KR101465476B1 - Phosphorus Compound with Novel Structure, Method for Preparing the Same and Flameproof Thermoplastic Resin Composition Comprising the Same - Google Patents
Phosphorus Compound with Novel Structure, Method for Preparing the Same and Flameproof Thermoplastic Resin Composition Comprising the Same Download PDFInfo
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- KR101465476B1 KR101465476B1 KR1020110129445A KR20110129445A KR101465476B1 KR 101465476 B1 KR101465476 B1 KR 101465476B1 KR 1020110129445 A KR1020110129445 A KR 1020110129445A KR 20110129445 A KR20110129445 A KR 20110129445A KR 101465476 B1 KR101465476 B1 KR 101465476B1
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- resin
- thermoplastic resin
- phosphorus compound
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- -1 Phosphorus Compound Chemical class 0.000 title claims abstract description 59
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 46
- 239000011574 phosphorus Substances 0.000 title claims abstract description 46
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 35
- 239000011342 resin composition Substances 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims description 32
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 30
- 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 claims description 26
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 229920006026 co-polymeric resin Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 6
- 238000002411 thermogravimetry Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- 229920005990 polystyrene resin Polymers 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- CTYOELISUWITTG-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.CCOC(=O)C=C.C=CC1=CC=CC=C1 CTYOELISUWITTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920013716 polyethylene resin Polymers 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000011968 lewis acid catalyst Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100323621 Drosophila melanogaster Drip gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- 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
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- 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
- C09K21/12—Organic materials containing phosphorus
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명에 따른 인계 화합물은 하기 화학식 1로 표시된다.
[화학식 1]
상기 식에서, R은 수소 또는 C1-C4의 알킬기임.The phosphorus compound according to the present invention is represented by the following general formula (1).
[Chemical Formula 1]
Wherein, R is an alkyl group of hydrogen or C 1 -C 4.
Description
본 발명은 새로운 구조를 갖는 인계 화합물, 이의 제조방법, 및 이를 포함하는 난연성 열가소성 수지 조성물에 관한 것이다. 보다 구체적으로 본 발명은 터셔리부틸기(tertiary butyl group)가 오쏘(ortho) 위치에 치환된 페닐기, 및 비페놀(biphenol) 링커(linker)를 포함하여 고온에서의 내가수분해성 및 내열성이 우수한 인계 화합물, 이의 제조방법, 및 이를 포함하는 난연성 열가소성 수지 조성물에 관한 것이다.
The present invention relates to a phosphorus compound having a novel structure, a process for producing the same, and a flame retardant thermoplastic resin composition containing the same. More specifically, the present invention relates to a process for producing a polyimide resin composition, which comprises a tertiary butyl group in the ortho position and a phenyl group substituted in the ortho position, and a biphenol linker, A method for producing the same, and a flame retardant thermoplastic resin composition containing the same.
환경 문제에 대한 관심이 대두되면서, 각 국가에서는 기존 할로겐계 난연제에 대한 규제가 점차 강화되고 있다. 이에 따라, 비할로겐계 난연제에 대한 연구가 활발하게 진행되고 있으며, 특히 비할로겐계 난연제의 대안으로 인계 난연제에 대한 연구가 더욱 집중적으로 이루어지고 있는 실정이다. As concerns about environmental issues have emerged, regulations on existing halogen-based flame retardants are increasingly being tightened in each country. As a result, studies on non-halogen flame retardants have been actively conducted, and in particular, studies on phosphorus flame retardants have been made more intensively as an alternative to non-halogen flame retardants.
이러한 인계 난연제로 가장 많이 사용되고 있는 것은 인산 에스테르로서 이의 예로는 비스페놀-A 비스(디페닐포스페이트)(BDP), 레조시놀 비스(디페닐포스페이트)(RDP), 레조시놀 비스(디-2,6-디메틸페닐포스페이트)(PX-200) 등이 있다. 이러한 인산 에스테르는 스티렌계 수지, 폴리카보네이트계 수지 등의 열가소성 수지에 적용되어 이들 수지에 난연성을 부여하고 있다. Phosphoric esters such as bisphenol-A bis (diphenylphosphate) (BDP), resorcinol bis (diphenylphosphate) (RDP), resorcinol bis (di- Dimethylphenylphosphate) (PX-200). These phosphate esters are applied to thermoplastic resins such as styrene resins and polycarbonate resins to impart flame retardancy to these resins.
그러나 여러 가지 특성(고내열성, 고광택성 등)을 갖춘 수지에 대한 요구가 늘어나면서 수지의 가공 온도가 높아지게 되고, 그에 따라 기존 인산에스테르계 난연제를 적용한 수지에는 고온 가공시 가스가 발생하거나, 분해되거나, 외관이 저하되는 등의 문제점이 발생하게 된다.However, as the demand for resins with various properties (high heat resistance, high gloss, etc.) increases, the processing temperature of the resin becomes higher. As a result, resins using existing phosphoric acid ester flame retardants are likely to generate, , The appearance is deteriorated, and the like.
이에 따라, 본 발명자는 상기 문제점을 해결하기 위해서, 터셔리부틸기(tertiary butyl group)가 오쏘(ortho) 위치에 치환된 페닐기, 및 비페놀(biphenol) 링커(linker)를 포함하여 고온에서의 내가수분해성 및 내열성이 우수한 인계 화합물, 이의 제조방법, 및 이를 포함하는 난연성 열가소성 수지 조성물을 개발하기에 이른 것이다.
In order to solve the above problems, the inventors of the present invention have found that when a tertiary butyl group includes a phenyl group substituted at an ortho position, and a biphenol linker, A method for producing the phosphorus compound, and a flame-retardant thermoplastic resin composition containing the phosphorus compound having excellent water-decomposability and heat resistance.
