CN117264130A - Expandable microsphere for low-temperature environment and preparation method thereof - Google Patents
Expandable microsphere for low-temperature environment and preparation method thereof Download PDFInfo
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- CN117264130A CN117264130A CN202311549582.4A CN202311549582A CN117264130A CN 117264130 A CN117264130 A CN 117264130A CN 202311549582 A CN202311549582 A CN 202311549582A CN 117264130 A CN117264130 A CN 117264130A
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- 229920000103 Expandable microsphere Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 42
- 239000004814 polyurethane Substances 0.000 claims abstract description 42
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 35
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 17
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims abstract description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002981 blocking agent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 35
- 238000005187 foaming Methods 0.000 abstract description 23
- 239000011257 shell material Substances 0.000 abstract description 13
- 239000004088 foaming agent Substances 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000006260 foam Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000087 stabilizing effect Effects 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 5
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses an expandable microsphere for a low-temperature environment and a preparation method thereof, belonging to the technical field of expandable microspheres, and comprising the following components in parts by weight: 3.2-3.6 parts of polyurethane with terminal double bonds, 8-10 parts of methacrylonitrile, 15-17 parts of acrylonitrile, 5-7 parts of butyl acrylate, 5-6 parts of methyl methacrylate, 0.26-0.38 part of dilauryl peroxide and 14-16 parts of pentane; the terminal double bond polyurethane is prepared by taking diphenylmethane-4, 4' -diisocyanate as a hard segment, polytetrahydrofuran and polyethylene glycol as soft segments and hydroxyethyl acrylate as a blocking agent. The invention provides a mode of adding polyurethane with terminal double bonds into a shell material, which realizes the improvement of the foamability of the foaming microsphere, and simultaneously selects pentane as a foaming agent, thereby realizing the technical effect of synthesizing the low-temperature foaming microsphere in a lower pressure environment.
Description
Technical Field
The invention belongs to the technical field of expanded microspheres, and particularly relates to an expandable microsphere for a low-temperature environment and a preparation method thereof.
Background
The heat expandable microsphere is a microsphere particle with a core-shell structure, the core of the microsphere particle is a foaming agent, the shell layer is a thermoplastic polymer, the boiling point of the core foaming agent is lower than the glass transition temperature of the thermoplastic polymer of the shell layer, the foaming agent is gasified or decomposed after the microsphere is heated, the shell layer is softened when reaching the glass transition temperature, is compressed and expanded and deformed, and after being cooled, the expansion state is kept unchanged, the volume increase density is reduced, and the microsphere particle has good expansion performance; the low-temperature thermal expansion microsphere is a microsphere used at a lower foaming temperature, a low-boiling point foaming agent is usually used for synthesizing a shell layer with a lower glass transition temperature, the low-temperature foaming agent is usually gaseous at room temperature, the synthesis is required in a low-temperature high-pressure environment, and the shell layer with the lower glass transition temperature is often poor in loose structure stability; the main influencing factors of the performance of the thermally expandable microsphere are respectively shell monomer, cross-linking agent, foaming agent, initiator and dispersing agent, wherein the reaction oil phase is the shell monomer, the cross-linking agent, the foaming agent and the initiator, and the dispersing phase is water and the dispersing agent.
The prior art mainly has the following problems: 1. the foaming performance of the low-temperature foaming microsphere is poor; 2. the low-temperature foaming microsphere uses a low-boiling point foaming agent, and a high-pressure environment is needed during heating synthesis.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides the expandable microsphere for the low-temperature environment and the preparation method thereof, and in order to solve the problem of poor foaming performance, the invention provides a method for adding the polyurethane with terminal double bonds into a shell material, so that the foamability of the expandable microsphere is improved, and meanwhile pentane is selected as a foaming agent, so that the technical effect of synthesizing the low-temperature expandable microsphere in a lower-pressure environment is realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides an expandable microsphere for a low-temperature environment, which comprises the following components in parts by weight: 3.2-3.6 parts of polyurethane with terminal double bonds, 8-10 parts of methacrylonitrile, 15-17 parts of acrylonitrile, 5-7 parts of butyl acrylate, 5-6 parts of methyl methacrylate, 0.26-0.38 part of dilauryl peroxide and 14-16 parts of pentane; the terminal double bond polyurethane is prepared by taking diphenylmethane-4, 4' -diisocyanate as a hard segment, polytetrahydrofuran and polyethylene glycol as soft segments and hydroxyethyl acrylate as a blocking agent.
