CN1304531C - 塑料用阻燃剂 - Google Patents
塑料用阻燃剂 Download PDFInfo
- Publication number
- CN1304531C CN1304531C CNB038247267A CN03824726A CN1304531C CN 1304531 C CN1304531 C CN 1304531C CN B038247267 A CNB038247267 A CN B038247267A CN 03824726 A CN03824726 A CN 03824726A CN 1304531 C CN1304531 C CN 1304531C
- Authority
- CN
- China
- Prior art keywords
- terpenoid compound
- plastic material
- bromination
- compound
- fire
- 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.)
- Expired - Fee Related
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 38
- 229920003023 plastic Polymers 0.000 title claims abstract description 38
- 239000003063 flame retardant Substances 0.000 title claims abstract description 31
- 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 title claims abstract description 14
- -1 terpenoid compound Chemical class 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 20
- 230000031709 bromination Effects 0.000 claims description 15
- 238000005893 bromination reaction Methods 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229930004069 diterpene Natural products 0.000 claims description 8
- 229930003658 monoterpene Natural products 0.000 claims description 8
- 150000002773 monoterpene derivatives Chemical class 0.000 claims description 8
- 235000002577 monoterpenes Nutrition 0.000 claims description 8
- 229930004725 sesquiterpene Natural products 0.000 claims description 8
- 150000004354 sesquiterpene derivatives Chemical class 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052794 bromium Inorganic materials 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 235000007586 terpenes Nutrition 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 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 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- WTVHAMTYZJGJLJ-UHFFFAOYSA-N (+)-(4S,8R)-8-epi-beta-bisabolol Natural products CC(C)=CCCC(C)C1(O)CCC(C)=CC1 WTVHAMTYZJGJLJ-UHFFFAOYSA-N 0.000 description 3
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 description 3
- 239000001169 1-methyl-4-propan-2-ylcyclohexa-1,4-diene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- RGZSQWQPBWRIAQ-LSDHHAIUSA-N alpha-Bisabolol Natural products CC(C)=CCC[C@@](C)(O)[C@@H]1CCC(C)=CC1 RGZSQWQPBWRIAQ-LSDHHAIUSA-N 0.000 description 3
- HHGZABIIYIWLGA-UHFFFAOYSA-N bisabolol Natural products CC1CCC(C(C)(O)CCC=C(C)C)CC1 HHGZABIIYIWLGA-UHFFFAOYSA-N 0.000 description 3
- 229940036350 bisabolol Drugs 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930009668 farnesene Natural products 0.000 description 3
- 235000001510 limonene Nutrition 0.000 description 3