본 발명의 목적은 새로운 구조를 갖는 인계 화합물 및 이의 제조방법을 제공하는 것이다.It is an object of the present invention to provide a phosphorus compound having a novel structure and a process for producing the same.
본 발명의 다른 목적은 고온에서의 내가수분해성 및 내열성이 우수한 인계 화합물 및 이의 제조방법을 제공하는 것이다. Another object of the present invention is to provide a phosphorus compound excellent in hydrolysis resistance and heat resistance at high temperatures and a method for producing the same.
본 발명의 또 다른 목적은 난연성, 고온에서의 내가수분해성 및 내열성이 우수한 열가소성 수지 조성물을 제공하는 것이다.Still another object of the present invention is to provide a thermoplastic resin composition which is excellent in flame retardancy, hydrolysis resistance at high temperature and heat resistance.
본 발명의 상기 및 기타의 목적들은 모두 하기 설명되는 본 발명에 의해서 달성될 수 있다.
The above and other objects of the present invention can be achieved by the present invention described below.
본 발명에 따른 인계 화합물은 하기 화학식 1로 표시된다.The phosphorus compound according to the present invention is represented by the following general formula (1).
[화학식 1] [Chemical Formula 1]
상기 식에서, R은 수소 또는 C1-C4의 알킬기임.Wherein, R is an alkyl group of hydrogen or C 1 -C 4.
본 발명의 일 구체예에서, 상기 인계 화합물과 물을 3:1의 중량비로 혼합한 혼합물을 93 ℃에서 48시간 동안 교반하였을 때 교반 전후의 산가 변화는 0 내지 0.9 mg KOH/g이고, 상기 인계 화합물과 물을 9:1의 중량비로 혼합한 혼합물을 280 ℃에서 1시간 동안 방치하였을 때 방치 전후의 산가 변화는 0 내지 0.8 mg KOH/g이다.In one embodiment of the present invention, when the mixture obtained by mixing the phosphorus compound and water in a weight ratio of 3: 1 is stirred at 93 ° C for 48 hours, the acid value change before and after stirring is 0 to 0.9 mg KOH / g, When the mixture in which the compound and water were mixed at a weight ratio of 9: 1 was left at 280 DEG C for 1 hour, the acid value change before and after standing was 0 to 0.8 mg KOH / g.
본 발명의 일 구체예에서, 열중량 분석법에 의하여 측정한 상기 인계 화합물의 350 ℃에서의 손실중량은 0 내지 15%이다.In one embodiment of the present invention, the loss weight of the phosphorus compound measured by thermogravimetric analysis at 350 DEG C is 0 to 15%.
본 발명에 따른 상기 화학식 1로 표시되는 인계 화합물의 제조방법은 포스포러스 옥시클로라이드, 하기 화학식 2로 표시되는 화합물 및 비페놀을 반응시키는 단계를 포함한다.The process for preparing a phosphorus compound represented by the formula (1) according to the present invention comprises reacting phosphorus oxychloride, a compound represented by the following formula (2) and biphenol.
[화학식 2] (2)
상기 식에서, R은 수소 또는 C1-C4의 알킬기임.Wherein, R is an alkyl group of hydrogen or C 1 -C 4.
본 발명의 일 구체예에서, 상기 인계 화합물의 제조방법은 포스포러스 옥시클로라이드 및 상기 화학식 2로 표시되는 화합물을 반응시키고; 그리고 상기 반응으로 생긴 생성물에 비페놀을 반응시키는 단계를 포함한다.In one embodiment of the present invention, the method for preparing the phosphorus compound comprises: reacting phosphorus oxychloride and the compound represented by Formula 2; And reacting the resultant product with biphenol.
본 발명의 일 구체예에서, 상기 포스포러스 옥시클로라이드 대 상기 화학식 2로 표시되는 화합물의 반응 몰비는 1:2이고, 상기 포스포러스 옥시클로라이드 대 상기 비페놀의 반응 몰비는 2:1이다.In one embodiment of the present invention, the reaction molar ratio of the phosphorus oxychloride to the compound represented by the formula (2) is 1: 2, and the molar ratio of the phosphorus oxychloride to the biphenol is 2: 1.
본 발명에 따른 난연성 열가소성 수지 조성물은 상기 인계 화합물을 포함한다.The flame retardant thermoplastic resin composition according to the present invention includes the phosphorus compound.
본 발명의 일 구체예에서, 상기 난연성 열가소성 수지 조성물은 열가소성 수지 100 중량부; 및 상기 인계 화합물 0.1 내지 50 중량부를 포함한다.In one embodiment of the present invention, the flame retardant thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; And 0.1 to 50 parts by weight of the phosphorus compound.
본 발명의 일 구체예에서, 상기 열가소성 수지는 폴리스티렌계 수지, 아크릴로니트릴-부타디엔-스티렌 공중합체 수지, 고강도 폴리스티렌 수지, 아크릴로니트릴-스티렌-아크릴레이트 공중합체 수지, 아크릴로니트릴-스티렌 공중합체 수지, 메틸메타크릴레이트-부타디엔-스티렌 공중합체 수지, 아크릴로니트릴-에틸아크릴레이트-스티렌 공중합체 수지, 폴리카보네이트계 수지, 폴리페닐렌에테르 수지, 폴리페닐렌설파이드 수지, 폴리에틸렌 수지, 폴리프로필렌 수지, 폴리에틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 폴리(메타)아크릴계 수지 및 폴리아미드계 수지로 이루어지는 군으로부터 하나 이상 선택된다.In one embodiment of the present invention, the thermoplastic resin is at least one selected from the group consisting of a polystyrene series resin, an acrylonitrile-butadiene-styrene copolymer resin, a high-strength polystyrene resin, an acrylonitrile-styrene- acrylate copolymer resin, an acrylonitrile- Butadiene-styrene copolymer resin, acrylonitrile-ethyl acrylate-styrene copolymer resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polyethylene resin, polypropylene resin , A polyethylene terephthalate resin, a polybutylene terephthalate resin, a poly (meth) acrylic resin and a polyamide resin.
