CN110713619A - Method for producing expandable styrene resin particles - Google Patents
Method for producing expandable styrene resin particles Download PDFInfo
- Publication number
- CN110713619A CN110713619A CN201910598826.5A CN201910598826A CN110713619A CN 110713619 A CN110713619 A CN 110713619A CN 201910598826 A CN201910598826 A CN 201910598826A CN 110713619 A CN110713619 A CN 110713619A
- Authority
- CN
- China
- Prior art keywords
- resin particles
- styrene
- styrene resin
- expandable styrene
- monomer
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 239000002245 particle Substances 0.000 title claims abstract description 58
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 125000004185 ester group Chemical group 0.000 claims abstract description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 18
- IYOVSGHZOIZSDC-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromo-2-methylpropoxy)phenyl]propan-2-yl]-2-(2,3-dibromo-2-methylpropoxy)benzene Chemical compound C1=C(Br)C(OCC(Br)(CBr)C)=C(Br)C=C1C(C)(C)C1=CC(Br)=C(OCC(C)(Br)CBr)C(Br)=C1 IYOVSGHZOIZSDC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 11
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 10
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 239000003063 flame retardant Substances 0.000 description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 11
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- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
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- 239000012964 benzotriazole Substances 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser 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
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- XESULCZVWZVTFC-UHFFFAOYSA-N n-[(4-ethenylphenyl)methyl]-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=C(C=C)C=C1 XESULCZVWZVTFC-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- 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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
- 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
Landscapes
- 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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a method for producing expandable styrene resin particles, which can inhibit the amount of unreacted and directly remained styrene monomer. The method for producing expandable styrene resin particles comprises: a step of obtaining styrene-based resin particles by suspension polymerization of a styrene-based monomer in the presence of 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane and a sulfonate containing an ester group; and a step of incorporating a blowing agent into the styrene resin particles during or after the suspension polymerization.
Description
Technical Field
The present invention relates to a method for producing expandable styrene resin particles.
Background
Expanded moldings of styrene resins obtained from expandable styrene resin particles are lightweight and have high heat insulation properties, and therefore are used in various fields such as building materials and household electric appliances.
On the other hand, organic compounds such as formaldehyde, toluene, xylene, and styrene which are volatilized from building materials and the like are pointed out to have adverse effects on human bodies, and therefore, it is required to suppress the amounts of these organic compounds contained in the styrene-based resin.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2007-9018
Disclosure of Invention
[ problems to be solved by the invention ]
For example, japanese patent laid-open No. 2007-9018 (patent document 1) describes a method of suppressing the amount of a styrene monomer that remains unreacted in expandable styrene resin particles, but it is desired to develop a technique that exceeds this method.
The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing expandable styrene resin particles, which can suppress the amount of unreacted styrene monomer that remains.
[ means for solving problems ]
In order to solve the above problems, a method for producing expandable styrene resin particles according to one aspect of the present invention includes: a step of obtaining styrene-based resin particles by suspension polymerization of a styrene-based monomer in the presence of 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane and a sulfonate containing an ester group; and a step of incorporating a blowing agent into the styrene resin particles during or after the suspension polymerization.
[ Effect of the invention ]
According to the present invention, the amount of the styrene monomer remaining in the expandable styrene resin particles without being reacted can be suppressed.
Detailed Description
First, the contents of the embodiments of the present invention are listed for explanation.
(1) A method for producing expandable styrene resin particles according to an embodiment of the present invention includes: a step of obtaining styrene-based resin particles by suspension polymerization of a styrene-based monomer in the presence of 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane and a sulfonate containing an ester group; and a step of incorporating a blowing agent into the styrene resin particles during or after the suspension polymerization.
By this method, the amount of the styrene monomer remaining in the obtained expandable styrene resin particles without being reacted can be suppressed.
(2) Preferably: in the step of obtaining styrene resin particles, 1 to 7 parts by mass of the ester group-containing sulfonate is used per 100 parts by mass of the 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane.
By this method, the amount of the styrene monomer remaining in the expandable styrene resin particles without being reacted can be further suppressed.
(3) Preferably: the sulfonate containing ester group is a polyester of polycarboxylic acid having a sulfonate structure.
By this method, the amount of the styrene monomer remaining in the expandable styrene resin particles without being reacted can be further suppressed.