- 229940087305 limonene Drugs 0.000 description 3
- 150000007875 phellandrene derivatives Chemical class 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MQFGIUKCEOGIGS-UHFFFAOYSA-N CC(C)C1=CCC(=C)C1C Chemical compound CC(C)C1=CCC(=C)C1C MQFGIUKCEOGIGS-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- 150000004141 diterpene derivatives Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NDVASEGYNIMXJL-UHFFFAOYSA-N sabinene Chemical compound C=C1CCC2(C(C)C)C1C2 NDVASEGYNIMXJL-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NDVASEGYNIMXJL-NXEZZACHSA-N (+)-sabinene Natural products C=C1CC[C@@]2(C(C)C)[C@@H]1C2 NDVASEGYNIMXJL-NXEZZACHSA-N 0.000 description 1
- JWQKMEKSFPNAIB-SNVBAGLBSA-N (5r)-1-methyl-5-prop-1-en-2-ylcyclohexene Chemical compound CC(=C)[C@@H]1CCC=C(C)C1 JWQKMEKSFPNAIB-SNVBAGLBSA-N 0.000 description 1
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- FIAXCDIQXHJNIX-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-ethylbenzene Chemical compound CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br FIAXCDIQXHJNIX-UHFFFAOYSA-N 0.000 description 1
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VMYXUZSZMNBRCN-AWEZNQCLSA-N Curcumene Natural products CC(C)=CCC[C@H](C)C1=CC=C(C)C=C1 VMYXUZSZMNBRCN-AWEZNQCLSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920004449 Halon® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007332 Podocarpus macrophyllus Species 0.000 description 1
- 235000016408 Podocarpus macrophyllus Nutrition 0.000 description 1
- UXZIDIYMFIBDKT-UHFFFAOYSA-N Sylvestrene Natural products CC(=C)C1CCCC(C)=C1 UXZIDIYMFIBDKT-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- KQAZVFVOEIRWHN-UHFFFAOYSA-N alpha-thujene Natural products CC1=CCC2(C(C)C)C1C2 KQAZVFVOEIRWHN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229930006737 car-3-ene Natural products 0.000 description 1
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 description 1
- 229930007796 carene Natural products 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N cis-p-Menthan-1,8-diol Natural products CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007823 ocimene derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229930006948 p-menthane-3,8-diol Natural products 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930006696 sabinene Natural products 0.000 description 1
- USDOQCCMRDNVAH-UHFFFAOYSA-N sigma-cadinene Natural products C1C=C(C)CC2C(C(C)C)CC=C(C)C21 USDOQCCMRDNVAH-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229950010257 terpin Drugs 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 description 1
