CN114573862A - Reinforced polystyrene foam ball and preparation method thereof - Google Patents
Reinforced polystyrene foam ball and preparation method thereof Download PDFInfo
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- CN114573862A CN114573862A CN202011369836.0A CN202011369836A CN114573862A CN 114573862 A CN114573862 A CN 114573862A CN 202011369836 A CN202011369836 A CN 202011369836A CN 114573862 A CN114573862 A CN 114573862A
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- 229920006327 polystyrene foam Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000835 fiber Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 25
- 239000011324 bead Substances 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 23
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 239000010410 layer Substances 0.000 claims abstract description 20
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- 238000001723 curing Methods 0.000 claims description 44
- 239000011268 mixed slurry Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 10
- 238000013035 low temperature curing Methods 0.000 claims description 7
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 238000007581 slurry coating method Methods 0.000 claims description 5
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 abstract description 10
- 229920002223 polystyrene Polymers 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000006260 foam Substances 0.000 description 10
- 230000002706 hydrostatic effect Effects 0.000 description 7
- 239000008188 pellet Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08J9/36—After-treatment
- C08J9/365—Coating
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a reinforced polystyrene foam ball, which comprises a core-shell structure, wherein the core of the core is a polystyrene foam ball, and the shell of the core is a thermosetting resin layer blended with fibers and optionally blended with hollow glass beads. The hollow glass beads can be selectively added into the polystyrene foam ball coating layer, so that the density of the reinforced polystyrene ball is reduced to a certain extent, and the strength requirement of the reinforced polystyrene ball in application is met.
Description
Technical Field
The invention relates to the field of light materials, in particular to a reinforced polystyrene foam ball and a preparation method thereof.
Background
The floating body for the marine device is mainly characterized in that hollow glass beads are added into a resin matrix through a certain preparation technology to obtain a composite material. Since the 21 st century, various countries in the world have been exploring and exploiting mineral resources in the marine field on a large scale. The solid buoyancy material is used as an important matching material of deep sea equipment, provides buoyancy for the deep sea equipment, and mainly reduces the density of the material by adding hollow glass beads, wherein the density can be as low as 0.35g/cm3It is difficult to reduce the density of the buoyancy material by further increasing the addition amount of the hollow glass beads, and the polystyrene foam beads have low density and volumeThe strength of the material can be further improved by reinforcing the material, and the material can be used as a filler to be applied to a buoyancy material, so that the density of the buoyancy material can be reduced, and the production cost can be reduced.
Chinese patent CN104059334A discloses a fiber pellet for a solid buoyancy material and a preparation method thereof, the method coats a layer of resin on the surface of a foam pellet to seal gaps on the surface of the foam pellet, and then the foam pellet and fiber slurry are mixed and stirred to enable the fiber slurry to coat the foam pellet, the method has a complex process, and the obtained foam pellet has high density.
Chinese patent CN108329511A adopts a spraying method to directly coat the fiber slurry on polystyrene foam balls, then the polystyrene foam balls are placed in dry chopped fibers to enable the surfaces of the polystyrene foam balls to be adhered with the dry chopped fibers, the process is repeated until the required ball diameter is reached, and the density can reach 0.16-0.32g/cm3The method is mainly applied to water depths within 1000 meters, the foam balls need to be placed well uniformly and then spraying is carried out, the operation method is difficult, and the efficiency is low. Therefore, it is desired to develop a polystyrene foam ball that can achieve a low density with simple operation.
Disclosure of Invention
One of the purposes of the invention is to solve the problem of high density of the existing foam ball and provide a reinforced polystyrene foam ball which can obviously reduce the density of the foam ball and has higher mechanical property. In addition, the coating layer adopts various curing systems, the first layer belongs to a medium-low temperature curing system, the curing time is short, the formation of a coating layer structure support is facilitated, and the operation is easy.
The invention also aims to solve the problem of complex and difficult operation process in the prior art, and provides a preparation method of the reinforced polystyrene foam ball to simplify the prior operation process. The coating layer of the invention adopts a rolling ball mode or a spray gun spraying mode, and the modes are simpler and more controllable to operate.
In order to achieve one of the purposes, the invention is realized by the following technical scheme:
the invention relates to a reinforced polystyrene foam ball, which comprises a core-shell structure, wherein the core of the core is a polystyrene foam ball, and the shell of the core is a thermosetting resin layer blended with fibers and optionally blended with hollow glass beads.