본 발명의 일 구체예에서, 상기 난연성 열가소성 수지 조성물은 상기 인계 화합물 이외의 난연제, 난연보조제, 활제, 가소제, 열안정제, 적하방지제, 산화방지제, 상용화제, 광안정제, 안료, 염료 및 무기 충전제로 이루어진 군으로부터 하나 이상 선택되는 첨가제를 더 포함한다.
In one embodiment of the present invention, the flame-retardant thermoplastic resin composition is used as a flame retardant, a flame-retardant aid, a lubricant, a plasticizer, a heat stabilizer, a dripping inhibitor, an antioxidant, a compatibilizer, a light stabilizer, a pigment, And at least one additive selected from the group consisting of
본 발명에 따른 인계 화합물은 새로운 구조를 가지며, 고온에서의 내가수분해성 및 내열성이 우수하다. 또한, 본 발명에 따른 열가소성 수지 조성물은 난연성, 고온에서의 내가수분해성 및 내열성이 우수하다.
The phosphorus compound according to the present invention has a novel structure and is excellent in hydrolysis resistance and heat resistance at high temperature. Further, the thermoplastic resin composition according to the present invention is excellent in flame retardance, hydrolysis resistance at high temperature, and heat resistance.
도 1은 실시예에 따른 인계 화합물의 1H-NMR 스펙트럼이다.1 is a 1 H-NMR spectrum of a phosphorus compound according to an embodiment.
인계 화합물Phosphorus compound
본 발명에 따른 인계 화합물은 하기 화학식 1로 표시된다.The phosphorus compound according to the present invention is represented by the following general formula (1).
[화학식 1] [Chemical Formula 1]
상기 식에서, R은 수소 또는 C1-C4의 알킬기임.Wherein, R is an alkyl group of hydrogen or C 1 -C 4.
본 발명에 따른 상기 인계 화합물은 터셔리부틸기(tertiary butyl group)가 오쏘(ortho) 위치에 치환된 페닐기와 비페놀(biphenol) 링커(linker)를 포함하며, 이로써 터셔리부틸기가 다른 위치에 치환된 페닐기를 포함하는 올리고머형 방향족 인산 에스테르; 터셔리부틸기가 아닌, 메틸기, 에틸기, 프로필기 또는 노말부틸기가 치환된 페닐기를 포함하는 올리고머형 방향족 인산 에스테르; 또는 링커로서 비페놀이 아닌, 하이드로퀴논, 레조시놀 또는 비스페놀-A를 포함하는 올리고머형 방향족 인산 에스테르에 비해 고온에서의 내가수분해성 및 내열성이 우수하다.The phosphorus compound according to the present invention includes a phenyl group and a biphenol linker in which a tertiary butyl group is substituted at an ortho position so that the tertiary butyl group is substituted at another position An oligomer type aromatic phosphate ester containing a phenyl group; An oligomer type aromatic phosphate ester including a phenyl group substituted with a methyl group, an ethyl group, a propyl group or a normal butyl group, not a tertiary butyl group; Or an oligomer type aromatic phosphate ester containing hydroquinone, resorcinol or bisphenol-A, which is not biphenol as a linker, is excellent in hydrolysis resistance and heat resistance at a high temperature.
본 발명에서 상기 R은 수소 또는 C1-C4의 알킬기이며, 바람직하게 수소, 메틸기, 에틸기이며, 더 바람직하게 수소이다.In the present invention, R is hydrogen or a C 1 -C 4 alkyl group, preferably hydrogen, a methyl group or an ethyl group, and more preferably hydrogen.
본 발명의 일 구체예에서, 상기 인계 화합물과 물을 3:1의 중량비로 혼합한 혼합물을 93 ℃에서 48시간 동안 교반하였을 때 교반 전후의 산가 변화는 0 내지 0.9 mg KOH/g, 바람직하게 0 내지 0.5 mg KOH/g, 더 바람직하게 0 내지 0.2 mg KOH/g, 가장 바람직하게 0 내지 0.1 mg KOH/g이다.In one embodiment of the present invention, when the mixture obtained by mixing the phosphorus compound and water at a weight ratio of 3: 1 is stirred at 93 캜 for 48 hours, the acid value change before and after stirring is 0 to 0.9 mg KOH / g, preferably 0 To 0.5 mg KOH / g, more preferably from 0 to 0.2 mg KOH / g, most preferably from 0 to 0.1 mg KOH / g.
본 발명의 일 구체예에서, 상기 인계 화합물과 물을 9:1의 중량비로 혼합한 혼합물을 280 ℃에서 1시간 동안 방치하였을 때 방치 전후의 산가 변화는 0 내지 0.8 mg KOH/g, 바람직하게 0 내지 0.4 mg KOH/g, 더 바람직하게 0 내지 0.1 mg KOH/g, 가장 바람직하게 0.00 mg KOH/g이다.In one embodiment of the present invention, when the mixture obtained by mixing the phosphorus compound and water in a weight ratio of 9: 1 is left at 280 DEG C for 1 hour, the acid value change before and after leaving is 0 to 0.8 mg KOH / g, preferably 0 To 0.4 mg KOH / g, more preferably from 0 to 0.1 mg KOH / g, most preferably 0.00 mg KOH / g.