- VMYXUZSZMNBRCN-UHFFFAOYSA-N α-curcumene Chemical compound CC(C)=CCCC(C)C1=CC=C(C)C=C1 VMYXUZSZMNBRCN-UHFFFAOYSA-N 0.000 description 1
- USDOQCCMRDNVAH-KKUMJFAQSA-N β-cadinene Chemical compound C1C=C(C)C[C@H]2[C@H](C(C)C)CC=C(C)[C@@H]21 USDOQCCMRDNVAH-KKUMJFAQSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/02—Monocyclic halogenated hydrocarbons
- C07C23/10—Monocyclic halogenated hydrocarbons with a six-membered ring
- C07C23/12—Hexachlorocyclohexanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/08—Organic materials containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S57/00—Textiles: spinning, twisting, and twining
- Y10S57/904—Flame retardant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明提供一种塑料用阻燃剂，在类萜化合物中所含的碳-碳双键上加成溴的溴化类萜化合物，作为可燃性塑料材料的阻燃剂比较有用。这些溴化合物没有令人不快的气味，在阻燃效果上例如可以与四溴环辛烷相媲美。
Description
技术领域
本发明涉及在可燃性塑料中配合而用于阻燃化的塑料用阻燃剂。
背景技术
在电气/电子设备、汽车、建筑材料、土木工程等各种领域内使用种类繁多的塑料。在这些塑料当中，从通用性、成本方面来看，苯乙烯类树脂、烯烃类树脂是被最多使用的树脂。对于这些材料，分别确定在使用领域中的阻燃规格，有必要对易燃的塑料进行阻燃化。在苯乙烯类树脂、烯烃类树脂的阻燃化中使用各种各样的阻燃剂，但最容易阻燃化且树脂物性受损少的阻燃剂是含有溴等卤素原子的化合物。这些化合物分为溴原子结合在芳香族的碳原子上的类型、和结合在(环状)烷基的碳原子上的类型。通常，结合在(环状)烷基的碳原子上的溴，其阻燃性能好于结合在芳香族上的溴。代表性化合物有六溴环十二烷(HBCD)或四溴环辛烷(TBCO)，一直以来都被用于建筑材料、土木工程、电气设备。其中，在建筑材料用发泡聚苯乙烯用途中大多使用HBCD，即便在最近的特开平2002-194130或特开平2002-30174中也使用HBCD作为阻燃剂。另一方面，限于TBCO的专利有特开平7-179647等。但是，HBCD的缺点是阻燃性还不充分，且比TBCO差，TBCO的缺点是该化合物具有令人不快的气味。
发明内容
因此，本发明的课题是提供一种因溴原子结合在脂肪族或脂环族烃基的碳原子上而具有高阻燃效果且不产生令人不快的气味的塑料用阻燃剂。
本发明提供一种溴化类萜化合物在塑料用阻燃剂中的应用，其中，所述类萜化合物是单萜、倍半萜或二萜烃，或者它们的醇、醛或酮衍生物，所述塑料是可燃性塑料材料。
另外，本发明还提供一种阻燃性塑料组合物，是在可燃性塑料材料中加入溴化类萜化合物，所述溴化类萜化合物的添加量是相对于100重量份可燃性塑料材料为0.1～20重量份，所述类萜化合物是单萜、倍半萜或二萜烃，或者它们的醇、醛或酮衍生物，所述可燃性塑料材料是苯乙烯类或烯烃类塑料。
另外本发明还提供一种可燃性塑料材料的阻燃化方法，在可燃性塑料材料100重量份中配合0.1～20重量份的溴化类萜化合物，所述类萜化合物是单萜、倍半萜或二萜烃，或者它们的醇、醛或酮衍生物，所述可燃性塑料材料是苯乙烯类或烯烃类塑料。
萜除了指广义上用通式(C5H8)n表示的萜烃之外，还指包含由其衍生的醇、醛、和酮的含氧化合物。在上述的通式中，n＝2的化合物称为单萜、n＝3的化合物称为倍半萜、n＝4的化合物称为二萜。
在本说明书中的使用的“萜化合物”的用语是指广义的“萜”或“类萜”，为了进行溴化而作为阻燃剂，优选例如桂叶烯、罗勒烯、柠檬烯、萜品二烯、水芹烯、桧烯、萜品烯、枞油烯、蒈烯等单萜，甜没药萜、法呢烯、姜黄烯、杜松烯、倍半扁柏烯等倍半萜，以及樟脑烯、罗汉松萜烯、陶塔烯等二萜。也可以是类似松节油的萜的混合物。
萜化合物具有不饱和双键，其每个双键上加成两个溴原子。溴的加成反应能够按照公知方法进行，例如使用类似异丁醇的醇类溶剂，类似二氯甲烷、氯仿、四氯化碳的卤化烃溶剂，向溴溶液中滴下搅拌下理论量的萜化合物，或者向上述溶剂中分开同时滴下萜化合物和理论量的溴使其发生反应。对反应没有限制，但最好能够在室温或者其以下的温度下进行。反应结束后，根据需要中和反应液，过滤反应产物并收集，水洗，干燥，能够得到目的溴化萜化合物。
如此获得的溴化萜化合物具有与TBCO相媲美的高阻燃性能，其中，还不具有类似TBCO那样的令人不快的气味。
对于本发明的阻燃剂，配合足以对可燃性塑料材料进行阻燃化的量，由此而可以广泛用于在要求阻燃化的领域中使用的塑料产品。对于作为对象的塑料，特别适合于只由类似苯乙烯、乙烯、丙烯、丁烯那样的碳和氢构成的烃单体的均聚物和共聚物的阻燃化。其添加量根据阻燃剂的溴含量、要求的阻燃化水平、是否和类似三氧化锑的阻燃助剂的合用等进行变动，但塑料原料100重量份优选0.1～20重量份，更优选0.5～10重量份，最优选1～5重量份。
具体实施方式
[实施例]
下面，举出不限于以下的实施例和比较例，例证本发明。
实施例中的溴含量通过基于JIS K 7229(含氯树脂中的氯的定量方法)的方法进行定量。另外，熔点是使用熔点测定器(FP 90/HT：メトラ一·トレド制)，以升温速度3℃/min实施。
实施例1