In the above technical solution, the thermosetting resin is at least one of epoxy resin, phenolic resin and unsaturated polyester resin, for example, one or two of the epoxy resin, phenolic resin and unsaturated polyester resin.
In the above technical solution, the fiber is at least one of glass fiber and carbon fiber, for example, one or two.
In the above technical solution, the thermosetting resin is at least one of, for example, one or two of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, thermosetting phenol resin, and unsaturated polyester resin.
In the above technical scheme, the fibers are chopped fibers.
The preferable scheme is as follows: as the polystyrene balls having a diameter of 8mm or less, chopped fibers having a diameter of 1mm or less are preferably used, and as the polystyrene foam balls having a diameter of 8mm or more, chopped fibers having a diameter of 2mm or less are preferably used.
In the technical scheme, the density of the hollow glass beads is 0.1-0.42g/cm3Preferably 0.2 to 0.32g/cm3。
In the above technical solution, the particle size range of the hollow glass beads is 11-135 μm, preferably 15-100 μm.
In the technical scheme, the bulk density of the polystyrene foam balls is 0.018-0.03 g/cm3。
In the technical scheme, the particle size range of the polystyrene foam balls is 2-50mm, and preferably 5-12 mm.
In the above-mentioned aspect, the chopped fibers preferably have a length of 2mm or less and a diameter of 5 to 7 μm.
In the technical scheme, the length-diameter ratio of the chopped fibers is (1-8): 1.
in the technical scheme, the density of the reinforced polystyrene foam ball is 200-500kg/m3Preferably 250 to 380kg/m3。
In the technical scheme, the average particle size of the reinforced polystyrene foam ball is 5-60mm, and preferably 8-15 mm.
In the technical scheme, the average thickness of the shell layer of the reinforced polystyrene foam ball is 1-10mm, and preferably 2-8 mm.
In order to achieve the second purpose, the invention is realized by the following technical scheme:
the preparation method of the reinforced polystyrene foam ball comprises the steps of wrapping mixed slurry containing thermosetting resin prepolymer of the fibers outside the polystyrene foam ball to form a mixed slurry wrapping layer, optionally mixing the fibers and/or hollow glass beads on the mixed slurry wrapping layer, and then curing to obtain the reinforced polystyrene foam ball.
In the technical scheme, the thermosetting resin prepolymer mixed slurry comprises the following components in parts by mass:
in the above technical solution, the thermosetting resin prepolymer is at least one of epoxy resin prepolymer or phenolic resin prepolymer and unsaturated polyester resin prepolymer, for example, one or two of the above prepolymers.
The curing agent may be a curing agent commonly used for thermosetting resins, preferably at least one selected from amine curing agents or anhydride curing agents, preferably at least one selected from T31 curing agents, isophorone diamine and methyl tetrahydrophthalic anhydride, for example, one or two.
The diluent may be a diluent commonly used for thermosetting resins, preferably selected from at least one of monoepoxy diluent and diepoxy diluent, preferably at least one, such as one or two, of diepoxy diluent JX-022 and diepoxy diluent JX-024. The preferable diluent can reduce the viscosity of the resin matrix, is beneficial to uniformly coating the surface of the polystyrene sphere and can reduce the thickness of a single-layer coating layer.
The coupling agent is at least one selected from silane coupling agents and titanate coupling agents, preferably at least one selected from silane coupling agents KH560 and KH550, such as one or two. Preferred coupling agents facilitate bonding between the resin matrix and the polystyrene spheres.
In the above technical scheme, the preparation method comprises the following steps:
(1) uniformly mixing the components including the fiber, the thermosetting resin prepolymer, the diluent, the coupling agent and the curing agent to form mixed slurry of the thermosetting resin prepolymer; preferably, the curing agent is mixed last;
(2) adding the polystyrene foam ball into the mixed slurry or spraying the mixed slurry on the polystyrene foam ball to form a uniform mixed slurry coating layer; optionally, uniformly mixing the fibers and/or the hollow glass microspheres on the mixed slurry coating layer;
(3) curing;
optionally, repeating steps (2) and (3) above. The operation times of the steps (2) and (3) can be 1-10 times, and preferably 2-6 times; the amount or thickness of the coating layer of the slurry mixed with the thermosetting resin prepolymer formed outside the polystyrene foam balls each time, and optionally the amount or thickness of the fiber and/or the hollow glass bead mixed each time are not particularly limited, and uniform coating and uniform mixing can be achieved, and finally the density of the reinforced polystyrene foam balls obtained is controlled within a required range.
