polymer material curing agent, and the curing agent is selected from one or more of imidazoles, acid anhydrides, polythiols, aromatic amines, polyetheramines, and aliphatic amine curing agents a mixture of species;
    更优选地，对于步骤2)加温条件为80-130℃时，固化剂选自咪唑、聚醚胺、间苯二甲胺；More preferably, for step 2) when the heating condition is 80-130°C, the curing agent is selected from imidazole, polyetheramine, m-xylylenediamine;
    更优选地，对于步骤2)加温条件为130℃以上时，固化剂选自咪唑类、酸酐类固化剂。More preferably, for step 2) when the heating condition is above 130° C., the curing agent is selected from imidazole and acid anhydride curing agents.
  8. 根据权利要求7所述的制备方法，其特征在于，步骤2）中保温时间为1-3小时；保温温度为80-180℃。 The preparation method according to claim 7, characterized in that, in step 2), the holding time is 1-3 hours; the holding temperature is 80-180°C.
  9. 根据权利要求7所述的制备方法，其特征在于，步骤2）中封闭的模具腔室的体积根据步骤1）中加入的热膨胀微球的质量选择，所述模具腔室的体积不大于：热膨胀微球的质量与基于热膨胀微球的有机复合材料的中热膨胀微球的密度的乘积，其中基于热膨胀微球的有机复合材料的中热膨胀微球的密度为0.021g/cm 3以上，优选为0.021-0.07 g/cm 3。 The preparation method according to claim 7, wherein the volume of the closed mold cavity in step 2) is selected according to the mass of the heat-expandable microspheres added in step 1), and the volume of the mold cavity is not greater than: the thermal expansion The product of the mass of the microspheres and the density of the heat-expandable microspheres of the heat-expandable microsphere-based organic composite material, wherein the density of the heat-expandable microspheres of the heat-expandable microsphere - based organic composite material is 0.021 g/cm or more, preferably 0.021 -0.07 g/cm 3 .
  10. 根据权利要求7所述的制备方法，其特征在于，步骤1）混料中还包括抑制低粘度流体、弹性体、热固性聚合物材料固化的抑制剂，或形成低粘度流体、弹性体以及热固性聚合物材料的前驱体固化的抑制剂， The preparation method according to claim 7, characterized in that, in step 1) the mixing further includes an inhibitor that inhibits the curing of low-viscosity fluids, elastomers, and thermosetting polymer materials, or forms low-viscosity fluids, elastomers, and thermosetting polymers. Inhibitors for the curing of precursors of biomaterials,
    优选地，抑制剂选自烯炔化合物、1,3,5,7-四甲基-1,3,5,7-四乙烯基环四硅氧烷或苯并三唑；Preferably, the inhibitor is selected from enyne compounds, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or benzotriazole;
    更优选地，烯炔化合物选自1-乙炔基-1-环己醇、2-甲基-3-丁炔基-2-醇、3-甲基-1-乙炔基-3-醇、3,5-二甲基-1-己炔基-3-醇、3-甲基-1-十二炔-3-醇、2-苯基-3-丁炔-2-醇等炔醇、3-甲基-3-戊烯-1-炔、3,5-二甲基-3-己烯-1-炔。More preferably, the enyne compound is selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, 3-methyl-1-ethynyl-3-ol, 3 , 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol, 2-phenyl-3-butyn-2-ol and other alkynols, 3 -Methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne.
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