상기 산가는 적정량의 시료를 에탄올 50ml에 녹이고 소량의 BTB 용액을 첨가한 후 0.1N NaOH 용액으로 적정하면서 NaOH 용액의 소비량을 측정하고 하기 식을 이용하여 구한다.The acid value is obtained by dissolving a proper amount of sample in 50 ml of ethanol, adding a small amount of BTB solution, measuring the consumption amount of NaOH solution while titrating with 0.1 N NaOH solution, and using the following equation.
산가 = ((0.1N-NaOH 용액 소비 ml) * (0.1N-NaOH 용액 Factor) * 5.61) / 시료량(g) Acid value = ((0.1N-NaOH solution consumption ml) * (0.1N-NaOH solution Factor) * 5.61) / sample amount (g)
본 발명의 일 구체예에서, 열중량 분석법에 의하여 측정한 상기 인계 화합물의 200 ℃에서의 손실중량은 0 내지 0.3%, 바람직하게 0 내지 0.2%, 더 바람직하게 0 내지 0.1%, 가장 바람직하게 0%이다.In one embodiment of the present invention, the loss weight of the phosphorus compound measured by thermogravimetric analysis at 200 캜 is 0 to 0.3%, preferably 0 to 0.2%, more preferably 0 to 0.1%, most preferably 0 %to be.
본 발명의 일 구체예에서, 열중량 분석법에 의하여 측정한 상기 인계 화합물의 250 ℃에서의 손실중량은 0 내지 0.6%, 바람직하게 0 내지 0.3%, 더 바람직하게 0 내지 0.1%, 가장 바람직하게 0%이다.In one embodiment of the present invention, the loss weight of the phosphorus compound measured by thermogravimetric analysis at 250 캜 is 0 to 0.6%, preferably 0 to 0.3%, more preferably 0 to 0.1%, most preferably 0 %to be.
본 발명의 일 구체예에서, 열중량 분석법에 의하여 측정한 상기 인계 화합물의 300 ℃에서의 손실중량은 0 내지 4%, 바람직하게 0 내지 1%, 더 바람직하게 0 내지 0.1%, 가장 바람직하게 0%이다.In one embodiment of the present invention, the loss weight of the phosphorus compound measured by thermogravimetric analysis at 300 캜 is 0 to 4%, preferably 0 to 1%, more preferably 0 to 0.1%, most preferably 0 %to be.
본 발명의 일 구체예에서, 열중량 분석법에 의하여 측정한 상기 인계 화합물의 350 ℃에서의 손실중량은 0 내지 15%, 바람직하게 0 내지 5%, 더 바람직하게 0 내지 1%, 가장 바람직하게 0 내지 0.1%이다.In one embodiment of the present invention, the loss weight of the phosphorus compound measured at 350 DEG C by thermogravimetric analysis is 0 to 15%, preferably 0 to 5%, more preferably 0 to 1%, most preferably 0 To 0.1%.
인계 화합물의 제조방법Method for producing phosphorus compound
본 발명에 따른 상기 화학식 1로 표시되는 인계 화합물의 제조방법은 포스포러스 옥시클로라이드, 하기 화학식 2로 표시되는 화합물 및 비페놀을 반응시키는 단계를 포함한다.The process for preparing a phosphorus compound represented by the formula (1) according to the present invention comprises reacting phosphorus oxychloride, a compound represented by the following formula (2) and biphenol.
[화학식 2] (2)
상기 식에서, R은 수소 또는 C1-C4의 알킬기임.Wherein, R is an alkyl group of hydrogen or C 1 -C 4.
본 발명의 일 구체예에서, 상기 인계 화합물의 제조방법은 포스포러스 옥시클로라이드 및 상기 화학식 2로 표시되는 화합물을 반응시키고; 그리고 상기 반응으로 생긴 생성물에 비페놀을 반응시키는 단계를 포함한다.In one embodiment of the present invention, the method for preparing the phosphorus compound comprises: reacting phosphorus oxychloride and the compound represented by Formula 2; And reacting the resultant product with biphenol.
예를 들어, 포스포러스 옥시클로라이드 및 2-터셔리부틸페놀을 반응시켜 디-2-터셔리부틸페닐 클로로 포스페이트를 제조하고; 그리고 상기 디-2-터셔리부틸페닐 클로로 포스페이트에 비페놀을 반응시켜 비페놀 비스(디-2-터셔리부틸페닐 포스페이트)를 제조할 수 있다.For example, phosphorus oxychloride and 2-tertiary butylphenol are reacted to prepare di-2-tert-butylphenylphenylchlorophosphate; Bisphenol bis (di-2-tert-butylphenylphosphate) can be prepared by reacting the di-2-tert-butylphenylphenylchlorophosphate with biphenol.
상기 인계 화합물의 제조방법에서 사용할 수 있는 용매는 110-200℃의 끓는점을 가지고 히드록시기가 없는 비양성자성 유기 용매이며, 바람직하게 방향족 화합물로 톨루엔, 크실렌, 클로로벤젠 또는 디클로로벤젠이며, 더 바람직하게 톨루엔, 크실렌, 클로로벤젠이다. 110 ℃보다 낮은 끓는점을 갖는 용매를 사용할 경우에 반응이 매우 느리게 진행될 수 있으며, 200 ℃보다 높은 끓는점을 갖는 용매를 사용할 경우에 반응 후 완전히 건조시키기 어렵고 제품의 색상이 변질될 수 있다. 상기 용매는 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. The solvent that can be used in the above-described method for preparing a phosphorus-containing compound is an aprotic organic solvent having a boiling point of 110-200 DEG C and having no hydroxy group, and is preferably an aromatic compound such as toluene, xylene, chlorobenzene or dichlorobenzene, , Xylene, and chlorobenzene. When using a solvent having a boiling point lower than 110 캜, the reaction may proceed very slowly, and when a solvent having a boiling point higher than 200 캜 is used, it is difficult to completely dry after the reaction and the color of the product may be changed. These solvents may be used alone or in combination of two or more.