More preferably, when repeating the step (2), other curing agent or the like may be added to the mixed slurry of the thermosetting resin prepolymer.
In the above technical solution, in the step (2), the mixing manner of mixing the fibers and/or the hollow glass beads on the coating layer of the mixed slurry may be a mixing manner commonly used in the prior art, such as spray coating, rolling ball, and the like.
In the above technical solution, the curing in the step (3) is low temperature curing and/or medium high temperature curing, preferably, the first curing is low temperature curing, and then optionally the medium high temperature curing is adopted.
Preferably, the low-temperature curing temperature is 0-30 ℃, and the curing time is 0.3-3 h.
In the technical scheme, the medium-high temperature curing temperature is 60-140 ℃, and the curing time is 1-6 h.
Compared with the prior art, the invention has the following beneficial effects: the medium-low temperature curing system adopted for the first coating is beneficial to the rapid curing and molding of the resin coating layer, and a uniform coating layer is formed on the surface of the polystyrene foam ball, so that the stability of the polystyrene foam shell structure is enhanced, and the performance of the subsequent polystyrene coating layer is improved. The slurry adopted in each coating layer contains a coupling agent, so that the polystyrene foam and the coating layer can be effectively mixed; the coating layer and the coating layer are tightly combined together, so that the performance of the product is improved. In addition, hollow glass beads can be selectively added into the polystyrene foam ball coating layer in the technology, so that the density of the reinforced polystyrene balls is reduced to a certain extent, and the strength requirement of the reinforced polystyrene balls in application is met.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The various raw materials and auxiliary agents used in the embodiments of the present invention are commercially available.
The raw material components are calculated according to the mass portion.
Example 1
Preparation of reinforced polystyrene foam balls:
1) uniformly mixing 3 parts of 1mm chopped polyacrylonitrile carbon fibers (with the diameter of 7 mu m) with 100 parts of epoxy resin E-51, 10 parts of diluent JX-022 and 3 parts of coupling agent KH560 by adopting a high-speed mixing stirrer, then grinding in a three-roll grinder, and further uniformly stirring in the high-speed mixing stirrer;
2)25 parts of curing agent isophorone diamineAdding into resin mixed slurry, mixing, spraying with spray gun to polystyrene foam ball (particle diameter range of 8-10mm, polystyrene foam ball bulk density of about 20 kg/m)3) Coating a layer of epoxy resin mixed slurry on the surface of the polystyrene foam ball uniformly, and then coating a layer of 0.23g/cm uniformly in a rolling ball mode3The hollow glass beads (the particle size range is 15-40 mu m) are solidified for 4 hours at the temperature of 60 ℃;
3) adding 80 parts of curing agent methyl tetrahydrophthalic anhydride and 1 part of accelerant DMP-30 into the resin mixed slurry, uniformly mixing, uniformly spraying a coating resin system onto the polystyrene foam balls by using a spray gun to uniformly coat a layer of epoxy resin mixed slurry on the surfaces of the polystyrene foam balls, and then uniformly coating a layer of 0.23g/cm3The hollow glass beads are cured for 2 hours at 80 ℃ and cured for 2 hours at 100 ℃;
repeating the step 3) for 4 times, and curing for 3 hours at 140 ℃.
The diameter of the reinforced polystyrene foam ball prepared in this example was measured with a vernier caliper to be 13mm to 16mm, and the density was measured with reference to GB/T1033.1-2008 using a drainage method to be 0.37g/cm3The hydrostatic strength of the reference MIL-S-24154A standard test is 15 MPa.