在添加了异丁醇35g并具备温度计、滴下漏斗(2处)、搅拌装置的100ml的四口烧瓶中，在20℃以下同时滴下柠檬烯13.1g和溴32.1g。滴下结束后，在20～30℃下进行1小时的反应。反应后，用单乙醇胺中和至pH7～8，过滤固体成分，水洗，干燥，得到下面称为化合物B-1的溴化柠檬烯。B-1的溴含量为70.6％，熔点为112℃。
实施例2
在添加了异丁醇35g并具备温度计、滴下漏斗(2处)、搅拌装置的100ml的四口烧瓶中，在20℃以下同时滴下水芹烯13.6g、溴32.1g。滴下结束后，在20～30℃下进行1小时的反应。反应后，用单乙醇胺中和至pH7～8，过滤固体成分，水洗，干燥，得到下面称为化合物B-2的溴化水芹烯。B-2的溴含量为70.8％，熔点为92℃。
实施例3
在添加了异丁醇35g并具备温度计、滴下漏斗(2处)、搅拌装置的100ml的四口烧瓶中，在20℃以下同时滴下甜没药萜14.3g、溴35.2g。滴下结束后，在20～30℃下进行1小时的反应。反应后，用单乙醇胺中和至pH7～8，蒸馏除去溶剂。然后，用二氯甲烷100ml再次溶解，水洗，蒸馏除去溶剂，得到下面称为化合物B-3的溴化甜没药萜。B-3是黄色粘稠液体，溴含量为52.3％。
实施例4
在添加了异丁醇35g并具备温度计、滴下漏斗(2处)、搅拌装置的100ml的四口烧瓶中，在20℃以下同时滴下法呢烯14.3g、溴46.3g。滴下结束后，在20～30℃下进行1小时的反应。反应后，用单乙醇胺中和至pH7～8，蒸馏除去溶剂。然后，用二氯甲烷100ml再次溶解，水洗，蒸馏除去溶剂，得到下面称为化合物B-4的法呢烯。B-4是黄色粘稠液体，溴含量为64.1％。
使用上述合成溴化萜和公知的阻燃剂对聚苯乙烯进行阻燃化，进行阻燃性评价和气味试验。使用的原料如下所示。
(A)聚苯乙烯
东洋スチロ一ルG220(东洋苯乙烯(株))
(B)阻燃剂
B-1：上述实施例1所述的化合物B-1
B-2：上述实施例2所述的化合物B-2
B-3：上述实施例3所述的化合物B-3
B-4：上述实施例4所述的化合物B-4
B-5：六溴环十二烷
B-6：四溴环辛烷
B-7：四溴双苯酚-A-双(2，3-二溴丙基醚)；ピロガ一ドSR-720(第一工业制药(株))
B-8：双(五溴苯基)乙烷；SAYTEX8010(アルベマ一ル)
B-9：溴化环氧树脂化合物：YDB-409(东都化成(株))
(C)树脂添加剂
C-1：阻燃化树脂稳定剂；スタンBM(N)(三共有机合成(株))
C-2：防氧化剂；アデカスタブPEP-36(旭电化工业(株))
阻燃性评价用试验片制作方法：相对(A)聚苯乙烯100重量份，添加(B)阻燃剂3重量份，C-10.05重量份，C-20.01重量份，利用热辊在200℃下进行5分钟的混炼，利用热压力机在200℃下施压3分钟，然后利用树脂切刀切出规定的试验片。
燃烧试验：以JIS K 7201为基准，求出氧指数(LOI)。
气味试验：气味试验是准备在50ml的样品瓶中分别放入上述阻燃剂(B-1～B-9)各10g的器具，用监视器对20人进行气味试验。根据20人当中感觉令人不快气味的人数进行评价。
16人以上：×
6～15人：△
0～5人：○
结果如下表所示。
| 实施例5 | 实施例6 | 实施例7 | 实施例8 | 比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 | |
| 阻燃剂 | B-1 | B-2 | B-3 | B-4 | B-5 | B-6 | B-7 | B-8 | B-9 |
| 燃烧试验(LOI)(％) | 26.9 | 26.6 | 25.3 | 25.8 | 23.0 | 25.8 | 22.3 | 19.6 | 18.4 |
| 气味试验 | ○ | ○ | ○ | ○ | △ | × | ○ | ○ | ○ |
讨论
化合物B-1～B-4的阻燃性出色，且不具有令人不快的气味。在比较例使用的溴化合物当中，化合物B-6虽满足阻燃效果，但具有令人不快的气味。其他化合物B-5、B-7至B-9都不满足阻燃性。
需要说明的是本说明书中的“以上、以下”均包括端点。
Claims (3)
1.一种溴化类萜化合物在塑料用阻燃剂中的应用，其中，所述类萜化合物是单萜、倍半萜或二萜烃，或者它们的醇、醛或酮衍生物，所述塑料是可燃性塑料材料。
2.一种阻燃性塑料组合物，其特征在于，
是在可燃性塑料材料中加入溴化类萜化合物，所述溴化类萜化合物的添加量是相对于100重量份可燃性塑料材料为0.1～20重量份，
所述类萜化合物是单萜、倍半萜或二萜烃，或者它们的醇、醛或酮衍生物，
所述可燃性塑料材料是苯乙烯类或烯烃类塑料。
3.一种可燃性塑料材料的阻燃化方法，其特征在于，
在可燃性塑料材料100重量份中配合0.1～20重量份的溴化类萜化合物，
所述类萜化合物是单萜、倍半萜或二萜烃，或者它们的醇、醛或酮衍生物，
所述可燃性塑料材料是苯乙烯类或烯烃类塑料。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP313690/2002 | 2002-10-29 | ||
| JP2002313690 | 2002-10-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1694942A CN1694942A (zh) | 2005-11-09 |
| CN1304531C true CN1304531C (zh) | 2007-03-14 |
Family
ID=32211590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038247267A Expired - Fee Related CN1304531C (zh) | 2002-10-29 | 2003-09-16 | 塑料用阻燃剂 |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1557456B1 (zh) |
| JP (1) | JP4203859B2 (zh) |
| KR (1) | KR100673345B1 (zh) |
| CN (1) | CN1304531C (zh) |
