CN117964836A - Expandable microsphere and preparation method and application thereof - Google Patents
Expandable microsphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN117964836A CN117964836A CN202311539067.8A CN202311539067A CN117964836A CN 117964836 A CN117964836 A CN 117964836A CN 202311539067 A CN202311539067 A CN 202311539067A CN 117964836 A CN117964836 A CN 117964836A
- Authority
- CN
- China
- Prior art keywords
- agent
- expandable
- suspending
- mass ratio
- foaming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000103 Expandable microsphere Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000000375 suspending agent Substances 0.000 claims abstract description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 11
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims abstract description 11
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 7
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical group CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 23
- 239000006260 foam Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 7
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 239000004005 microsphere Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides an expandable microsphere, a preparation method and application thereof, and belongs to the field of foaming materials. The expandable microspheres are products obtained by mixing an oil phase and a water phase and then carrying out suspension polymerization, wherein the oil phase comprises a monomer, a foaming agent, a cross-linking agent and an initiator, and the water phase comprises a suspending agent, a suspending aid, an electrolyte and water; the monomer consists of acrylonitrile, methacrylonitrile, hydroxyethyl methacrylate and N, N-dimethylacrylamide, wherein the mass ratio of the acrylonitrile to the methacrylonitrile to the hydroxyethyl methacrylate to the N, N-dimethylacrylamide is (50-85): (15-35): (10-30): (10-25). The expandable microsphere foam stabilizer Wen Chenggao provided by the invention has a foaming multiplying power of up to 30 at 60 ℃ and has a wide application prospect in the preparation of a foaming agent with light weight and wide application temperature range.
Description
Technical Field
The invention belongs to the field of foaming materials, and particularly relates to an expandable microsphere, a preparation method and application thereof.
Background
The thermal expansion microsphere is a capsule type micron particle which takes low boiling alkane as a core material and a polymer material as a shell wall. After heating, the foaming agent is gasified first, so that the pressure in the microsphere is increased, the temperature is continuously increased to the glass transition temperature (Tg) of the polymer shell wall, the shell wall is softened, and the microsphere begins to expand under the action of the difference between the internal pressure and the external pressure until the internal pressure and the external pressure reach the balance, and the microsphere reaches the maximum foaming state. When the external temperature falls below the Tg of the shell polymer, the segment movement of the shell polymer is frozen, and therefore the microspheres remain in their expanded state even at normal temperature. The thermal expansion microsphere has the characteristic of obvious volume change before and after expansion, so that the thermal expansion microsphere has important application value in the aspects of material weight reduction, patterning, three-dimensional and the like.
In terms of application research, researchers have performed a great deal of work. For example, ahmad et al incorporate thermoplastic thermally-expandable microspheres into vinyl plastic substrates to increase the elasticity of the material, which is of value in many applications such as automotive underbody coatings, gaskets, sports goods, and the like. Whinnery et al, starting from commercially available Expancel thermally expandable microspheres, produced a number of large rigid foams of varying densities and mechanical properties by simple heating in a specific mold, which provided a new method for the preparation of large foams. Wu Minghua et al blend the thermally expansive microspheres into the printing paste and use it to print the fabric, thereby increasing the three-dimensional effect and improving the quality of the product on the basis of maintaining the original effect of the pattern.
The application field and market value of the thermal expansion microsphere are closely related to the foaming performance, the dispersibility in matrix polymer and other attributes. The foaming performance mainly comprises the foaming temperature, the foaming multiplying power and the like of the microsphere. The microsphere foaming temperature determines the processing temperature of the corresponding material with the microsphere as an additive, and the foaming ratio determines the lowest density of the lightweight material. Foam stabilizer Wen Chengshi refers to the difference between the initial temperature of expansion (T start) and the temperature at which maximum expansion is achieved (T max) of the thermally expanded microspheres, and represents the temperature range in which the thermally expanded microspheres can foam without breaking the foam. The higher foaming ratio and wider foam stabilizing temperature range are pursued by the academia, and the development of the thermal expansion microsphere with higher foaming ratio and wider foam stabilizing Wen Chengde has important significance.