Preferably, the terminal double bond polyurethane comprises the following components in parts by weight: 35-40 parts of diphenylmethane-4, 4' -diisocyanate, 6-9 parts of polytetrahydrofuran, 4-6 parts of polyethylene glycol, 0.6-0.8 part of pentamethyldiethylenetriamine, 3-5 parts of 1, 6-hexanediol and 4-5 parts of hydroxyethyl acrylate.
Preferably, the preparation method of the polyurethane with terminal double bonds specifically comprises the following steps:
s1, adding diphenylmethane-4, 4' -diisocyanate into a reactor, charging nitrogen to remove oxygen, heating for melting, adding polytetrahydrofuran polyethylene glycol, and stirring in a water bath to obtain a mixture;
s2, adding pentamethyldiethylenetriamine into the mixture obtained in the step S1, and stirring in a water bath to obtain an oligomer;
s3, adding the 1, 6-hexanediol agent into the oligomer obtained in the S2, and continuing water bath stirring to obtain an isocyanate-terminated oligomer;
and S4, adding hydroxyethyl acrylate into the isocyanate-terminated oligomer obtained in the step S3, and continuing water bath stirring to obtain the polyurethane with terminal double bonds.
Preferably, in S1, the heating melting temperature is 60-80 ℃ and the heating time is 8-12min.
Preferably, in S1, the water bath temperature is 70-80 ℃, the stirring speed is 200-300rpm, and the time is 25-35min.
Preferably, in S2, the water bath temperature is 76-88 ℃, the stirring speed is 70-80rpm, and the time is 100-140min.
Preferably, in S3, the water bath temperature is 80-86 ℃, the stirring speed is 80-90rpm, and the time is 3-5min.
Preferably, in S4, the water bath temperature is 50-60 ℃, the stirring speed is 30-50rpm, and the time is 80-100min.
The invention also provides a preparation method of the expandable microsphere for a low-temperature environment, which comprises the following steps:
(1) Completely dissolving the prepared polyurethane with terminal double bonds with methacrylonitrile, acrylonitrile, butyl acrylate, methyl methacrylate, dilauroyl peroxide and pentane to obtain an oil phase;
(2) Adding hydroxypropyl methyl cellulose into a sodium chloride aqueous solution with the mass fraction of 16-22% in an adding amount of 6-8g/L, stirring and dissolving to obtain a mixed solution, adding nano silicon dioxide with the mass fraction of 8-12% into the mixed solution, and stirring and dispersing to obtain a dispersed phase;
(3) Mixing the oil phase obtained in the step (1) and the disperse phase obtained in the step (2), emulsifying for 6-8min at a rotating speed of 7000-9000rpm to obtain a suspension, adding the suspension into a reaction kettle, introducing nitrogen to remove air, pressurizing to 0.22-0.25mpa, and heating at 60-65 ℃ for 18-22h to obtain a reaction product;
(4) And (3) cooling, filtering and washing the reaction product obtained in the step (3), and then putting the reaction product into an oven to be dried for 10-15 hours at 50 ℃ to obtain the expandable microspheres used in a low-temperature environment.
