CN115485325A - 包含聚合的溴化阻燃剂的可膨胀苯乙烯聚合物 - Google Patents
包含聚合的溴化阻燃剂的可膨胀苯乙烯聚合物 Download PDFInfo
- Publication number
- CN115485325A CN115485325A CN202180029733.6A CN202180029733A CN115485325A CN 115485325 A CN115485325 A CN 115485325A CN 202180029733 A CN202180029733 A CN 202180029733A CN 115485325 A CN115485325 A CN 115485325A
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- China
- Prior art keywords
- flame retardant
- brominated
- brominated flame
- styrene
- bromination
- 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
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 239000003063 flame retardant Substances 0.000 title description 14
- 230000031709 bromination Effects 0.000 claims abstract description 32
- 238000005893 bromination reaction Methods 0.000 claims abstract description 32
- 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 class 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 claims abstract description 31
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 20
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 238000010097 foam moulding Methods 0.000 claims description 8
- 238000005227 gel permeation chromatography Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical group C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 230000001698 pyrogenic effect Effects 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 6
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 229920001400 block copolymer Polymers 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 125000002897 diene group Chemical group 0.000 description 4
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- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
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- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SGXVTRUKGXCZQB-UHFFFAOYSA-N Br[Br-]Br.CC[N+](CC)(CC)CC Chemical compound Br[Br-]Br.CC[N+](CC)(CC)CC SGXVTRUKGXCZQB-UHFFFAOYSA-N 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
- JQRYUMGHOUYJFW-UHFFFAOYSA-N pyridine;trihydrobromide Chemical compound [Br-].[Br-].[Br-].C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1 JQRYUMGHOUYJFW-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- 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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- 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
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- C08F8/20—Halogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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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)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
包含聚合的溴化阻燃剂的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂包含至少一种具有33％至75％的溴化程度的溴化聚丁二烯嵌段，基于溴化前的聚丁二烯嵌段的双键计；一种通过悬浮聚合制备所述可膨胀苯乙烯聚合物的方法和由其制成的微粒泡沫成型品。
Description
本发明涉及包含聚合的溴化阻燃剂的可膨胀苯乙烯聚合物，通过悬浮聚合制备所述可膨胀苯乙烯聚合物的方法，和由其制成的微粒泡沫模制品。
背景技术
WO 2007/058736公开了热稳定的溴化苯乙烯/丁二烯共聚物以及它们用于发泡和非发泡的聚合物组合物中作为阻燃剂添加物的用途，其包含阻燃量的溴化丁二烯共聚物以替代六溴环十二烷(HBCD)。但是这种阻燃剂在悬浮聚合的可膨胀聚苯乙烯中具有很强的成核作用，其结果是聚苯乙烯泡沫具有很小的孔径和差的隔绝性能。
US 2012/0253914 A1公开了阻燃性可膨胀苯乙烯聚合物和泡沫，其中包含1至10重量％的红外吸收剂和至少一种卤代聚合物作为阻燃剂。
WO 2015/065393公开了在泡沫体(发泡苯乙烯聚合物)通过使用溴化苯乙烯-丁二烯嵌段共聚物作为阻燃剂的熔融挤出方法而制成的情况下，包含少量非溴化乙烯基芳族/丁二烯嵌段共聚物可提高发泡苯乙烯聚合物的孔径均匀性并且降低其密度。
WO 2018/210961和WO 2018/210965提出改善溴化嵌段共聚物和聚苯乙烯基质的混溶性以增大聚苯乙烯泡沫中的孔径。所述混溶性是通过使用不同的溴化嵌段共聚物的混合物或是在溴化之前调整苯乙烯和丁二烯嵌段的分子量而得以改善的。计量加入或者制备溴化嵌段共聚物的方法是费力的。
考虑到上述现有技术，本发明的目的是提供阻燃性可膨胀苯乙烯聚合物，其能够通过悬浮聚合方法来制备，并且能够转化成具有增大孔径的泡沫颗粒和具有低的热导率和良好的隔绝性能的阻燃性颗粒泡沫模制品。
为了解决这些问题，本发明提供了包含聚合的溴化阻燃剂的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂包含至少一种具有33％至75％的溴化程度的溴化聚丁二烯嵌段，基于溴化前的聚丁二烯嵌段的双键计。
溴化程度是指在聚丁二烯嵌段中非芳族双键的百分比，该聚丁二烯嵌段是已溴化的。溴化程度可以通过1H-NMR光谱测定。为此，确定与残余双键的质子有关的信号以及与已溴化的聚丁二烯中质子有关的信号的积分面积的比率。
或者，溴化程度(BrD)可以由总溴含量(Br％)、非芳族双键数量(NDB)或者溴化前聚合物的分子量(MP)以及丁二烯的百分比(BD％)根据以下等式计算得到：
Br％＝(BrD*NDB*160)/((BrD*NDB*160)+MP)
其中
NDB＝(MP*BD％)/54
或
BrD＝3375*Br％/(BD％(100％–Br％))
优选的实施方案被描述于权利要求2至7中。
优选地，聚合的溴化阻燃剂具有的总溴含量在40重量％至60重量％的范围内，更优选为50重量％至55重量％。聚合的溴化阻燃剂的总溴含量可以通过元素分析，即通过燃烧和银量分析来确定。
合适的聚合的溴化阻燃剂是，其中包含至少一种乙烯基芳族嵌段S(特别是聚苯乙烯嵌段)和至少一种溴化二烯聚合物嵌段BB的溴化乙烯基芳族-二烯嵌段共聚物(Br-SBC)。
以下可用作嵌段S的乙烯基芳族单体：苯乙烯、α-甲基苯乙烯、p-甲基苯乙烯、乙基苯乙烯、叔丁基苯乙烯、乙烯基甲苯或者是它们的混合物。优选使用苯乙烯。
用作嵌段BB的优选的二烯如下：丁二烯、异戊二烯、2,3-二甲基丁二烯、1,3-戊二烯或1,3-己二烯或者它们的混合物。特别优选使用1,3-丁二烯。
优选地，乙烯基芳族-二烯嵌段共聚物(SBC)在溴化前包含20至50重量％的聚合的乙烯基芳族单体单元，特别是苯乙烯单体单元，和包含50至80重量％的聚合的二烯单元，特别是丁二烯单元。最优选地，乙烯基芳族-二烯嵌段共聚物(SBC)在溴化前包含25至45重量％的聚合的乙烯基芳族单体单元，特别是苯乙烯单体单元，和包含55至75重量％的聚合的二烯单元，特别是丁二烯单元。
乙烯基芳族-二烯嵌段共聚物(SBC)可以具有线型或者对称或不对称的星型结构。乙烯基芳族-二烯嵌段共聚物(SBC)的掺混物可在溴化前或溴化后使用。
优选地，聚合的溴化阻燃剂选自溴化苯乙烯-丁二烯-苯乙烯三嵌段共聚物。
优选地，聚合的溴化阻燃剂包含50至85重量％的溴化聚丁二烯嵌段。
优选地，聚合的溴化阻燃剂在溴化前测定的重均分子量Mw为80000至180000g/mol。
聚合的溴化阻燃剂最优选地选自溴化苯乙烯-丁二烯-苯乙烯三嵌段共聚物S1-B-S2，所述S1-B-S2具有20至50重量％(特别是25至45重量％)的总苯乙烯嵌段含量，并且嵌段S1与S2的重均分子量Mw的差值小于10000g/mol。
重均分子量Mw在溴化前通过凝胶渗透色谱(GPC)根据ISO 16014-3:2012，在四氢呋喃中在25℃下相对于聚苯乙烯标准品测定。
优选地，所述至少一种溴化聚丁二烯嵌段的乙烯基含量为50至95％，基于在溴化前的聚丁二烯嵌段的双键计。乙烯基含量是指在溴化前的Br-SBC嵌段共聚物的1,2键合的二烯单元的相对比例，基于1,2-、1,4-顺式以及1,4-反式键合的全部的二烯单元计。
乙烯基芳香族-二烯嵌段共聚物(SBC)的溴化可以按照WO 2007/058736所记载的进行实施。优选地，本发明的溴化丁二烯共聚物通过选择性溴化，特别是在温和条件之下的选择性溴化来制备。溴化优选以离子方式进行。
一旦达到了需要的溴化程度，特别是在使用三溴化物(例如四烷基三溴化铵或三溴化吡啶盐)作为溴化剂时，副产物例如四烷基一溴化铵或吡啶氢溴酸盐可以通过洗涤、倾析、过滤从反应溶液中去除。
控制溴化程度的优点在于，可以使用多种聚丁二烯嵌段共聚物作为用于制备具有以下性质的聚合的溴化阻燃剂的前驱体，即，所述聚合的溴化阻燃剂与聚苯乙烯基质具有充分的混溶性并且能够增大聚苯乙烯泡沫中的孔径。
本发明的另一个主题是制备可膨胀苯乙烯聚合物的方法。优选的方法记载于权利要求8至10中。
一种制备可膨胀苯乙烯聚合物的优选的方法包括：在聚合的溴化阻燃剂存在下，使乙烯基芳族单体在含水的悬浮液中发生聚合，其中聚合的溴化阻燃剂包含至少一种具有33％至75％的溴化程度的溴化聚丁二烯嵌段，基于溴化前的聚丁二烯嵌段的双键计。
对于水性悬浮聚合而言，以下可以用作乙烯基芳族单体：苯乙烯、α-甲基苯乙烯、p-甲基苯乙烯、乙基苯乙烯、叔丁基苯乙烯、乙烯基甲苯或它们的混合物。优选使用苯乙烯单体。
水性悬浮聚合可以使用含磷的酸的无机盐作为皮克林稳定剂(Pickeringstabilizer)来进行。优选地，使用磷酸三钙和/或焦磷酸镁。聚合也可以在另外的有机悬浮剂存在下进行，例如羟基乙基纤维素、聚乙烯吡咯烷酮或聚乙烯醇。
最优选地，在基于乙烯基芳族单体计0.5至10重量％的无热颗粒(athermanicparticle)(例如炭黑、焦炭、煅烧焦炭、石墨化焦炭、天然和/或合成石墨，或它们的混合物)，优选在石墨的存在下进行聚合。在将这些无热颗粒加入到聚合物基质之前，也可以将其加入到无机聚合物(例如矿物聚合物)中。
聚合的溴化阻燃剂的量的优选为0.25至5重量％，基于乙烯基芳族单体计。聚合的溴化阻燃剂的量最优选为0.5至2重量％。
优选地，加入用于聚合物溴化的增效剂。该增效剂是一种在120至270℃温度下半衰期为一小时的成分(在单氯苯中测定)。优选地，增效剂选自过氧化二异丙苯、二(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二(过氧化叔丁基)己烷、2,3-二甲基-2,3-二苯基丁烷和它们的混合物。
在水性悬浮聚合期间，发泡剂优选在乙烯基芳族单体转化率为至少20％之后加入。发泡剂选自含有3至6个碳原子的脂肪族烃或环脂族烃，例如正戊烷、异戊烷、环戊烷和它们的混合物。
本发明的另一个主题是苯乙烯聚合物泡沫模型品，其通过将上述可膨胀苯乙烯聚合物进行预发泡和粘结而可获得。优选地，苯乙烯聚合物泡沫模制品的平均孔径为120至250微米。
平均孔径可通过显微镜测定来确定。平均数通过以下方法得到：在透射光显微镜放大60倍的条件下，对在泡沫模制品的切片的一条线上的至少25个孔计数，然后将线的长度除以孔的数量。
实施例
在下文中，对本发明的说明更加详细，并且参照实施例进行具体地说明，但是这些并不意欲于限制本发明。
溴化苯乙烯-丁二烯-苯乙烯三嵌段共聚物Br-SBS
根据WO 2007/058736，将包含33重量％的聚合的苯乙烯单元以及67重量％的聚合的丁二烯单元(其中有78重量％的1,2-单元和22重量％的1,4-单元)且总的重均分子量Mw为130000g/mol(根据ISO 16014-3:2012，在溴化前于25℃在四氢呋喃中，相对于聚苯乙烯标准品，通过GPC测定)的苯乙烯-丁二烯-苯乙烯三嵌段共聚物SBS用不同摩尔比例的四乙基三溴化铵进行溴化，获得溴化SBS嵌段共聚物，其特征示于表1中。
Br-SBS三嵌段共聚物中的总溴含量通过燃烧和银量分析测定得出。
非芳香族双键的溴化程度是通过1H-NMR光谱并且比较残余双键质子和已溴化聚丁二烯的质子的信号的积分面积而测定。
重均分子摩尔质量Mw通过凝胶渗透色谱方法(GPC)，根据ISO16014-3:2012测定，使用来自Polymer Labs公司的混合B(Mixed B)型聚苯乙烯凝胶柱，在20℃室温下使用单分散聚苯乙烯标准品以及四氢呋喃作为洗脱剂。
表1：Br-SBS三嵌段共聚物：
实施例1和2与对比例C1-C3
可膨胀聚苯乙烯的制备(白色EPS)
将15g过氧化苯甲酰(来自Nouryon的Perkadox L-W75)、115g过氧化二异丙苯(来自Nouryon的
BC-FF)以及如表2所示的量的Br-SBS三嵌段共聚物溶于22.8kg的苯乙烯中。将该有机相倒入55升搅拌容器中的17.5kg的去矿物质水中。在此液相中还包含36g焦磷酸镁(由焦磷酸钠和硫酸镁制备而成)。将此混合物在搅拌下、于110分钟内加热至104℃，然后在255分钟之内加热至134℃。在达到80℃105分钟后，计量加入73g的2重量％的乳化剂E30溶液(来自Lanxess公司的
H40)。再在46分钟后，计量加入1.21kg的戊烷(来自ExxonMobil公司的
pentanes 80)。然后在最终温度134℃下继续搅拌一小时完成聚合。倾析出所获得的可膨胀聚苯乙烯并且干燥。
然后将珠粒涂覆上0.3％(w/w)的由60％(w/w)三硬脂酸甘油酯(来自IOI Oleo公司的
3168)、30％(w/w)单硬脂酸甘油酯(来自IOI Oleo公司的
3995)和10％(w/w)硬脂酸锌(来自Baerlocher的
5)组成的混合物。
实施例3和4与对比例C4-C6
含石墨的可膨胀聚苯乙烯的制备(灰色EPS)
将22.4g过氧化二(十六烷基)二碳酸酯(来自Nouryon的
24-FL)、11.3g乙基己酸叔丁酯(来自Nouryon的
21S)、100g过氧化二异丙苯(来自Nouryon的
BCFF)、825g石墨(来自Graphit Kropfmühl的UF 99.5)以及表2所示的量的Br-SBS三嵌段共聚物溶于16.5kg苯乙烯中。将该有机相倒入55升搅拌容器中的20.8kg的去矿物质水中。在此液相中还包含50g焦磷酸镁(由焦磷酸钠和硫酸镁制备而成)。将此混合物在搅拌下、于90分钟内加热至94℃，然后在254分钟之内加热至135℃。在达到80℃95分钟后，计量加入73g的2重量％的乳化剂E30溶液(来自Lanxess公司的
H40)。再在110分钟后，计量加入1.25kg的戊烷(来自ExxonMobil公司的
pentanes80)。然后，在最终温度135℃下继续搅拌一小时完成聚合。倾析出所获得的可膨胀聚苯乙烯且干燥。
然后将珠粒涂覆上0.3％(w/w)的由60％(w/w)三硬脂酸甘油酯(来自IOI Oleo公司的
3168)、30％(w/w)单硬脂酸甘油酯(来自IOI Oleo公司的
3995)和10％(w/w)硬脂酸锌(来自Baerlocher的
5)组成的混合物。
表2：实施例1至4以及对比例C1至C6中Br-SBS三嵌段聚合物的用量
| 实施例 | BR-SBS | 量[g] |
| 1 | FR 59 | 235g |
| 2 | FR 62 | 235g |
| C1 | FR 78 | 213g |
| C2 | FR 96 | 199g |
| C3 | FR 100 | 195g |
| 3 | FR 59 | 277g |
| 4 | FR 62 | 277g |
| C4 | FR 78 | 251g |
| C5 | FR 96 | 235g |
| C6 | FR 100 | 230g |
颗粒泡沫模制品的制备
在流动蒸汽中，将包含发泡剂的由实施例1至4以及对比例C1至C6制备的珠粒进行预发泡。贮存12小时之后，使预发泡的颗粒在有蒸汽的封闭模具中粘结，得到的颗粒泡沫模制品具有约15kg/m3密度的白色EPS和约20kg/m3密度的灰色EPS。结果归纳于表3。
根据EN 13238对于20mm厚度的样品进行的燃烧行为的测定是在根据EN 11925-2进行15秒的边缘燃烧的调节条件下进行。
样品热导率的测定是根据EN 12667利用防护热板装置和50mm厚度的样品在10℃的平均测试温度下进行。
平均孔径通过显微镜测定法确定。
与实施例1和2比较，对比例C1至C3(其包含具有至少78％的溴化程度的Br-SBC嵌段共聚物作为阻燃剂)示出更低的孔径和更高的热导率。在比较对比例C4至C6与实施例3和4时，对于由包含石墨的EPS制成的泡沫制品也显示出相同的效果。
表3：颗粒泡沫模制品的分析结果
Claims (12)
1.包含聚合的溴化阻燃剂的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂包含至少一种具有33％至75％的溴化程度的溴化聚丁二烯嵌段，基于溴化前的聚丁二烯嵌段的双键计。
2.根据权利要求1所述的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂所具有的总溴含量在40至60重量％的范围内。
3.根据权利要求1或2所述的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂选自溴化苯乙烯-丁二烯-苯乙烯三嵌段共聚物。
4.根据权利要求1至3中任一项所述的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂包含50至85重量％的溴化聚丁二烯嵌段。
5.根据权利要求1至4中任一项所述的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂的重均分子量Mw为80000至180000g/mol，通过凝胶渗透色谱法根据ISO 16014-3:2012在溴化前测定。
6.根据权利要求1至5中任一项所述的可膨胀苯乙烯聚合物，其中聚合的溴化阻燃剂选自溴化苯乙烯-丁二烯-苯乙烯三嵌段共聚物S1-B-S2，所述S1-B-S2具有20至50重量％的总苯乙烯嵌段含量，并且嵌段S1和S2的重均分子量Mw的差值小于10000g/mol，在溴化前通过凝胶渗透色谱法根据ISO 16014-3:2012测定。
7.根据权利要求1至6中任一项所述的可膨胀苯乙烯聚合物，其中至少一种溴化聚丁二烯嵌段具有50至95％的1,2-乙烯基含量，基于聚丁二烯嵌段在溴化之前的双键计。
8.一种制备权利要求1至7所述的可膨胀苯乙烯聚合物的方法，其通过在聚合的溴化阻燃剂存在下，使乙烯基芳族单体在含水的悬浮液中发生聚合而进行，其中聚合的溴化阻燃剂包含至少一种具有33％至75％的溴化程度的溴化聚丁二烯嵌段，基于溴化前的聚丁二烯嵌段的双键计。
9.根据权利要求8所述的方法，其中在0.5至10重量％的无热颗粒的存在下进行聚合，基于乙烯基芳族单体计。
10.根据权利要求8或9所述的方法，其中聚合的溴化阻燃剂的量为0.25至5重量％，基于乙烯基芳族单体计。
11.苯乙烯聚合物泡沫模制品，其可通过权利要求1至7中任一项所述的可膨胀苯乙烯聚合物的预发泡和粘结而获得。
12.根据权利要求11所述的苯乙烯聚合物泡沫模制品，其中平均孔径为120至250μm，通过显微镜测量而确定。
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| EP20170494.7 | 2020-04-21 | ||
| EP20170494 | 2020-04-21 | ||
| PCT/EP2021/060016 WO2021213950A1 (en) | 2020-04-21 | 2021-04-19 | Expandable styrene polymers comprising polymeric brominated flame-retardant |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080287559A1 (en) * | 2005-11-12 | 2008-11-20 | King Bruce A | Brominated Butadiene/Vinyl Aromatic Copolymers, Blends of Such Copolymers with a Vinyl Aromatic Polymer and Polymeric Foams Formed From Such Blends |
| CN102656220A (zh) * | 2009-12-18 | 2012-09-05 | 巴斯夫欧洲公司 | 阻燃聚合物泡沫 |
| US20160229970A1 (en) * | 2013-10-30 | 2016-08-11 | Dow Global Technologies Llc | Foamed styrenic polymers containing a brominated styrene-butadiene copolymer and having enhanced cell size homogeneity |
| WO2018210961A1 (de) * | 2017-05-17 | 2018-11-22 | Basf Se | Bromierte flammschutzmittel |
| WO2018210965A1 (de) * | 2017-05-17 | 2018-11-22 | Basf Se | Bromierte flammschutzmittel |
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| US20120253914A1 (en) | 2011-03-29 | 2012-10-04 | Visa International Service Association | Universal loyalty program device |
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- 2021-04-19 US US17/918,584 patent/US20230146413A1/en active Pending
- 2021-04-19 EP EP21718149.4A patent/EP4139381A1/en active Pending
- 2021-04-19 KR KR1020227040597A patent/KR20230008128A/ko active Search and Examination
- 2021-04-19 MX MX2022013269A patent/MX2022013269A/es unknown
- 2021-04-19 CN CN202180029733.6A patent/CN115485325A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080287559A1 (en) * | 2005-11-12 | 2008-11-20 | King Bruce A | Brominated Butadiene/Vinyl Aromatic Copolymers, Blends of Such Copolymers with a Vinyl Aromatic Polymer and Polymeric Foams Formed From Such Blends |
| CN102656220A (zh) * | 2009-12-18 | 2012-09-05 | 巴斯夫欧洲公司 | 阻燃聚合物泡沫 |
| US20160229970A1 (en) * | 2013-10-30 | 2016-08-11 | Dow Global Technologies Llc | Foamed styrenic polymers containing a brominated styrene-butadiene copolymer and having enhanced cell size homogeneity |
| WO2018210961A1 (de) * | 2017-05-17 | 2018-11-22 | Basf Se | Bromierte flammschutzmittel |
| WO2018210965A1 (de) * | 2017-05-17 | 2018-11-22 | Basf Se | Bromierte flammschutzmittel |
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| US20230146413A1 (en) | 2023-05-11 |
| KR20230008128A (ko) | 2023-01-13 |
| MX2022013269A (es) | 2022-11-14 |
| EP4139381A1 (en) | 2023-03-01 |
| WO2021213950A1 (en) | 2021-10-28 |
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