| AU (1) | AU2003264447A1 (zh) |
| TW (1) | TWI312795B (zh) |
| WO (1) | WO2004039917A1 (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359349A (zh) * | 2018-02-05 | 2018-08-03 | 罗宇强 | 一种水性防腐涂料及其制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1396657A (en) * | 1972-02-23 | 1975-06-04 | Velsicol Chemical Corp | Fire retardant compositions |
| EP0117186A1 (fr) * | 1983-02-18 | 1984-08-29 | Rhone-Poulenc Chimie | Procédé de préparation de dérivés du cyclopropane |
| JPS60181037A (ja) * | 1984-02-27 | 1985-09-14 | Kuraray Co Ltd | 環状不飽和臭素化物の製造方法 |
| JPS61223055A (ja) * | 1985-03-29 | 1986-10-03 | Showa Denko Kk | 熱可塑性樹脂組成物 |
| JPH09183878A (ja) * | 1995-12-28 | 1997-07-15 | Nippon Steel Chem Co Ltd | フェノール樹脂及びこれを配合したスチレン系樹脂組成物 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919356A (en) * | 1968-12-09 | 1975-11-11 | Borg Warner | Halogenated norbornene-methanonaphthalene derivatives and their applications |
| DE2104867C3 (de) * | 1971-02-03 | 1980-08-14 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von schwerentflammbaren expandierbaren Styrolpolymerisaten |
| US3932543A (en) * | 1973-04-13 | 1976-01-13 | Scm Corporation | Process for halogenation of conjugated dienes to dihalogenated butene products |
| GB1600414A (en) * | 1977-05-12 | 1981-10-14 | Shell Int Research | Preparation of dihalocyclopropane derivatives |
| JPS55157519A (en) * | 1979-05-25 | 1980-12-08 | Kuraray Co Ltd | Bromination of terpene compound |
| DE2940073A1 (de) * | 1979-10-03 | 1981-04-30 | Basf Ag, 6700 Ludwigshafen | Flammgeschuetzte styrolpolymerisate |
| DE3122341A1 (de) * | 1981-06-05 | 1982-12-23 | Chemische Werke Hüls AG, 4370 Marl | Feinteilige expandierbare styrolpolymerisate |
| DE10123584C2 (de) * | 2001-05-15 | 2003-09-11 | Hawo Oekologische Rohstoffe Gm | Flammschutzmittel und Verfahren zu dessen Herstellung |
| EP1537191A1 (de) * | 2002-08-02 | 2005-06-08 | Hawo Ökologische Produktions-, Handels- & Logistik GmbH & Co KG | Flammschutzmittel und verfahren zu dessen herstellung |
-
2003
- 2003-09-15 TW TW092125400A patent/TWI312795B/zh not_active IP Right Cessation
- 2003-09-16 JP JP2004548014A patent/JP4203859B2/ja not_active Expired - Fee Related
- 2003-09-16 AU AU2003264447A patent/AU2003264447A1/en not_active Abandoned
- 2003-09-16 WO PCT/JP2003/011786 patent/WO2004039917A1/ja active Application Filing
- 2003-09-16 CN CNB038247267A patent/CN1304531C/zh not_active Expired - Fee Related
- 2003-09-16 EP EP03809845.5A patent/EP1557456B1/en not_active Expired - Lifetime