The beneficial effects obtained by the invention are as follows: the preparation method has the advantages that the preparation terminal double bond polyurethane is added into a shell material, the initial foaming temperature, the foam stabilizing temperature range and the foaming multiplying power of the microsphere are improved, diphenylmethane-4, 4 '-diisocyanate is used as a hard segment, polytetrahydrofuran and polyethylene glycol are used as soft segments, and hydroxyethyl acrylate is used as a blocking agent to prepare the terminal double bond polyurethane as a long-chain cross-linking agent, wherein the diphenylmethane-4, 4' -diisocyanate contains a diphenyl ring structure, the material strength can be improved, the polytetrahydrofuran contains an ether bond structure, the carbon-oxygen molecular structure can freely rotate to enhance the softness of the material, the use of the polyethylene glycol further increases the distance of terminal double bonds, the elasticity of the shell material is improved, the shell is not easy to crack, and the foam stabilizing temperature range is improved; the boiling point of pentane under normal pressure is 36.1 ℃, the pentane is liquid under normal temperature, and pentane is used as a foaming agent, so that the low-temperature foaming microsphere can be synthesized under a lower pressure environment, and the requirement on equipment is reduced; the shell material with lower glass transition temperature can be obtained by taking methacrylonitrile, acrylonitrile, butyl acrylate and methyl methacrylate as polymerization monomers and dilauroyl peroxide as an initiator, and the foaming temperature is reduced.
Drawings
FIG. 1 is a graph showing the results of the initial foaming temperatures of microspheres of examples 1 to 3 and comparative examples 1 to 2 according to the present invention;
FIG. 2 is a graph showing the results of the bubble temperature course of the microspheres of examples 1-3 and comparative examples 1-2 according to the present invention;
FIG. 3 is a graph showing the results of the expansion ratio of microspheres of examples 1 to 3 and comparative examples 1 to 2 according to the present invention;
FIG. 4 is a graph showing the result of the electron microscope of the microsphere in example 1 of the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials and test strains used in the examples described below, unless otherwise specified, were commercially available.
Diphenylmethane-4, 4' -diisocyanate (CasNo: 101-68-8), commercially available from Beijing enokia technologies Co., ltd., cat# A95462;
polytetrahydrofuran (CasNo: 25190-06-1), available from Beijing Inock technologies Co., ltd., cat# A95364;
polyethylene glycol (CasNo: 25322-68-3), available from Beijing enokie technologies Co., ltd., cat# A35872;
pentamethyldiethylenetriamine (CasNo: 3030-47-5), available from Beijing enokia technologies Co., ltd., cat. No. A49288;
1, 6-hexanediol (CasNo: 629-11-8), available from Beijing Enoka technologies Co., ltd., cat. No. A12439;
hydroxyethyl acrylate (CasNo. 818-61-1), available from Beijing enokie technologies Co., ltd., cat# A70293;
methacrylonitrile (CasNo. 126-98-7), available from Beijing enokie technologies Co., ltd., cat# 131-08945;
acrylonitrile (CasNo: 107-13-1), available from Beijing enokio technologies Co., ltd., product number A77066;
butyl acrylate (CasNo: 141-32-2), available from Beijing Inocover technologies Inc., cat# A80112;
methyl methacrylate (CasNo. 80-62-6), available from Beijing enokie technologies Co., ltd., cat# A67112;
dilauryl peroxide (CasNo: 105-74-8), available from Beijing Inocai technologies Co., ltd., cat# A29592;
pentane (CasNo: 109-66-0), available from Beijing InocKai technologies Co., ltd., cat# A84282;
hydroxypropyl methylcellulose (CasNo. 9004-65-3), commercially available from Beijing Inock technologies Co., ltd., cat# 42323;
nano-silica (CasNo: 60676-86-0), available from Beijing enokie technologies Inc., cat No. N817574.
Example 1
An expandable microsphere for use in a low temperature environment comprises the following components in parts by weight: 3.6 parts of polyurethane with terminal double bonds, 10 parts of methacrylonitrile, 17 parts of acrylonitrile, 7 parts of butyl acrylate, 6 parts of methyl methacrylate, 0.38 part of dilauroyl peroxide and 16 parts of pentane.
The terminal double bond polyurethane comprises the following components in parts by weight: 40 parts of diphenylmethane-4, 4' -diisocyanate, 9 parts of polytetrahydrofuran, 6 parts of polyethylene glycol, 0.8 part of pentamethyldiethylenetriamine, 5 parts of 1, 6-hexanediol and 5 parts of hydroxyethyl acrylate.