Hereinafter, embodiments of the present invention will be described in more detail.
In the production method of the present embodiment, expandable styrene resin particles containing 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane and a sulfonate containing an ester group are obtained by suspension polymerization of a styrene monomer in the presence of 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane and a sulfonate containing an ester group.
The styrene monomer of the present embodiment is not particularly limited, and includes: aromatic vinyl monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α -methylstyrene, α -methyl-p-methylstyrene, 1-diphenylethylene, p- (N, N-diethylaminoethyl) styrene, p- (N, N-diethylaminomethyl) styrene, vinylpyridine and vinylnaphthalene. These may be used singly or in combination of 2 or more. Styrene is particularly preferable as the styrene monomer in the present embodiment.
In the present embodiment, another vinyl monomer copolymerizable with the styrene monomer may be used in combination. Examples of such vinyl monomers include acrylic acid esters and methacrylic acid esters of alcohols, acrylonitrile, maleic acid esters, vinyl acetate, and olefins.
Further, for the purpose of forming a crosslinked structure, a 2-functional type monomer may also be used in combination. Examples thereof include divinylbenzene and alkanediol di (meth) acrylates.
Since 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane is less likely to interfere with the polymerization reaction of styrene monomers by a chain transfer reaction (chain transfer reaction), the use of this compound as a flame retardant can improve the flame retardancy of a styrene resin foam molded article (hereinafter, also simply referred to as "foam molded article") while suppressing the increase of unreacted styrene monomers.
In the production method of the present embodiment, the amount of 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane used is preferably 0.2 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the styrene-based monomer, from the viewpoint of improving the flame retardancy of the foam molded product and suppressing an increase in unreacted styrene-based monomer.
In the production method of the present embodiment, for example, a sulfonate containing an ester group is used as the dispersant. Sulfonate salts containing ester groups are believed to provide better dispersion of styrenic monomers and 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane as a flame retardant in the suspension.
By better dispersing the styrenic monomers in the suspension, the styrenic monomers can be effectively polymerized with each other, and thus the amount of unreacted styrenic monomers can be reduced.
Further, by dispersing 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane as a flame retardant in a suspension, the flame retardant can contribute to flame retardancy with good efficiency.
In the production method of the present embodiment, the amount of the ester group-containing sulfonate to be used is preferably 0.5 to 50 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 1 to 7 parts by mass, and even more preferably 1 to 4 parts by mass, based on 100 parts by mass of the flame retardant, from the viewpoint of suppressing the amount of unreacted styrene-based monomer.
In the production method of the present embodiment, the amount of the ester group-containing sulfonate to be used is preferably 0.001 to 0.05 parts by mass, more preferably 0.003 to 0.04 parts by mass, even more preferably 0.004 to 0.03 parts by mass, and still more preferably 0.005 to 0.02 parts by mass, based on 100 parts by mass of the styrene-based monomer to be used, from the viewpoint of suppressing the amount of unreacted styrene-based monomer.
The ester group-containing sulfonate used in the present embodiment is not particularly limited, and 1 kind may be used singly, or 2 or more kinds may be used in combination. The ester group-containing sulfonate is preferably a polyester of a polycarboxylic acid having a sulfonate structure such as sodium dioctyl sulfosuccinate, sodium didecyl sulfosuccinate, or sodium dihexyl sulfosuccinate, and more preferably a diester of a dicarboxylic acid having a sulfonate structure such as sodium dioctyl sulfosuccinate or sodium didecyl sulfosuccinate, from the viewpoint of suppressing the amount of unreacted styrene-based monomer.
In the production method of the present embodiment, a suspending agent may be used. The suspending agent is not particularly limited, and includes: hydrophilic polymers such as polyvinyl alcohol, methyl cellulose and polyvinyl pyrrolidone, and sparingly water-soluble inorganic salts such as tricalcium phosphate, magnesium pyrophosphate, hydroxyapatite, alumina, talc, kaolin and bentonite. The amount of the suspending agent used is not particularly limited, but is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the styrene-based monomer.
In the production method of the present embodiment, for example, various other additives may be used in suspension polymerization. The additives are not particularly limited, and include: polyethylene wax, talc, silica, ethylene bis stearamide, methyl methacrylate copolymer, a bubble nucleating agent such as silicone, liquid paraffin, glycerol diacetyl monolaurate (glycerol diacetyl monolaurate), glycerol tristearate, plasticizers such as di-2-ethylhexyl phthalate and di-2-ethylhexyl adipate, chain transfer agents such as dodecylmercaptan and alpha-methylstyrene dimer, antistatic agents such as alkyldiethanolamine, glycerol fatty acid ester and sodium alkylsulfonate, antioxidants such as phenol, phosphorus and sulfur, ultraviolet absorbers such as benzotriazole and benzophenone, light stabilizers such as hindered amine, conductive carbon black, graphite powder, copper-zinc alloy powder, copper powder, silver powder, gold powder, conductive fillers such as IPBC, TBZ, BCM and TPN, organic antibacterial agents such as silver, copper, zinc, etc., conductive fillers such as IPBC, TBZ, BCM and TPN, and antibacterial agents such as silver, copper, zinc, etc, Inorganic antibacterial agents such as titanium oxide.
Further, rubber components such as butadiene rubber, styrene-butadiene rubber, isoprene rubber, ethylene-propylene rubber and the like may be added.
In the present embodiment, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane and another flame retardant may be used in combination as the flame retardant. The other flame retardant is not particularly limited, and includes: halogen flame retardants such as hexabromobenzene, tetrabromocyclooctane, hexabromocyclododecane, tetrabromobutane, hexabromocyclohexane, tribromophenol, tetrabromobisphenol A, ethylenebisbromide 2, 2-bis (4- (3, 5-dibromo-4-hydroxyphenyl) propane condensate, 2-bis (4- (2, 3-dibromopropoxy) -3, 5-dibromophenyl) propane, decabromodiphenyl ether, octabromodiphenyl ether, perchlorocyclopentadecane, chlorinated polyethylene, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (isopropylphenyl) phosphate, non-halogen phosphorus flame retardants such as tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, tetrabromobisphenol A, and ethylene bisbromide, Halogen-containing phosphorus flame retardants such as tris (2, 3-dibromopropyl) phosphate and tris (tribromoneopentyl) phosphate, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, calcium aluminate, antimony trioxide, expandable graphite, and red phosphorus.
Further, a flame retardant auxiliary such as 2, 3-dimethyl-2, 3-diphenylbutane may be used as necessary within the range in which the intended effect of the present embodiment is achieved.
In the production method of the present embodiment, a polymerization initiator may be used. The polymerization initiator is not particularly limited, and includes: benzoyl peroxide, tert-butyl peroxy-2-ethylhexyl monocarbonate, and the like.
In the production method of the present embodiment, expandable styrene resin particles can be obtained by adding a foaming agent to styrene resin particles during or after suspension polymerization of a styrene monomer to thereby incorporate the foaming agent into the styrene resin particles.
The blowing agent of the present embodiment is not particularly limited, and includes: aliphatic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, n-hexane, and cyclohexane, ethers such as dimethyl ether, diethyl ether, and furan, alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol, and halogenated hydrocarbons such as HCFC-141b, HCFC-142b, HCFC-124, HFC-152a, and HFC-134 a. These blowing agents may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The content of the foaming agent in the expandable styrene resin particles is not particularly limited, but is preferably 1 to 20 wt%, more preferably 2 to 10 wt%.
The timing of adding the blowing agent may be any of before, during and after the polymerization reaction, and from the viewpoint of suppressing the amount of unreacted styrene-based monomer, the blowing agent is preferably added at a stage at which the polymerization conversion of the styrene-based monomer is 70% or more, more preferably at a stage at which the polymerization conversion is 80% or more, and still more preferably at a stage at which the polymerization conversion is 90% or more.
The molecular weight of the polystyrene resin constituting the styrene resin particles of the present embodiment is preferably in the range of 150,000 to 350,000, and more preferably 180,000 to 300,000 in terms of weight average molecular weight (Mw). When Mw is less than 150,000, the strength of the obtained expanded bead molded article may be reduced. When Mw exceeds 350,000, the expanded particles are less likely to fuse together during molding, and the strength of the molded article may be reduced.
The expandable styrene resin particles of the present embodiment preferably have a size of 0.3mm to 3mm, more preferably 0.5mm to 2.0 mm.
The foamed molded article of the present embodiment is obtained, for example, by foaming expandable styrene resin particles to produce foamed particles, filling the foamed particles into a mold, and heating and foaming the foamed particles to weld the foamed particles to each other.
The method of foaming the expandable styrene resin particles is not particularly limited, and examples thereof include a method of foaming by heating with Steam (Steam) or the like using a foaming machine equipped with a stirring device. The method for producing the foamed molded article is not particularly limited, and examples thereof include an in-mold molding method in which a metal mold is filled with foamed particles and heated with steam or the like.
[ examples ]
The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "part" or "%" is used as a mass basis unless otherwise specified.
Table 1 shows the types of styrene-based monomers, flame retardants and dispersants used in examples 1 to 6 and comparative example 1, their use ratios, and quantitative results of unreacted styrene monomers contained in the obtained expandable styrene-based resin particles.
Referring to table 1, the method for producing styrene resin particles of examples 1 to 6 and comparative example 1 will be described.
(example 1)
16kg of deionized water, 20g of tricalcium phosphate (manufactured by Taiping chemical industries, Ltd.) as a suspending agent, and 2.1g of dioctyl sodium sulfosuccinate (manufactured by first Industrial pharmaceutical industries, Ltd.) as a dispersant, which is a sulfonate containing an ester group, were put into an autoclave having an internal volume of 50L and equipped with a stirrer.
43g of a benzoyl peroxide water-diluted powder (manufactured by Nippon fat and oil Co., Ltd.) and 27g of t-butyl peroxy-2-ethylhexyl monocarbonate (manufactured by Nippon fat and oil Co., Ltd.), 102g of 2, 2-bis [4- (2, 3-dibromo-2-methylpropoxy) -3, 5-dibromophenyl ] propane (described as "TBBPA/BMP" in the table) as a flame retardant, 130g of liquid paraffin (manufactured by Sonmuran Petroleum institute Co., Ltd.) as a plasticizer, and 3.4g of polyethylene wax (manufactured by Toyo-Petrolite Co., Ltd.) as a nucleating agent were dissolved in 17kg of a styrene monomer, and the resulting solution was put into an autoclave while stirring. After the autoclave was purged with nitrogen, the temperature was raised to 90 ℃.
After the temperature in the autoclave reached 90 ℃, the temperature was raised to 100 ℃, then further raised to 115 ℃, kept at 115 ℃ for a while, and then cooled to 30 ℃.
340g of pentane (a mixture of 80% n-pentane and 20% i-pentane) and 1200g of butane (a mixture of 70% n-butane and 30% i-butane) as blowing agents were introduced into the autoclave at the same time as the temperature was increased from 90 ℃ to 100 ℃. Shortly after the end of the addition of the blowing agent, the stirring speed was reduced to 180 rpm. After cooling, the contents were taken out, dehydrated by a centrifuge, and water adhered to the surface was removed by a fluidized drying apparatus to obtain expandable styrene resin particles having an average particle diameter of about 1 mm.
The obtained expandable styrene resin particles were screened, 0.7mm to 1.4mm particles were taken out, 0.005 part by weight of N, N-bis (2-hydroxyethyl) alkylamine as an antistatic agent was added to 100 parts by weight of the expandable styrene resin particles, and the particles were further coated with a mixture of 0.1 part by weight of zinc stearate, 0.05 part by weight of glycerol tristearate and 0.05 part by weight of glycerol monostearate. Thereby, expandable styrene resin particles to be used for quantitative determination of unreacted styrene monomer are obtained.
(example 2)
Expandable styrene resin particles were obtained in the same manner as in example 1, except that 1.5g of sodium dioctyl sulfosuccinate was used as a dispersant.
(example 3)
Expandable styrene resin particles were obtained in the same manner as in example 1, except that 2.6g of sodium dioctyl sulfosuccinate was used as a dispersant.
(example 4)
Expandable styrene resin particles were obtained in the same manner as in example 1, except for using 153g of 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane as a flame retardant.
(example 5)
Expandable styrene resin beads were obtained in the same manner as in example 1, except that 2.1g of sodium didecyl sulfosuccinate was used as a dispersant.
(example 6)
Expandable styrene resin particles were obtained in the same manner as in example 1, except that 2.1g of sodium dihexyl sulfosuccinate was used as a dispersant.
Comparative example 1
Expandable styrene resin particles were obtained in the same manner as in example 1, except that 2.1g of sodium alpha olefin sulfonate (manufactured by first industrial pharmaceutical products, inc. "naoko (neo) a 0-90") was used as a dispersant.
The following describes the quantitative determination of the unreacted styrene-based monomer contained in the styrene-based resin particles of examples 1 to 6 and comparative example 1.
The unreacted styrene-based monomer is obtained by dissolving the obtained expandable styrene-based resin particles in Dimethylformamide (DMF) and then quantitatively determining the amount by gas chromatography.
The quantitative determination by gas chromatography is specifically performed by the following procedure.
1. Cyclopentanol was precisely weighed in a 100mL volumetric flask (volumetric flash) at about 5g to the 3 rd position below the decimal point (the weight at this time was Wi), and DMF was added to make the whole volume 100 mL. The DMF solution was further diluted 100 times with DMF to prepare an internal standard solution.
2. From about 1g to the 3 rd position below decimal point of the measurement sample, the weight of the measurement sample is ws (g).
3. Accurately weighed samples were dissolved in about 18mL of DMF and the internal standard solution made in 1 was added exactly 2mL through a single-mark pipette (one-mark pipette).
4. This solution was collected by 1. mu.L using a micro syringe (micro system) and introduced into a gas chromatograph to obtain a chromatogram. The peak areas of the unreacted styrene monomer and the internal standard were determined by chromatography, and the concentrations of the respective components were determined by the following equation (3).
The concentration of each component (wt%) [ (Wi/10000) × 2] × [ An/Ai ] × Fn ÷ WS × 100 … (3)
(wherein Wi: cyclopentanol weight (g) when An internal standard solution was prepared, WS: sample weight (g) dissolved in DMF, An: peak area of styrene monomer in gas chromatograph, Ai: peak area of internal standard substance in gas chromatograph, Fn: correction coefficient of styrene monomer obtained from calibration curve prepared in advance)
Further, the conditions of the gas chromatography are as follows.
The use equipment comprises the following steps: GC-2014 gas chromatograph manufactured by Shimadzu corporation
The pipe column is made of: glass tubular column with length of 5000mm
Column packing agent: FFAP (liquid phase name), impregnation rate of liquid phase of 15%, Uniport HP (carrier name) and 60/80 mesh
Injection port temperature: 250 deg.C
Temperature of the pipe column: 120 deg.C
Temperature of the detection part: 250 deg.C
Carrier gas: n is a radical of2And the flow rate is 40m/min.
A detector: flame Ionization Detector (FID)
From the quantitative results of the unreacted styrene-based monomers shown in table 1, it can be seen that: the expandable styrene resin beads of examples 1 to 6 have a smaller content of unreacted styrene monomer than the expandable styrene resin beads of comparative example 1. That is, the amount of unreacted styrene-based monomers is successfully reduced by using a sulfonate containing an ester group as a dispersant.
[ Table 1]
Claims (3)
1. A method for producing expandable styrene resin particles, comprising:
a step of obtaining styrene-based resin particles by suspension polymerization of a styrene-based monomer in the presence of 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane and a sulfonate containing an ester group; and
and a step of adding a blowing agent to the styrene resin particles during or after the suspension polymerization.
2. The method for producing expandable styrene resin particles according to claim 1, wherein in the step of obtaining styrene resin particles, 1 to 7 parts by mass of the ester group-containing sulfonate is used per 100 parts by mass of the 2, 2-bis [4- (2, 3-dibromo-2-methylpropyloxy) -3, 5-dibromophenyl ] propane.
3. The method for producing expandable styrene resin particles according to claim 1 or 2, wherein the ester group-containing sulfonate is a polyester of a polycarboxylic acid having a sulfonate structure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| PL442025A1 (en) * | 2022-08-17 | 2024-02-19 | Zachodniopomorski Uniwersytet Technologiczny W Szczecinie | Foamed polystyrene with improved properties containing a mineral nanofiller and method for producing foamed polystyrene with improved properties containing a mineral nanofiller |
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| PL442025A1 (en) * | 2022-08-17 | 2024-02-19 | Zachodniopomorski Uniwersytet Technologiczny W Szczecinie | Foamed polystyrene with improved properties containing a mineral nanofiller and method for producing foamed polystyrene with improved properties containing a mineral nanofiller |
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