- 2003-09-16 KR KR1020057007444A patent/KR100673345B1/ko active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1396657A (en) * | 1972-02-23 | 1975-06-04 | Velsicol Chemical Corp | Fire retardant compositions |
| EP0117186A1 (fr) * | 1983-02-18 | 1984-08-29 | Rhone-Poulenc Chimie | Procédé de préparation de dérivés du cyclopropane |
| JPS60181037A (ja) * | 1984-02-27 | 1985-09-14 | Kuraray Co Ltd | 環状不飽和臭素化物の製造方法 |
| JPS61223055A (ja) * | 1985-03-29 | 1986-10-03 | Showa Denko Kk | 熱可塑性樹脂組成物 |
| JPH09183878A (ja) * | 1995-12-28 | 1997-07-15 | Nippon Steel Chem Co Ltd | フェノール樹脂及びこれを配合したスチレン系樹脂組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100673345B1 (ko) | 2007-01-24 |
| KR20050062644A (ko) | 2005-06-23 |
| JPWO2004039917A1 (ja) | 2006-03-02 |
| EP1557456A1 (en) | 2005-07-27 |
| EP1557456B1 (en) | 2016-01-13 |
| CN1694942A (zh) | 2005-11-09 |
| TW200406450A (en) | 2004-05-01 |
| JP4203859B2 (ja) | 2009-01-07 |
| TWI312795B (en) | 2009-08-01 |
| EP1557456A4 (en) | 2010-07-07 |
| WO2004039917A1 (ja) | 2004-05-13 |
| AU2003264447A1 (en) | 2004-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1277788C (zh) | 通过采用离子液体的萃取或洗涤分离物质的方法 | |
| Yu et al. | The effect of decabromodiphenyl oxide and antimony trioxide on the flame retardation of ethylene–propylene–diene copolymer/polypropylene blends | |
| US8648140B2 (en) | Toluene and styrene derived telomer distributions and brominated flame retardants produced therefrom | |
| CN113382864B (zh) | 制备低挥发性增黏剂组合物的方法 | |
| CN106810762A (zh) | 一种无卤阻燃pp复合材料及其制备方法 | |
| JP2012111855A (ja) | 天然繊維複合体組成物、天然繊維複合体組成物から得られる成形体、および天然繊維複合体組成物の製造方法 | |
| CN1304531C (zh) | 塑料用阻燃剂 | |
| CN111087679B (zh) | 一种低voc低气味聚丙烯树脂组合物及其制备方法 | |
| KR910004461B1 (ko) | 고기능성 재생 셀룰로오스 조성물 | |
| JP6609614B2 (ja) | 臭素含有重合体の調製およびその難燃剤としての応用 | |
| CN107540898B (zh) | 一种易加工阻燃型丁苯橡胶及其制备方法 | |
| Sohn et al. | Flame retarding PC/ABS resins having superior thermomechanical properties | |
| CN107540899B (zh) | 易加工阻燃型丁苯橡胶的制备方法 | |
| KR102583281B1 (ko) | 열분해유의 정제방법 및 그 방법에 의해 생성된 정제 열분해유 | |
| CN107540765B (zh) | 一种丁腈橡胶用阻燃型增塑剂的制备方法 | |
| CN107540893B (zh) | 一种易加工的阻燃型丁腈橡胶及其制备方法 | |
| CN111117198B (zh) | 一种pc/abs阻燃复合材料及其制备方法 | |
| RU2301817C1 (ru) | Пластификатор полимерных материалов и полимерный материал | |
| US3915932A (en) | Flame-retardant composition | |
| KR920008528B1 (ko) | 비할로겐화 난연제를 함유한 난연성 폴리스티렌 수지조성물 | |
| CN117343580A (zh) | 一种阻燃型粉末涂料及其制备方法 | |
| JP2015209531A (ja) | 天然化合物の架橋促進剤を含有したゴム組成物および架橋ゴム製品 | |
| CN107540896A (zh) | 易加工阻燃型丁腈橡胶的制备方法 | |
| JPH03115446A (ja) | 制振材組成物 | |
| Antonov et al. | The action of high-molecular bromine-containing fire-retardants in styrene plastics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070314 |