Preferably, the preparation method of the polyurethane with terminal double bonds specifically comprises the following steps:
s1, adding diphenylmethane-4, 4' -diisocyanate into a reactor, charging nitrogen to remove oxygen, heating at 80 ℃ for 12min to melt, adding polytetrahydrofuran and polyethylene glycol, and stirring at 300rpm in a water bath at 80 ℃ for 35min to obtain a mixture;
s2, adding pentamethyldiethylenetriamine into the mixture obtained in the step S1, and stirring in a water bath at 88 ℃ for 140min at a speed of 80rpm to obtain an oligomer;
s3, adding a1, 6-hexanediol agent into the oligomer obtained in the S2, and stirring in a 86 ℃ water bath at a speed of 90rpm for 5min to obtain an isocyanate-terminated oligomer;
and S4, adding hydroxyethyl acrylate into the isocyanate-terminated oligomer obtained in the step S3, and stirring in a water bath at 60 ℃ for 100 minutes at a speed of 50rpm to obtain the polyurethane with terminal double bonds.
The invention also provides a preparation method of the expandable microsphere for a low-temperature environment, which comprises the following steps:
(1) Completely dissolving the prepared polyurethane with terminal double bonds with methacrylonitrile, acrylonitrile, butyl acrylate, methyl methacrylate, dilauroyl peroxide and pentane to obtain an oil phase;
(2) Adding hydroxypropyl methyl cellulose into a sodium chloride aqueous solution with the mass fraction of 22% in an adding amount of 8g/L, stirring and dissolving to obtain a mixed solution, adding nano silicon dioxide with the mass fraction of 12% into the mixed solution, and stirring and dispersing to obtain a dispersed phase;
(3) Mixing the oil phase obtained in the step (1) and the disperse phase obtained in the step (2), emulsifying for 8min at a rotating speed of 9000rpm to obtain a suspension, adding the suspension into a reaction kettle, introducing nitrogen to remove air, pressurizing to 0.25mpa, and heating at 65 ℃ for 22h to obtain a reaction product;
(4) And (3) cooling, filtering and washing the reaction product obtained in the step (3), and then putting the reaction product into an oven to be dried for 15 hours at 50 ℃ to obtain the expandable microspheres used in a low-temperature environment.
Example 2
An expandable microsphere for use in a low temperature environment comprises the following components in parts by weight: 3.2 parts of polyurethane with terminal double bonds, 8 parts of methacrylonitrile, 15 parts of acrylonitrile, 5 parts of butyl acrylate, 5 parts of methyl methacrylate, 0.26 part of dilauroyl peroxide and 14 parts of pentane.
The terminal double bond polyurethane comprises the following components in parts by weight: 35 parts of diphenylmethane-4, 4' -diisocyanate, 6 parts of polytetrahydrofuran, 4 parts of polyethylene glycol, 0.6 part of pentamethyldiethylenetriamine, 3 parts of 1, 6-hexanediol and 4 parts of hydroxyethyl acrylate.
Preferably, the preparation method of the polyurethane with terminal double bonds specifically comprises the following steps:
s1, adding diphenylmethane-4, 4' -diisocyanate into a reactor, charging nitrogen to remove oxygen, heating at 60 ℃ for 8min to melt, adding polytetrahydrofuran and polyethylene glycol, and stirring at 200rpm in a70 ℃ water bath for 25min to obtain a mixture;
s2, adding pentamethyldiethylenetriamine into the mixture obtained in the step S1, and stirring in a water bath at 76 ℃ for 100min at a speed of 70rpm to obtain an oligomer;
s3, adding a1, 6-hexanediol agent into the oligomer obtained in the S2, and stirring in a water bath at 80 ℃ for 3min at a speed of 80rpm to obtain an isocyanate-terminated oligomer;
and S4, adding hydroxyethyl acrylate into the isocyanate-terminated oligomer obtained in the step S3, and stirring in a water bath at 50 ℃ for 80 minutes at a speed of 30rpm to obtain the polyurethane with terminal double bonds.
The invention also provides a preparation method of the expandable microsphere for a low-temperature environment, which comprises the following steps:
(1) Completely dissolving the prepared polyurethane with terminal double bonds with methacrylonitrile, acrylonitrile, butyl acrylate, methyl methacrylate, dilauroyl peroxide and pentane to obtain an oil phase;
(2) Adding hydroxypropyl methyl cellulose into a sodium chloride aqueous solution with the mass fraction of 16% in an adding amount of 6g/L, stirring and dissolving to obtain a mixed solution, adding nano silicon dioxide with the mass fraction of 8% into the mixed solution, and stirring and dispersing to obtain a dispersed phase;
(3) Mixing the oil phase obtained in the step (1) and the disperse phase obtained in the step (2), emulsifying for 6min at 7000rpm to obtain a suspension, adding the suspension into a reaction kettle, introducing nitrogen to remove air, pressurizing to 0.22mpa, and heating at 60 ℃ for 18h to obtain a reaction product;
(4) And (3) cooling, filtering and washing the reaction product obtained in the step (3), and then putting the reaction product into an oven to be dried for 10 hours at 50 ℃ to obtain the expandable microspheres used in a low-temperature environment.
Example 3
An expandable microsphere for use in a low temperature environment comprises the following components in parts by weight: 3.4 parts of polyurethane with terminal double bonds, 9 parts of methacrylonitrile, 16 parts of acrylonitrile, 6 parts of butyl acrylate, 5.5 parts of methyl methacrylate, 0.32 part of dilauroyl peroxide and 15 parts of pentane.
The terminal double bond polyurethane comprises the following components in parts by weight: 37 parts of diphenylmethane-4, 4' -diisocyanate, 8 parts of polytetrahydrofuran, 5 parts of polyethylene glycol, 0.7 part of pentamethyldiethylenetriamine, 4 parts of 1, 6-hexanediol and 4 parts of hydroxyethyl acrylate.
Preferably, the preparation method of the polyurethane with terminal double bonds specifically comprises the following steps:
s1, adding diphenylmethane-4, 4' -diisocyanate into a reactor, charging nitrogen to remove oxygen, heating at 70 ℃ for 10min to melt, adding polytetrahydrofuran and polyethylene glycol, and stirring at 250rpm in a 75 ℃ water bath for 30min to obtain a mixture;
s2, adding pentamethyldiethylenetriamine into the mixture obtained in the step S1, and stirring in a water bath at 85 ℃ for 100-140min at a speed of 75rpm to obtain an oligomer;
s3, adding a1, 6-hexanediol agent into the oligomer obtained in the S2, and stirring in a water bath at 80-86 ℃ for 4min at a speed of 85rpm to obtain an isocyanate-terminated oligomer;
and S4, adding hydroxyethyl acrylate into the isocyanate-terminated oligomer obtained in the step S3, and stirring in a water bath at 55 ℃ for 90 minutes at a speed of 40rpm to obtain the polyurethane with terminal double bonds.
The invention also provides a preparation method of the expandable microsphere for a low-temperature environment, which comprises the following steps:
(1) Completely dissolving the prepared polyurethane with terminal double bonds with methacrylonitrile, acrylonitrile, butyl acrylate, methyl methacrylate, dilauroyl peroxide and pentane to obtain an oil phase;
(2) Adding hydroxypropyl methyl cellulose into a sodium chloride aqueous solution with the mass fraction of 20% in an adding amount of 7g/L, stirring and dissolving to obtain a mixed solution, adding nano silicon dioxide with the mass fraction of 10% into the mixed solution, and stirring and dispersing to obtain a dispersed phase;
(3) Mixing the oil phase obtained in the step (1) and the disperse phase obtained in the step (2), emulsifying for 7min at a rotating speed of 8000rpm to obtain a suspension, adding the suspension into a reaction kettle, introducing nitrogen to remove air, pressurizing to 0.23mpa, and heating at 62 ℃ for 20h to obtain a reaction product;
(4) And (3) cooling, filtering and washing the reaction product obtained in the step (3), and then putting the reaction product into an oven to be dried for 13 hours at 50 ℃ to obtain the expandable microspheres used in a low-temperature environment.
Comparative example 1
This comparative example provides an expandable microsphere which differs from example 1 only in that the terminal double bond polyurethane is not included in the components, the remaining components, component contents being the same as in example 1.
Comparative example 2
This comparative example provides an expandable microsphere differing from example 1 only in that the terminal double bond polyurethane is not included in the component, and trimethylolpropane trimethacrylate having a mole fraction of 0.25% is added as a crosslinking agent, and the remaining components and the component contents are the same as example 1.
Experimental example
The expandable microspheres obtained in examples 1 to 3 and comparative examples 1 to 2 were tested with a micro-melting point apparatus, the initial heating rate was 5℃per minute, the heating rate after 70℃was adjusted to 2℃per minute, the initial foaming temperature and the capsule breaking temperature of the microspheres were recorded, and the average particle diameter before foaming of the expandable microspheres was measured by a metallographic analysis system and recorded as d 0 The average particle size before the inflatable microspheres are broken is measured and recorded as d;
the bubble temperature plateau of the expandable microspheres was calculated by the following formula:
foam stabilization temperature range = initial foaming temperature-breaking temperature;
the expansion ratio of the expandable microspheres was calculated by the following formula:
expansion ratio=d/d 0 。
FIG. 1 is a graph showing the results of the initial foaming temperatures of the microspheres of examples 1 to 3 and comparative examples 1 to 2 according to the present invention, wherein the initial foaming temperatures of the microspheres of examples 1 to 3 are 86℃and 88℃and 85℃respectively, and the initial foaming temperatures of the microspheres of comparative examples 1 to 2 are 98℃and 106℃respectively; the initial foaming temperature of the microspheres of examples 1-3 is significantly lower than that of comparative examples 1-2, indicating that the use of the terminal double bond polyurethane reduces the initial foaming temperature of the microspheres and can be used at lower foaming temperatures; the terminal double bond polyurethane has low glass transition temperature and can reduce foaming temperature.
FIG. 2 is a graph showing the results of the foam stabilizing temperature ranges of the microspheres of examples 1-3 and comparative examples 1-2 according to the present invention, wherein the foam stabilizing temperature ranges of the microspheres of examples 1-3 are 62 ℃, 61 ℃, 62 ℃ and the foam stabilizing temperature ranges of the microspheres of comparative examples 1-2 are 10 ℃ and 34 ℃ respectively; the foam stabilizing temperature range of the microspheres in the examples 1-3 is obviously lower than that in the comparative examples 1-2, which shows that the use of polyurethane with terminal double bonds improves the foam stabilizing temperature range of the microspheres; the hard segment diphenylmethane-4, 4' -diisocyanate monomer of the polyurethane with terminal double bonds contains a double benzene ring structure, has high rigidity and can improve the strength of the material.
FIG. 3 is a graph showing the results of the expansion ratio of the microspheres of examples 1-3 and comparative examples 1-2 according to the present invention, wherein the expansion ratio of the microspheres of examples 1-3 is 6.1, 6.3 and 6.3, and the expansion ratio of the microspheres of comparative examples 1-2 is 2.6 and 4.2, respectively; the use of the polyurethane with terminal double bonds is illustrated to improve the foaming ratio of the microsphere; the soft segment polytetrahydrofuran of the polyurethane with terminal double bonds contains ether bonds, carbon and oxygen atoms can rotate freely, the flexibility of the material is improved, the molecular symmetry of the diphenylmethane-4, 4' -diisocyanate is good, and the polyurethane with terminal double bonds has good crystallinity and air tightness.
FIG. 4 is a graph showing the results of the electron microscope of the microspheres of example 1 according to the present invention, wherein the microspheres of example 1 have uniform particle size distribution and complete spherical shape.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (9)
1. An expandable microsphere for use in a cryogenic environment, characterized by: comprises the following components in parts by weight: 3.2-3.6 parts of polyurethane with terminal double bonds, 8-10 parts of methacrylonitrile, 15-17 parts of acrylonitrile, 5-7 parts of butyl acrylate, 5-6 parts of methyl methacrylate, 0.26-0.38 part of dilauryl peroxide and 14-16 parts of pentane; the terminal double bond polyurethane is prepared by taking diphenylmethane-4, 4' -diisocyanate as a hard segment, polytetrahydrofuran and polyethylene glycol as soft segments and hydroxyethyl acrylate as a blocking agent.
2. The expandable microsphere for use in a low temperature environment according to claim 1, wherein: the terminal double bond polyurethane comprises the following components in parts by weight: 35-40 parts of diphenylmethane-4, 4' -diisocyanate, 6-9 parts of polytetrahydrofuran, 4-6 parts of polyethylene glycol, 0.6-0.8 part of pentamethyldiethylenetriamine, 3-5 parts of 1, 6-hexanediol and 4-5 parts of hydroxyethyl acrylate.
3. A method for preparing expandable microspheres in a low temperature environment, comprising the steps of: the method specifically comprises the following steps:
(1) Completely dissolving the prepared polyurethane with terminal double bonds with methacrylonitrile, acrylonitrile, butyl acrylate, methyl methacrylate, dilauroyl peroxide and pentane to obtain an oil phase;
(2) Adding hydroxy methyl cellulose into a sodium chloride aqueous solution with the mass fraction of 16-22% in an adding amount of 6-8g/mL, stirring and dissolving to obtain a mixed solution, adding nano silicon dioxide with the mass fraction of 8-12% into the mixed solution, and stirring and dispersing to obtain a dispersed phase;
(3) Mixing the oil phase obtained in the step (1) and the disperse phase obtained in the step (2), emulsifying for 6-8min at a rotating speed of 7000-9000rpm to obtain a suspension, adding the suspension into a reaction kettle, introducing nitrogen to remove air, pressurizing to 0.22-0.25mpa, and heating at 60-65 ℃ for 18-22h to obtain a reaction product;
(4) And (3) cooling, filtering and washing the reaction product obtained in the step (3), and then putting the reaction product into an oven to be dried for 10-15 hours at 50 ℃ to obtain the expandable microspheres used in a low-temperature environment.
4. A method of preparing expandable microspheres for use in a cryogenic environment according to claim 3, wherein: the preparation method of the polyurethane with terminal double bonds specifically comprises the following steps:
s1, adding diphenylmethane-4, 4' -diisocyanate into a reactor, charging nitrogen to remove oxygen, heating for melting, adding polytetrahydrofuran polyethylene glycol, and stirring in a water bath to obtain a mixture;
s2, adding pentamethyldiethylenetriamine into the mixture obtained in the step S1, and stirring in a water bath to obtain an oligomer;
s3, adding the 1, 6-hexanediol agent into the oligomer obtained in the S2, and continuing water bath stirring to obtain an isocyanate-terminated oligomer;
and S4, adding hydroxyethyl acrylate into the isocyanate-terminated oligomer obtained in the step S3, and continuing water bath stirring to obtain the polyurethane with terminal double bonds.
5. The method of preparing expandable microspheres for use in a low temperature environment according to claim 4, wherein: in S1, the heating melting temperature is 60-80 ℃ and the heating time is 8-12min.
6. The method of preparing expandable microspheres for use in a low temperature environment according to claim 5, wherein: in S1, the water bath temperature is 70-80 ℃, the stirring speed is 200-300rpm, and the time is 25-35min.
7. The method of preparing expandable microspheres for use in a cryogenic environment according to claim 6, wherein: in S2, the water bath temperature is 76-88 ℃, the stirring speed is 70-80rpm, and the time is 100-140min.
8. The method of preparing expandable microspheres for use in a cryogenic environment according to claim 7, wherein: in S3, the water bath temperature is 80-86 ℃, the stirring speed is 80-90rpm, and the time is 3-5min.