Example 2
Preparation of reinforced polystyrene foam balls:
1) uniformly mixing 1.5 parts of 2mm chopped polyacrylonitrile carbon-carbon fiber (diameter is 7 mu m), 100 parts of epoxy resin E-51, 12 parts of diluent JX-022 and 2 parts of coupling agent KH-560 by using a high-speed mixing stirrer, then grinding in a three-roll grinder, and further uniformly stirring in the high-speed mixing stirrer;
2) adding 25 parts of curing agent isophorone diamine into the resin mixed slurry, uniformly mixing, and adding polystyrene foam balls (the particle size ranges from 20 mm to 23mm, and the bulk density of the polystyrene foam balls is about 20kg/m3) Adding into the mixed slurry, stirring thoroughly to coat a layer of epoxy resin mixed slurry on the surface of polystyrene foam ball, placing into a ball rolling machine with the above chopped fiber, and coating a layer of epoxy resin mixed slurry on the surfaceChopped fibers are put into a 60 ℃ oven for curing;
3) adding 80 parts of curing agent methyl tetrahydrophthalic anhydride and 1 part of accelerator DMP30 into resin mixed slurry, uniformly mixing, adding the foam balls obtained in the step 2) into the mixed slurry, fully and uniformly stirring, putting into a ball rolling machine with the above chopped fibers, uniformly coating a layer of chopped fibers on the surface of the foam balls, and then putting into an oven at 100 ℃ for curing for 3 hours;
repeating the step 3) for 2 times, and curing for 4 hours at 140 ℃;
4) and cleaning the surface of the coated polystyrene foam ball by using acetone.
The reinforced polystyrene foam beads prepared in this example had a diameter ranging from 22mm to 25mm as measured by a vernier caliper and a density of 0.32g/cm as measured by a drainage method3The hydrostatic strength of the reference MIL-S-24154A standard test is 8 MPa.
Example 3
Preparation of reinforced polystyrene foam balls:
1) 1 part of 1mm chopped polyacrylonitrile carbon fiber (diameter is 5 mu m), 100 parts of epoxy resin E-51, 8 parts of diluent JX-024 and 1 part of coupling agent KH550 are uniformly mixed by a high-speed mixing stirrer, and then the mixture is put into a three-roll grinder for grinding and then is further uniformly stirred in the high-speed mixing stirrer;
2) adding 30 parts of curing agent isophorone diamine into the resin mixed slurry, uniformly mixing, and uniformly spraying a coating system onto polystyrene foam balls (the particle size range is 8-10mm, and the bulk density of the polystyrene foam balls is about 20 kg/m) by using a spray gun3) Coating a layer of epoxy resin mixed slurry on the surface of the polystyrene foam ball uniformly, and then coating a layer of 0.23g/cm uniformly in a rolling ball mode3The hollow glass beads (the particle size range is 15-40 mu m) are solidified for 3 hours at the temperature of 60 ℃;
3) adding 30 parts of curing agent isophorone diamine into the resin mixed slurry, uniformly mixing, uniformly spraying a coating resin system onto the polystyrene foam balls by using a spray gun to uniformly coat a layer of epoxy resin mixed slurry on the surfaces of the polystyrene foam balls, and then uniformly coating a layer of 0.23g/cm3The hollow glass beads are cured for 2 hours at 80 ℃ and cured for 2 hours at 100 ℃;
repeating the step 3) for 4 times, and curing for 3 hours at 130 ℃.
4) And cleaning the surface of the coated polystyrene foam ball by using acetone.
The reinforced polystyrene foam beads prepared in this example had a diameter range of 12mm to 16mm as measured by a vernier caliper and a density of 0.36g/cm as measured by a drainage method3And the hydrostatic strength is 13MPa according to the reference MIL-S-24154A standard test.
Comparative example 1
Unlike example 1, the reagent raw material thermosetting resin prepolymer used was free of fibers and hollow glass beads in the subsequent steps.
The density of the reinforced polystyrene foam ball prepared in this comparative example was 0.40g/cm3And the hydrostatic strength is 11 MPa. The resulting reinforced polystyrene spheres had higher density and lower hydrostatic strength than example 1.
Comparative example 2
Unlike example 1, the reagent raw material thermosetting resin prepolymer used was free of fibers, and step (3) in example 1 was repeated 5 times.
The density of the reinforced polystyrene foam ball prepared in this comparative example was 0.315g/cm3And the hydrostatic pressure strength is 6.5 MPa. Compared with example 1, the density of the reinforced polystyrene ball is basically consistent, and the hydrostatic strength is reduced.
Claims (10)
1. The reinforced polystyrene foam ball includes core-shell structure, polystyrene foam ball as core and thermosetting resin layer with blended fiber and optionally blended hollow glass bead as shell.