Liu Jinlin and the like, low-boiling alkane is used as a foaming agent, acrylonitrile is used as a main monomer, methyl methacrylate, N-dimethylacrylamide and methacrylic acid are used as comonomers, a high molecular compound containing divinyl is used as a crosslinking agent, magnesium hydroxide is used as a dispersing agent, and a suspension polymerization method is adopted to prepare the heat-resistant high-temperature thermal expansion microsphere with the foaming temperature higher than 180 ℃, the diameter foaming multiplying power of 4-5 times (the volume foaming multiplying power of 20 times) and the high-temperature foam stabilizing time of approximately 30 minutes. However, the foam stabilizing temperature range of the heat-resistant high-temperature thermal expansion microsphere is narrower (only 45 ℃), and the foaming ratio is still to be further improved.
Disclosure of Invention
The invention aims to provide an expandable microsphere with stable foam Wen Chengkuan and high foaming multiplying power, and a preparation method and application thereof.
The invention provides an expandable microsphere, which is a product obtained by mixing an oil phase and a water phase and then carrying out suspension polymerization, wherein the oil phase comprises a monomer, a foaming agent, a crosslinking agent and an initiator, and the water phase comprises a suspending agent, a suspending aid, an electrolyte and water; the monomer consists of acrylonitrile, methacrylonitrile, hydroxyethyl methacrylate and N, N-dimethylacrylamide, wherein the mass ratio of the acrylonitrile to the methacrylonitrile to the hydroxyethyl methacrylate to the N, N-dimethylacrylamide is (50-85): (15-35): (10-30): (10-25).
Further, the mass ratio of the acrylonitrile, the methacrylonitrile, the hydroxyethyl methacrylate and the N, N-dimethylacrylamide is (54-81): (20-30): (13-24): (12-22);
The mass ratio of the monomer, the foaming agent, the cross-linking agent, the initiator, the suspending agent, the suspending aid, the electrolyte and the water is (110-140): (10-40): (0.03-0.05): (2-3): (50-52): (0.5-0.7): (65-75): (450-550).
Further, the mass ratio of the acrylonitrile, the methacrylonitrile, the hydroxyethyl methacrylate and the N, N-dimethylacrylamide is 54:30:24:12;
the mass ratio of the monomer, the foaming agent, the cross-linking agent, the initiator, the suspending agent, the suspending aid, the electrolyte and the water is 120:30:0.0407:2.45:50.86: (0.59-0.6): 70:500.
Further, the foaming agent is isopentane, the crosslinking agent is 1, 6-hexanediol dimethacrylate, the initiator is azobisisobutyronitrile, and the electrolyte is sodium chloride.
Further, the suspending agent is one or a mixture of two of magnesium chloride hexahydrate and sodium hydroxide.
Further, the suspending agent is a mixture of magnesium chloride hexahydrate and sodium hydroxide, wherein the mass ratio of the magnesium chloride hexahydrate to the sodium hydroxide is 3:1.
Further, the suspending aid is one or a mixture of two of polyvinylpyrrolidone and sodium dodecyl sulfate.
Further, the suspending aid is a mixture of polyvinylpyrrolidone and sodium dodecyl sulfate, wherein the mass ratio of polyvinylpyrrolidone to sodium dodecyl sulfate is (3.2-5.6): 1.
Further, the mass ratio of polyvinylpyrrolidone to sodium dodecyl sulfate is (5-5.6): 1.
The invention also provides a method for preparing the expandable microsphere, which comprises the following steps: mixing the oil phase and the water phase, emulsifying to obtain suspension, performing high-pressure reaction, acidifying, filtering, washing, and drying to obtain the expandable microsphere.
The invention also provides the use of the expandable microspheres as a blowing agent.
Experimental results show that the expandable microsphere foam stabilizer Wen Chengkuan provided by the invention has high foaming multiplying power, wherein the expandable microsphere foam stabilizer Wen Chenggao obtained in the embodiment 5 reaches 60 ℃ and the (volume) foaming multiplying power is as high as 30. The expandable microsphere has wide application prospect in preparing the foaming agent with light weight and wide application temperature range.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Detailed Description
Unless otherwise indicated, the materials and equipment used in the present invention are known products and are obtained by purchasing commercially available products.
Examples 1-6, preparation of Expandable microspheres
The formulation of the expandable microspheres is shown in table 1.