상기 포스포러스 옥시클로라이드 및 상기 화학식 2로 표시되는 화합물을 반응시키는 단계, 상기 반응으로 생긴 생성물에 비페놀을 반응시키는 단계 또는 이들 모두에 사용할 수 있는 촉매는 루이스산 촉매 또는 염기 촉매이다.The catalyst which can be used in the step of reacting the phosphorus oxychloride and the compound represented by the formula 2, the step of reacting biphenol with the product resulting from the reaction, or both of them can be a Lewis acid catalyst or a base catalyst.
상기 루이스산 촉매로서 금속 염화물이나 금속 산화물을 사용할 수 있으며, 바람직하게 마그네슘 클로라이드, 알루미늄 클로라이드, 칼슘 클로라이드 등의 금속 염화물을 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다. 상기 루이스산 촉매는 반응물 전체의 몰수에 대하여 0.1-10 mol %, 바람직하게 0.5-5 mol%, 더 바람직하게 1-2 mol%로 사용될 수 있다. 상기 루이스산 촉매가 상기 범위 내에서 사용되는 경우에, 반응속도가 우수해지고 반응 후 촉매 제거도 유리해질 수 있다.As the Lewis acid catalyst, metal chlorides and metal oxides can be used, and metal chlorides such as magnesium chloride, aluminum chloride and calcium chloride can be preferably used, but not always limited thereto. The Lewis acid catalyst may be used in an amount of 0.1-10 mol%, preferably 0.5-5 mol%, more preferably 1-2 mol%, based on the molar amount of the reactants. When the Lewis acid catalyst is used within the above range, the reaction rate becomes excellent and the removal of the catalyst after the reaction may be favorable.
상기 염기 촉매로서 유기아민 화합물을 사용할 수 있으며, 바람직하게 피리딘, 루티딘과 같은 방향족 아민과 트리알킬아민류의 삼가아민 등을 사용할 수 있으며, 가장 바람직하게 피리딘 또는 트리에틸아민을 사용할 수 있다. 상기 염기 촉매는 사용되는 원료의 염소 원소 양에 대하여 1-3 당량비, 바람직하게 1.1-2 당량비, 더 바람직하게 1.2-1.5 당량비로 사용될 수 있다. 상기 염기 촉매가 상기 범위 내에서 사용되는 경우에, 반응의 완결성을 높일 수 있고, 부산물을 최소화할 수 있다.As the base catalyst, an organic amine compound can be used, and aromatic amines such as pyridine and lutidine, and triarylamines such as trialkylamines can be used, and pyridine or triethylamine can be most preferably used. The base catalyst may be used in an amount of 1 to 3 equivalents, preferably 1.1 to 2 equivalents, more preferably 1.2 to 1.5 equivalents, based on the amount of chlorine in the raw material used. When the base catalyst is used within the above range, the completeness of the reaction can be enhanced and by-products can be minimized.
본 발명의 일 구체예에서, 상기 포스포러스 옥시클로라이드와 상기 화학식 2로 표시되는 화합물의 반응 온도, 상기 반응으로 생긴 생성물과 비페놀의 반응 온도 또는 이들 모두는 80∼170 ℃, 바람직하게 100∼160 ℃, 더 바람직하게 120∼140 ℃이다. In one embodiment of the present invention, the reaction temperature of the phosphorus oxychloride and the compound represented by the formula (2), the reaction temperature of the product formed by the reaction and the biphenol, or both are 80 to 170 ° C, preferably 100 to 160 Deg.] C, more preferably 120 to 140 [deg.] C.
본 발명의 일 구체예에서, 상기 포스포러스 옥시클로라이드 대 상기 화학식 2로 표시되는 화합물의 반응 몰비는 1:2이고, 상기 포스포러스 옥시클로라이드 대 상기 비페놀의 반응 몰비는 2:1이다. 반응물들이 상기 범위 내에서 사용되는 경우에, 반응의 완결성을 높일 수 있으며, 부산물을 최소화 할 수 있다.In one embodiment of the present invention, the reaction molar ratio of the phosphorus oxychloride to the compound represented by the formula (2) is 1: 2, and the molar ratio of the phosphorus oxychloride to the biphenol is 2: 1. When the reactants are used within the above range, the completeness of the reaction can be enhanced and by-products can be minimized.
난연성 열가소성 수지 조성물Flame retardant thermoplastic resin composition
본 발명에 따른 난연성 열가소성 수지 조성물은 상기 인계 화합물을 포함하며, 상기 인계 화합물이 고온에서의 내가수분해성 및 내열성이 우수하기 때문에, 열가소성 수지로서 주로 고온에서 가공되는 수지를 사용하더라도, 상기 인계 화합물을 포함하는 열가소성 수지 조성물의 가공시 인계 화합물로 인해 가스가 발생하거나, 분해되거나, 외관이 저하되는 등의 문제점을 미연에 방지할 수 있다. 특히, 상기 인계 화합물은 산소를 함유하는 열가소성 수지에 바람직하게 적용할 수 있다.Since the flame retardant thermoplastic resin composition according to the present invention contains the phosphorus compound and the phosphorus compound is excellent in hydrolysis resistance and heat resistance at high temperatures, even when a resin which is mainly processed as a thermoplastic resin at high temperature is used, It is possible to prevent problems such as generation of gas, decomposition or deterioration of appearance due to the phosphorus compound in the processing of the thermoplastic resin composition containing it. In particular, the phosphorus compound is preferably applicable to a thermoplastic resin containing oxygen.
본 발명의 일 구체예에서, 상기 난연성 열가소성 수지 조성물은 열가소성 수지 100 중량부; 및 상기 인계 화합물 0.1 내지 50 중량부, 바람직하게 1 내지 30 중량부, 더 바람직하게 5 내지 15 중량부를 포함한다.In one embodiment of the present invention, the flame retardant thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; And 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 5 to 15 parts by weight of the phosphorus compound.
본 발명의 일 구체예에서, 상기 열가소성 수지는 폴리스티렌계 수지, 아크릴로니트릴-부타디엔-스티렌 공중합체 수지, 고강도 폴리스티렌 수지, 아크릴로니트릴-스티렌-아크릴레이트 공중합체 수지, 아크릴로니트릴-스티렌 공중합체 수지, 메틸메타크릴레이트-부타디엔-스티렌 공중합체 수지, 아크릴로니트릴-에틸아크릴레이트-스티렌 공중합체 수지, 폴리카보네이트계 수지, 폴리페닐렌에테르 수지, 폴리페닐렌설파이드 수지, 폴리에틸렌 수지, 폴리프로필렌 수지, 폴리에틸렌 테레프탈레이트 수지, 폴리부틸렌 테레프탈레이트 수지, 폴리(메타)아크릴계 수지 및 폴리아미드계 수지로 이루어지는 군으로부터 하나 이상 선택된다.In one embodiment of the present invention, the thermoplastic resin is at least one selected from the group consisting of a polystyrene series resin, an acrylonitrile-butadiene-styrene copolymer resin, a high-strength polystyrene resin, an acrylonitrile-styrene- acrylate copolymer resin, an acrylonitrile- Butadiene-styrene copolymer resin, acrylonitrile-ethyl acrylate-styrene copolymer resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polyethylene resin, polypropylene resin , A polyethylene terephthalate resin, a polybutylene terephthalate resin, a poly (meth) acrylic resin and a polyamide resin.
본 발명의 일 구체예에서, 상기 난연성 열가소성 수지 조성물은 상기 인계 화합물 이외의 난연제, 난연보조제, 활제, 가소제, 열안정제, 적하방지제, 산화방지제, 상용화제, 광안정제, 안료, 염료 및 무기 충전제로 이루어진 군으로부터 하나 이상 선택되는 첨가제를 더 포함하며, 상기 첨가제는 상기 열가소성 수지 100 중량부에 대하여 0 내지 30 중량부, 바람직하게 0 내지 15 중량부로 포함될 수 있다.In one embodiment of the present invention, the flame-retardant thermoplastic resin composition is used as a flame retardant, a flame-retardant aid, a lubricant, a plasticizer, a heat stabilizer, a dripping inhibitor, an antioxidant, a compatibilizer, a light stabilizer, a pigment, And the additive may be added in an amount of 0 to 30 parts by weight, preferably 0 to 15 parts by weight, based on 100 parts by weight of the thermoplastic resin.
상기 인계 화합물 이외의 난연제, 난연보조제 및 적하방지제의 예로는 일반적으로 널리 상용화된 할로겐 함유 유기 화합물, 시아누레이트 화합물, 금속염, 불소화 폴리올레핀계 수지 등이 있다. 상기 난연보조제로 사용 가능한 금속염은 통상적으로 널리 알려진 술폰산 금속염, 술폰 술폰산 금속염 등이 있으며, 상기 적하방지제로 사용 가능한 불소화 폴리올레핀계 수지는 종래의 이용 가능한 수지로서 폴리테트라플루오로에틸렌, 폴리비닐리덴플루오라이드, 테트라플루오로에틸렌/비닐리덴플루오로라이드 공중합체, 테트라플루오로에틸렌/헥사플루오로프로필렌 공중합체, 에틸렌/테트라플루오로에틸렌 공중합체 등이 있다. 상기 무기 충전제의 예로는 유리섬유, 탈크, 세라믹 또는 황산염 등이 있다.Examples of flame retardants, flame-retardant auxiliaries, and anti-dripping agents other than the phosphorus compounds include halogen-containing organic compounds, cyanurate compounds, metal salts, fluorinated polyolefin resins and the like which are generally widely used. Examples of the metal salt that can be used as the flame retardant adjuvant include commonly known sulfonic acid metal salts and sulfonesulfonic acid metal salts. The fluorinated polyolefin resin that can be used as the drip inhibitor may be polytetrafluoroethylene, polyvinylidene fluoride , Tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, and the like. Examples of the inorganic filler include glass fiber, talc, ceramic or sulfate.
본 발명에서, 상기 난연성 열가소성 수지 조성물은 구성성분들과 첨가제들을 혼합한 후, 압출기 내에서 용융 압출하는 방식에 의해서 펠렛 또는 칩 형태로 제조될 수 있다. 또한, 상기 난연성 열가소성 수지 조성물을 이용하여 플라스틱 성형품을 제조하는 방법에는 특별한 제한이 없으며, 예를 들어, 압출, 사출 또는 캐스팅 성형 방법을 이용하여 플라스틱 성형품을 제조할 수 있다.In the present invention, the flame-retardant thermoplastic resin composition can be produced in the form of pellets or chips by mixing components and additives, followed by melt-extrusion in an extruder. There is no particular limitation on the method for producing a plastic molded article using the flame-retardant thermoplastic resin composition. For example, a plastic molded article can be produced by extrusion, injection molding, or casting molding.
본 발명에 따른 열가소성 수지 조성물은 난연성뿐만 아니라, 내열성 및 내가수분해성이 우수하기 때문에, 여러 가지 제품에 바람직하게 적용될 수 있다. 예를 들어, 상기 열가소성 수지 조성물은 TV, 오디오, 핸드폰, 디지털 카메라, 내비게이션, 세탁기, 컴퓨터, 모니터, MP3, 비디오 플레이어, CD 플레이어, 세척기 등과 같은 전기ㆍ전자 제품의 하우징; 또는 복사기, 팩시밀리, 프린터 등과 같은 사무자동화 기기의 하우징에 바람직하게 적용될 수 있다.The thermoplastic resin composition according to the present invention can be suitably applied to various products because it has not only flame retardancy but also excellent heat resistance and hydrolysis resistance. For example, the thermoplastic resin composition may be applied to a housing of an electric / electronic product such as TV, audio, cellular phone, digital camera, navigation, washing machine, computer, monitor, MP3, video player, CD player, Or a housing of an office automation machine such as a copier, a facsimile machine, a printer, or the like.
본 발명은 하기의 실시예에 의해 보다 구체화될 것이나, 하기의 실시예는 본 발명을 예시하기 위한 목적으로 사용될 뿐이며 본 발명의 보호범위를 한정하고자 하는 것은 아니다.The present invention will be further illustrated by the following examples, but the following examples are used for the purpose of illustrating the present invention and are not intended to limit the scope of protection of the present invention.
실시예Example
반응기에 포스포러스 옥시클로라이드(Aldrich사 제품) 2 당량, 2-터셔리부틸페놀(Aldrich사 제품) 4 당량, 트리에틸아민(Samchun사 제품) 4.4 당량 및 톨루엔(Samchun사 제품) 20 당량을 투입한 후, 반응기를 130 ℃로 승온 후 10시간 이상 교반하였다. 반응이 완료되면 온도를 상온으로 내리고 반응기에 비페놀(송원산업사 제품) 1 당량, 트리에틸아민 2.2 당량 및 톨루엔 10 당량을 투입한 후, 반응기를 130 ℃로 승온 후 10시간 이상 교반하였다. 반응이 완료되면 온도를 상온으로 내리고 반응기에 물 15 당량을 투입하여 3회 세척하였다. 물층을 버리고 유기층을 감압하여 트리에틸아민과 톨루엔을 제거하였다. 아세톤을 투입하고 60 ℃로 승온하여 생성물을 모두 녹인 후, 0 ℃ 이하로 냉각하여 생성물을 재결정하였다. 여과 후 하기 화학식 1-1로 표시되는 고상의 최종 생성물을 얻었으며(수율: 97%), 이 생성물의 1H-NMR 스펙트럼(Bruker사 300MHz)을 도 1에 나타내었다.The reactor was charged with 2 equivalents of phosphorus oxychloride (Aldrich), 4 equivalents of 2-tertiary butylphenol (Aldrich), 4.4 equivalents of triethylamine (Samchun) and 20 equivalents of toluene (Samchun) Thereafter, the reactor was heated to 130 캜 and stirred for 10 hours or longer. After the reaction was completed, the temperature was lowered to room temperature, and 1 equivalent of biphenol (manufactured by Songwon Industrial Co., Ltd.), 2.2 equivalents of triethylamine and 10 equivalents of toluene were added to the reactor, and then the reactor was heated to 130 캜 and stirred for 10 hours or longer. When the reaction was completed, the temperature was lowered to room temperature, and the reactor was washed three times with 15 equivalents of water. The water layer was discarded and the organic layer was reduced in pressure to remove triethylamine and toluene. Acetone was added and the temperature was raised to 60 ° C to dissolve all the product. The product was cooled to 0 ° C or lower and the product was recrystallized. 1 H-NMR spectrum (Bruker 300 MHz) of the product was shown in FIG. 1.
[화학식 1-1][Formula 1-1]
비교실시예Comparative Example 1-2 1-2
물성 비교를 위해서, 비스페놀-A 비스(디페닐포스페이트)(BDP)(비교실시예 1) 및 레조시놀 비스(디-2,6-디메틸페닐포스페이트)(PX-200)(비교실시예 2)를 사용하였다. Bisphenol-A bis (diphenylphosphate) (BDP) (Comparative Example 1) and resorcinol bis (di-2,6-dimethylphenylphosphate) (PX-200) (Comparative Example 2) Were used.
실시예에 의해서 제조된 인계 화합물 및 비교실시예 1-2의 인계 화합물의 고온에서의 내가수분해성 및 내열성을 하기와 같은 방법으로 측정하였으며, 그 결과를 표 1에 나타내었다.The hydrolysis resistance and heat resistance at high temperature of the phosphorus compound prepared in the Example and the phosphorus compound of Comparative Example 1-2 were measured by the following methods, and the results are shown in Table 1.
(1) 고온에서의 내가수분해성: 인계 화합물 75 g과 증류수 25 g의 혼합물을 93 ℃에서 48시간 동안 교반하였을 때 교반 전후의 산가 변화와, 인계 화합물 10 g과 증류수 90 g의 혼합물을 280 ℃에서 1시간 동안 방치하였을 때 방치 전후의 산가 변화를 측정하였으며, 여기에서 산가는 적정량의 시료를 에탄올 50ml에 녹이고 소량의 BTB 용액을 첨가한 후 0.1N NaOH 용액으로 적정하면서 NaOH 용액의 소비량을 측정하고 하기 식을 이용하여 구한다.(1) Hydrolysis resistance at high temperature: When a mixture of 75 g of phosphorus compound and 25 g of distilled water was stirred at 93 캜 for 48 hours, the mixture of 10 g of the phosphorus compound and 90 g of distilled water was stirred at 280 캜 , The acid value was measured before and after the incubation for 1 hour. The acid value was measured by dissolving the appropriate amount of sample in 50 ml of ethanol, adding a small amount of BTB solution, measuring the consumption of NaOH solution while titrating with 0.1 N NaOH solution Is obtained by using the following equation.
* 산가 (mg KOH/g) = ((0.1N-NaOH 용액 소비 ml) * (0.1N-NaOH 용액 Factor) * 5.61) / 시료량(g) * Acid value (mg KOH / g) = ((0.1N NaOH solution consumption ml) * (0.1N NaOH solution Factor * 5.61) / Amount of sample (g)
(2) 내열성: 열중량 분석기를 이용하여 인계 화합물의 200 ℃, 250 ℃, 300 ℃ 및 350 ℃에서의 손실중량(%)을 측정하였다.(2) Heat resistance: The loss weight (%) of the phosphorus compound at 200 ° C, 250 ° C, 300 ° C and 350 ° C was measured using a thermogravimetric analyzer.
(mg KOH/g, 93 ℃, 48h)Acid value variation
(mg KOH / g, 93 < 0 > C, 48 h)
(mg KOH/g, 280 ℃, 1h)Acid value variation
(mg KOH / g, 280 DEG C, 1 h)
상기 표 1을 보면, 실시예에 따른 인계 화합물은 비교실시예 1-2에 따른 인계 화합물에 비해 고온에서의 내가수분해성 및 내열성이 우수함을 알 수 있다.Table 1 shows that the phosphorus compounds according to the Examples are superior in hydrolysis resistance and heat resistance at high temperatures as compared with the phosphorus compounds according to Comparative Example 1-2.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (11)
상기 반응으로 생긴 생성물에 비페놀을 반응시키는;
단계를 포함하는 하기 화학식 1로 표시되는 인계 화합물의 제조방법:
[화학식 2]
상기 식에서, R은 수소 또는 C1-C4의 알킬기임.
[화학식 1]
상기 식에서, R은 수소 또는 C1-C4의 알킬기임.
Phosphorus oxychloride and a compound represented by the following formula (2); And
Reacting the product resulting from the reaction with biphenol;
(1), comprising the steps of:
(2)
Wherein, R is an alkyl group of hydrogen or C 1 -C 4.
[Chemical Formula 1]
Wherein, R is an alkyl group of hydrogen or C 1 -C 4.
5. The process according to claim 4, wherein the reaction molar ratio of the phosphorus oxychloride to the compound represented by the formula (2) is 1: 2, and the molar ratio of the phosphorus oxychloride to the biphenol is 2: ≪ / RTI >
A flame-retardant thermoplastic resin composition comprising a phosphorus compound produced by the method of any one of claims 4 to 5.
The flame-retardant thermoplastic resin composition according to claim 6, wherein the flame-retardant thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; And 0.1 to 50 parts by weight of the phosphorus compound.
The thermoplastic resin composition according to claim 7, wherein the thermoplastic resin is selected from the group consisting of a polystyrene resin, an acrylonitrile-butadiene-styrene copolymer resin, a high-strength polystyrene resin, an acrylonitrile-styrene- acrylate copolymer resin, an acrylonitrile- Butadiene-styrene copolymer resin, acrylonitrile-ethyl acrylate-styrene copolymer resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polyethylene resin, polypropylene resin, polyethylene Wherein the flame retardant thermoplastic resin composition is at least one selected from the group consisting of terephthalate resin, polybutylene terephthalate resin, poly (meth) acrylic resin and polyamide resin.
A phosphorus compound prepared by the method according to claim 4, wherein when the phosphorus compound and water are mixed at a weight ratio of 3: 1, the acid value change before and after stirring is 0 to 0.9 mg KOH / g, and the phosphoric acid compound and water are mixed at a weight ratio of 9: 1, and the acid value change before and after standing at 280 DEG C for 1 hour is 0 to 0.8 mg KOH / g.
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| US5420327A (en) * | 1992-09-14 | 1995-05-30 | Akzo Nobel N.V. | Process for forming hydrocarbyl bisphosphate compound |
| JPH1036645A (en) * | 1996-07-22 | 1998-02-10 | Polyplastics Co | Polybutylene terephthalate resin composition |
| US20020137824A1 (en) * | 1998-09-02 | 2002-09-26 | Cheil Industries Inc. | Flameproof styrene-containing graft resin compositions having a particular nitrile content distribution |
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| JP2552780B2 (en) * | 1991-04-16 | 1996-11-13 | 大八化学工業株式会社 | Method and application for producing aromatic diphosphate |
| JP3383159B2 (en) * | 1996-07-30 | 2003-03-04 | 大八化学工業株式会社 | Method for producing aromatic bisphosphate |
| KR100552999B1 (en) * | 2003-08-04 | 2006-02-15 | 제일모직주식회사 | Flameproof Thermoplastic Resin Composition |
| WO2005017030A1 (en) * | 2003-08-14 | 2005-02-24 | Cheil Industries Inc. | Flameproof rubber-reinforced styrenic resin composition |
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| US5420327A (en) * | 1992-09-14 | 1995-05-30 | Akzo Nobel N.V. | Process for forming hydrocarbyl bisphosphate compound |
| JPH1036645A (en) * | 1996-07-22 | 1998-02-10 | Polyplastics Co | Polybutylene terephthalate resin composition |
| US20020137824A1 (en) * | 1998-09-02 | 2002-09-26 | Cheil Industries Inc. | Flameproof styrene-containing graft resin compositions having a particular nitrile content distribution |
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