2. The reinforced polystyrene foam ball of claim 1,
the thermosetting resin is at least one of epoxy resin, phenolic resin and unsaturated polyester resin; and/or the presence of a gas in the gas,
the fibers are at least one of glass fibers and carbon fibers.
3. The reinforced polystyrene foam ball of claim 2,
the thermosetting resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, thermosetting phenolic resin and unsaturated polyester resin; and/or the presence of a gas in the gas,
the fibers are chopped fibers.
4. The reinforced polystyrene foam ball of claim 1,
the density of the hollow glass beads is 0.1-0.42g/cm3Preferably 0.2 to 0.32g/cm3(ii) a And/or the presence of a gas in the gas,
the particle size range of the hollow glass beads is 11-135 μm, preferably 15-100 μm; and/or the presence of a gas in the gas,
the bulk density of the polystyrene foam balls is 0.018-0.03 g/m3(ii) a And/or the presence of a gas in the gas,
the particle size range of the polystyrene foam ball is 2-50mm, preferably 5-12 mm; and/or the presence of a gas in the gas,
the length of the chopped fiber is less than 2mm, and the diameter of the chopped fiber is 5-7 mu m; and/or the presence of a gas in the gas,
the length-diameter ratio of the chopped fiber is (1-8): 1.
5. the reinforced polystyrene foam ball as claimed in any one of claims 1 to 4,
the density of the reinforced polystyrene foam ball is 200-500kg/m3Preferably 250-380kg/m3(ii) a And/or the presence of a gas in the gas,
the particle size range of the reinforced polystyrene foam ball is 5-60mm, and preferably 8-15 mm; and/or the presence of a gas in the gas,
the average thickness of the shell layer of the reinforced polystyrene foam ball is 1-10mm, and preferably 2-8 mm.
6. The method for preparing the reinforced polystyrene foam ball according to any one of claims 1 to 5, comprising wrapping a mixed slurry of a thermosetting resin prepolymer containing the fiber on the outside of the polystyrene foam ball to form a mixed slurry coating layer, optionally mixing the fiber and/or hollow glass beads on the mixed slurry coating layer, and then curing to obtain the reinforced polystyrene foam ball of the invention.
7. The preparation method of claim 6, wherein the thermosetting resin prepolymer mixed slurry comprises the following components in parts by mass:
8. the production method according to claim 7,
the thermosetting resin prepolymer is at least one of epoxy resin prepolymer, phenolic resin prepolymer and unsaturated polyester resin prepolymer; and/or the presence of a gas in the gas,
the curing agent is at least one selected from amine curing agents or anhydride curing agents, preferably at least one selected from T31 curing agents, isophorone diamine and methyl tetrahydrophthalic anhydride; and/or the presence of a gas in the gas,
the diluent is at least one selected from a monoepoxy diluent and a diepoxy diluent, and preferably at least one selected from a diepoxy diluent JX-022 and a diepoxy diluent JX-024; and/or the presence of a gas in the gas,
the coupling agent is at least one selected from silane coupling agents and titanate coupling agents, and preferably at least one selected from silane coupling agents KH560 and KH 550.
9. A method according to any one of claims 6 to 8, comprising the steps of:
(1) uniformly mixing the components including the fiber, the thermosetting resin prepolymer, the diluent, the coupling agent and the curing agent to form mixed slurry of the thermosetting resin prepolymer; preferably, the curing agent is mixed last;
(2) adding the polystyrene foam ball into the mixed slurry or spraying the mixed slurry on the polystyrene foam ball to form a mixed slurry coating layer; optionally, mixing the fibers and/or hollow glass microspheres on a coating layer of the mixed slurry;
(3) curing;
optionally, repeating steps (2) and (3) above.
10. The method of claim 9, wherein:
the steps (2) and (3) can be performed for 1-10 times, preferably 2-6 times; and/or the presence of a gas in the gas,
the curing in the step (3) is low-temperature curing and/or medium-high-temperature curing,
preferably, the low-temperature curing temperature is 0-30 ℃, and the curing time is 0.3-3 h; and/or the presence of a gas in the atmosphere,
the medium-high temperature curing temperature is 60-140 ℃, and the curing time is 1-6 h.
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