TABLE 1 formulation of expandable microspheres (Unit: g)
The preparation method of the expandable microspheres comprises the following steps:
(1) Oil phase configuration: sequentially adding monomers (acrylonitrile, methacrylonitrile, hydroxyethyl methacrylate and N, N-dimethylacrylamide), a cross-linking agent, an initiator and a foaming agent, and stirring for 30min under ice bath condition to obtain an oil phase.
(2) Aqueous phase configuration: deionized water, sodium chloride, suspending agent (magnesium chloride hexahydrate and sodium hydroxide), suspending aid (polyvinylpyrrolidone (K30) and sodium dodecyl sulfate) were mixed, and stirred in ice bath for 30min to obtain water phase.
(3) Emulsification: mixing the oil phase and the water phase, and emulsifying for 5min by a homogenizer to obtain a suspension.
(4) High pressure reaction: the suspension is added into a high-pressure reaction kettle, the reaction temperature is 55-65 ℃, the time is 24 hours, and the pressure is 0.48MPa.
(5) Post-treatment: and (3) adding hydrochloric acid into the wet material after the reaction to acidify to pH 3, filtering, washing and drying to obtain the thermally expandable microspheres.
The following experiments prove the beneficial effects of the expandable microspheres of the invention.
Experimental example 1 Performance test of the expandable microspheres of the present invention
1. Experimental method
Characterization method of initial temperature of expansion (T start), temperature at which maximum expansion is reached (T max), and bubble stability temperature course: a polarizing microscope (model: DM4P, manufacturer: leika, germany) with a heat stage was used, the heat stage heating rate was 10 ℃/min, the temperature range was room temperature-250 ℃, the objective magnification was 10 times, and the first pellet expansion temperature (T start) and the expansion temperature at the time of maximum (T max) were recorded. Bubble temperature range = T max-Tstart.
The (volume) foaming ratio characterization method comprises the following steps: 1ml of the sample was weighed into a 50ml graduated cylinder, placed into an oven for foaming, and the foaming was recorded to the maximum scale V of the graduated cylinder, foaming ratio = V/1ml.
2. Experimental results
TABLE 2 Performance test results of the expandable microspheres of the invention
As can be seen from Table 2, the temperature range of the expandable microspheres provided in examples 1-6 of the present invention is 41-60 ℃, wherein the temperature range of the expandable microspheres obtained in example 5 is Wen Chenggao to 60 ℃; the expansion ratio of the expandable microspheres (volume) provided in the examples 1-6 is 22-30, wherein the expansion ratio of the expandable microspheres (volume) obtained in the example 5 is as high as 30.
In summary, the invention provides the expandable microsphere with stable foam Wen Chengkuan and high expansion ratio, which has wide application prospect in preparing the foaming agent with light weight and wide application temperature range.
Claims (10)
1. The expandable microsphere is characterized in that the expandable microsphere is a product obtained by suspension polymerization after mixing an oil phase and an aqueous phase, wherein the oil phase comprises a monomer, a foaming agent, a crosslinking agent and an initiator, and the aqueous phase comprises a suspending agent, a suspending aid, an electrolyte and water; the monomer consists of acrylonitrile, methacrylonitrile, hydroxyethyl methacrylate and N, N-dimethylacrylamide, wherein the mass ratio of the acrylonitrile to the methacrylonitrile to the hydroxyethyl methacrylate to the N, N-dimethylacrylamide is (50-85): (15-35): (10-30): (10-25).
2. The expandable microspheres according to claim 1, wherein the mass ratio of acrylonitrile, methacrylonitrile, hydroxyethyl methacrylate and N, N-dimethylacrylamide is (54-81): (20-30): (13-24): (12-22);
The mass ratio of the monomer, the foaming agent, the cross-linking agent, the initiator, the suspending agent, the suspending aid, the electrolyte and the water is (110-140): (10-40): (0.03-0.05): (2-3): (50-52): (0.5-0.7): (65-75): (450-550).
3. The expandable microspheres of claim 2, wherein the mass ratio of acrylonitrile, methacrylonitrile, hydroxyethyl methacrylate, and N, N-dimethylacrylamide is 54:30:24:12;
the mass ratio of the monomer, the foaming agent, the cross-linking agent, the initiator, the suspending agent, the suspending aid, the electrolyte and the water is 120:30:0.0407:2.45:50.86: (0.59-0.6): 70:500.