9. The method of preparing expandable microspheres for use in a cryogenic environment according to claim 8, wherein: in S4, the water bath temperature is 50-60 ℃, the stirring speed is 30-50rpm, and the time is 80-100min.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2354355A1 (en) * | 1973-10-30 | 1975-05-07 | Dow Chemical Co | Synthetic paper - contg expandable thermoplastic microspheres |
| CN102070868A (en) * | 2009-11-25 | 2011-05-25 | 第一毛织株式会社 | Thermally-expandable microspheres having good foaming characteristics and uniform microsphere diameter and methods of preparing the same |
| CN103665419A (en) * | 2013-12-06 | 2014-03-26 | 四川达威科技股份有限公司 | Synthesis method and application method of low-medium temperature thermal expansion microspheres |
| CN104014287A (en) * | 2014-06-12 | 2014-09-03 | 合肥工业大学 | Thermal expansion type foaming micro-sphere and preparation method thereof |
| US20150322226A1 (en) * | 2012-05-30 | 2015-11-12 | Akzo Nobel Chemicals International B.V. | Microspheres |
| CN108699422A (en) * | 2016-02-19 | 2018-10-23 | 松本油脂制药株式会社 | Heat-expandable microsphere and application thereof |
| US20200216631A1 (en) * | 2017-09-04 | 2020-07-09 | Nouryon Chemicals International B.V. | Thermally expandable microspheres prepared from bio-based monomers |
| CN113304704A (en) * | 2021-05-10 | 2021-08-27 | 万华化学集团股份有限公司 | Self-reinforcing thermal expansion microsphere and preparation method thereof |
| CN113801366A (en) * | 2020-06-12 | 2021-12-17 | 万华化学集团股份有限公司 | Thermal expansion microsphere and preparation method thereof |
-
2023
- 2023-11-21 CN CN202311549582.4A patent/CN117264130A/en not_active Withdrawn
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2354355A1 (en) * | 1973-10-30 | 1975-05-07 | Dow Chemical Co | Synthetic paper - contg expandable thermoplastic microspheres |
| CN102070868A (en) * | 2009-11-25 | 2011-05-25 | 第一毛织株式会社 | Thermally-expandable microspheres having good foaming characteristics and uniform microsphere diameter and methods of preparing the same |
| US20150322226A1 (en) * | 2012-05-30 | 2015-11-12 | Akzo Nobel Chemicals International B.V. | Microspheres |
| CN103665419A (en) * | 2013-12-06 | 2014-03-26 | 四川达威科技股份有限公司 | Synthesis method and application method of low-medium temperature thermal expansion microspheres |
| CN104014287A (en) * | 2014-06-12 | 2014-09-03 | 合肥工业大学 | Thermal expansion type foaming micro-sphere and preparation method thereof |
| CN108699422A (en) * | 2016-02-19 | 2018-10-23 | 松本油脂制药株式会社 | Heat-expandable microsphere and application thereof |
| US20210189090A1 (en) * | 2016-02-19 | 2021-06-24 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microspheres and applications thereof |
| US20200216631A1 (en) * | 2017-09-04 | 2020-07-09 | Nouryon Chemicals International B.V. | Thermally expandable microspheres prepared from bio-based monomers |
| CN113801366A (en) * | 2020-06-12 | 2021-12-17 | 万华化学集团股份有限公司 | Thermal expansion microsphere and preparation method thereof |
| CN113304704A (en) * | 2021-05-10 | 2021-08-27 | 万华化学集团股份有限公司 | Self-reinforcing thermal expansion microsphere and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BAI, X ET AL.: "Thermo-expandable microcapsules with polyurethane as the shell", JOURNAL OF POLYMER RESEARCH, vol. 27, no. 7, pages 185, XP037188217, DOI: 10.1007/s10965-020-02160-y * |
| 周凯军等: "聚氨酯/丙烯酸酯热膨胀微球的制备与性能研究", 塑料工业, vol. 44, no. 6, pages 21 - 25 * |
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