4. An expandable microsphere according to any one of claims 1-3, wherein the blowing agent is isopentane, the cross-linking agent is 1, 6-hexanediol dimethacrylate, the initiator is azobisisobutyronitrile, and the electrolyte is sodium chloride.
5. An expandable microsphere according to any one of claims 1-3, wherein the suspending agent is one or a mixture of two of magnesium chloride hexahydrate and sodium hydroxide.
6. The expandable microspheres of claim 5, wherein the suspending agent is a mixture of magnesium chloride hexahydrate and sodium hydroxide, wherein the mass ratio of magnesium chloride hexahydrate to sodium hydroxide is 3:1.
7. An expandable microsphere according to any one of claims 1-3, wherein the suspending aid is one or a mixture of two of polyvinylpyrrolidone, sodium dodecyl sulfate.
8. The expandable microspheres of claim 7, wherein the suspending aid is a mixture of polyvinylpyrrolidone and sodium lauryl sulfate, wherein the mass ratio of polyvinylpyrrolidone to sodium lauryl sulfate is (3.2-5.6): 1.
9. A method of making the expandable microspheres of any one of claims 1-8, the method comprising the steps of: mixing the oil phase and the water phase, emulsifying to obtain suspension, performing high-pressure reaction, acidifying, filtering, washing, and drying to obtain the expandable microsphere.
10. Use of expandable microspheres according to any one of claims 1-8 as a blowing agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311539067.8A CN117964836A (en) | 2023-11-17 | 2023-11-17 | Expandable microsphere and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311539067.8A CN117964836A (en) | 2023-11-17 | 2023-11-17 | Expandable microsphere and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117964836A true CN117964836A (en) | 2024-05-03 |
Family
ID=90865084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311539067.8A Pending CN117964836A (en) | 2023-11-17 | 2023-11-17 | Expandable microsphere and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117964836A (en) |
-
2023
- 2023-11-17 CN CN202311539067.8A patent/CN117964836A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108047480B (en) | High-temperature expanded polymer microsphere and preparation method thereof | |
US9605125B2 (en) | Thermally foamable microsphere, method of producing the same, and use thereof | |
KR20110058095A (en) | Heat-expandable microparticles having good expandability and even particle diameter | |
CN108097182B (en) | Superfine environment-friendly thermal expansion microcapsule and preparation method thereof | |
JP5534576B2 (en) | Thermally expansible microsphere and method for producing the same, additive and molded article | |
CN110820068B (en) | Preparation method of phase change fiber | |
US3503908A (en) | Method of making expandable polymers | |
JP2002012693A (en) | Thermally foaming micro-sphere and method for producing the same | |
US3389097A (en) | Expandable polymers | |
CN108884376B (en) | Microsphere, thermally foamable resin composition, and foam molded body and method for producing same | |
JP7279210B2 (en) | Thermally expandable polyvinylidene chloride microspheres | |
CN111019028A (en) | Monodisperse micron-sized polystyrene particles and preparation method thereof | |
JP2976500B2 (en) | Resin particles and method for producing the same | |
JP6672166B2 (en) | Method for preparing solid particulate vinyl aromatic polymer composition for preparation | |
CN117964836A (en) | Expandable microsphere and preparation method and application thereof | |
JP6495958B2 (en) | Acrylic processing aid, method for producing the same, and vinyl chloride resin composition containing the same | |
JP6276423B2 (en) | Thermally foamable microspheres and compositions and molded bodies containing the same | |
CN117417480A (en) | Method for preparing thermal expansion microsphere with narrow particle size distribution | |
CN114149608A (en) | Heat-expandable microsphere with particle size of 1-100 microns prepared by emulsion polymerization | |
JP2004323854A (en) | Heat-expandable microcapsule and method for producing the same | |
JPS6338063B2 (en) | ||
JP4587499B2 (en) | Expandable styrenic resin particles and process for producing the same | |
JP4587499B6 (en) | Expandable styrene resin particles and process for producing the same | |
JPS60156736A (en) | Primarily expanded particle of styrene based resin and production of expansion molded article | |
JPH11152364A (en) | Preparation of foamable styrenic polymer particle |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination |