KR100845119B1 - Process for the preparation of cyclic phosphonate flame retardant - Google Patents
Process for the preparation of cyclic phosphonate flame retardant Download PDFInfo
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- KR100845119B1 KR100845119B1 KR1020050013926A KR20050013926A KR100845119B1 KR 100845119 B1 KR100845119 B1 KR 100845119B1 KR 1020050013926 A KR1020050013926 A KR 1020050013926A KR 20050013926 A KR20050013926 A KR 20050013926A KR 100845119 B1 KR100845119 B1 KR 100845119B1
- Authority
- KR
- South Korea
- Prior art keywords
- phosphate ester
- flame retardant
- reaction
- bicyclic
- formula
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 title 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 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 abstract description 21
- 125000004122 cyclic group Chemical group 0.000 title abstract description 3
- 230000008569 process Effects 0.000 title description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title 1
- -1 cyclic phosphate ester Chemical class 0.000 claims abstract description 58
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 41
- 239000010452 phosphate Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000004383 yellowing Methods 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000002619 bicyclic group Chemical group 0.000 claims description 15
- 239000002841 Lewis acid Substances 0.000 claims description 12
- 150000007517 lewis acids Chemical class 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 2
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000006462 rearrangement reaction Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- HPUPGAFDTWIMBR-UHFFFAOYSA-N [methyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C)OC1=CC=CC=C1 HPUPGAFDTWIMBR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- 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)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 폴리에스터, 폴리아마이드 또는 폴리스티렌계 범용 수지에 사용되는 유기인계 난연제의 새로운 합성방법에 관한 것으로, 고온에서도 수지의 기본 물성을 저하 시키지 않는 내열성과 기초수지와의 균일한 혼합성등 가공성이 뛰어난 사이클릭 인산에스터 형태의 유기인계 난연제를 합성할 수 있는 방법으로서, 촉매조건에 따라 사이클릭 인산에스터기가 단일치환 및 이중 치환된 형태의 물질 비를 조절할 수 있는 방법으로서 기존의 방법들 보다 온화한 조건에서 황변현상 없이 반응시킬 수 있는 잇점을 갖는 유용한 합성방법이다.The present invention relates to a new synthetic method of organophosphorus flame retardant used in polyester, polyamide or polystyrene-based general-purpose resin, the processability such as heat resistance and uniform mixing with the base resin does not reduce the basic physical properties of the resin at high temperature A method for synthesizing an organophosphorous flame retardant in the form of an excellent cyclic phosphate ester. A method in which a cyclic phosphate ester group can control a mono- and double-substituted material ratio according to catalytic conditions. It is a useful synthetic method that has the advantage of being able to react without yellowing at.
유기인계, 난연제, 사이클릭 인산에스터, 난연성, 촉매, 내열성 Organophosphorus, flame retardant, cyclic phosphate, flame retardant, catalyst, heat resistant
Description
본 발명은 유기인계 난연제의 새로운 합성방법에 관한 것으로 폴리에스터, 폴리아마이드 또는 폴리스티렌계 범용 수지에 사용되는 유기인계 난연제의 새로운 합성방법에 관한 것이다. 본 발명에서 합성하는 유기인계 난연제는 수지에 난연성을 부여함으로써 화재 발생을 미연에 방지하고, 화재가 발생한 경우에는 화염의 발생을 억제함으로써 화재의 확산을 방지하는 역할을 하는 것으로서, 고온에서도 수지의 기본 물성을 저하 시키지 않는 내열성과 기초수지와의 균일한 혼합성등 가공성이 뛰어난 사이클릭 인산에스터(cyclic phosphonate ester)형태의 유기인계 난연제를 합성하는 방법을 제공한다. The present invention relates to a new method for synthesizing an organophosphorous flame retardant and a new method for synthesizing an organophosphorous flame retardant used in polyester, polyamide or polystyrene general purpose resins. The organophosphorus flame retardant synthesized in the present invention prevents the occurrence of fire in advance by providing flame retardancy to the resin, and prevents the spread of fire by suppressing the occurrence of flame in the case of a fire, the basic of the resin even at high temperatures The present invention provides a method for synthesizing an organophosphorous flame retardant in the form of a cyclic phosphonate ester having excellent processability, such as heat resistance that does not degrade physical properties and uniform mixing with a base resin.
일반적으로, 주로 고분자 수지에 응용해온 난연제는 할로겐, 그중에서도 브롬(Br)이 포함되어 있는 Br계 난연제가 주로 사용되어 왔다. 이들의 난연성은 만족스러웠지만 연소시 유독가스 발생과 다이옥신이나 벤조퓨란과 같은 유해물질 발생등 환경에 대한 문제점이 대두 되었고, 수지와의 좋지 못한 상용성 등으로 인해 비 할로겐 난연제의 필요성이 점차 요구되어졌으며 이 방면의 연구가 다방면에서 활발하게 전개되어왔다. In general, a flame retardant mainly applied to a polymer resin has been mainly used a halogen flame, Br-based flame retardant containing bromine (Br). Their flame retardancy was satisfactory, but environmental problems such as the generation of toxic gas during combustion and the generation of harmful substances such as dioxin and benzofuran have emerged, and the necessity of non-halogen flame retardants has been gradually required due to poor compatibility with resins. This research has been actively developed in various fields.
비 할로겐 난연제로서는 무기수화물, 질소화합물, 인계 난연제 및 유기인계 난연제를 들 수 있는데, 무기 수화물의 경우는 바람직한 난연효과를 얻기 위해 너무 많은 양의 무기수화물을 사용해야 하고 그로 인해 성형가공성이 불량해지는 단점이 지적되고 있다. 질소산화물을 난연제로 사용하는 경우는 난연효과가 다소 미흡할뿐만 아니라 연소시의 유독가스도 문제점으로 대두되고 있는 상황이며, 적인을 주로 사용하는 인계 난연제는 수지의 기본 물성을 저하시킬 뿐만 아니라 적인 자체가 열이나 마찰충격에 민감하여 취급이나 저장, 혼합 등이 위험하고 작업환경이 양호하지 못한 단점이 있다. 유기인계 난연제는 여전히 개선되어야할 점들이 있기는 하지만 할로겐계 난연제를 대체할 수 있는 가장 바람직한 대안으로 인식되어 가장 활발한 연구가 진행되어 왔다. Non-halogen flame retardants include inorganic hydrates, nitrogen compounds, phosphorus flame retardants, and organophosphorous flame retardants. In the case of inorganic hydrates, too much inorganic hydrate must be used to obtain a desirable flame retardant effect, which results in poor moldability. It is pointed out. In the case of using nitrogen oxide as a flame retardant, not only the flame retardant effect is somewhat insufficient, but also toxic gas during combustion has become a problem. Phosphorus-based flame retardants using mainly red phosphorus not only lower the basic physical properties of the resin but also It is sensitive to heating and frictional shock, so it is dangerous to handle, store and mix, and the working environment is not good. Although organophosphorus flame retardants are still in need of improvement, they have been recognized as the most desirable alternatives to halogen flame retardants.
대표적인 유기인계 난연제인 트리페닐포스페이트(TPP)와 같은 트리아릴 포스페이트류는 가공중에 수지와 브릿지(bridge) 형성으로 수지 조성물의 물성에 좋지않은 영향을 미쳐왔고 열악한 내열성등으로 인해 가공 후 성형품 내에서의 불균일 분포로 인하여 충격강도의 저하와 같은 바람직하지 못한 물성이 문제점으로 지적되었다. 이러한 문제점을 극복하기위한 방안으로서 사이클릭 인산에스터 (cyclic phosphonate ester)형태를 합성하게 되었는데, 미국특허 제3,141,032호 에서는 펜타에리스리톨 (pentaerythritol)을 인계화합물( phosphite류)과 반응시켜 사이클릭 인산에스터를 합성하여 난연제로 사용하였지만 구조상의 문제로인해 여러 종류의 고분자 수지에 응용하기에는 한계가 있었다. 미국특허 제 3,789,091호 에서는 다음의 화학식 (I) 및 (II)와 같은 사이클릭 인산에스터의 구조를 제안하였고 미국특허 제 3,849,368호 에서는 이구조의 유기인계 난연제를 포함하는 수지 조성물을 제안하였는데, 이 구조는 지금까지도 내열성 및 내가수분해성 등이 우수하여 Br계 난연제를 대체할 수 있는 바람직한 유기인계 난여제로 평가되고 있지만, 이 물질을 합성하기 위해서는 고온의 질소 분위기하에서 장시간 반응시켜야 하고 제품외형의 황변현상이 자주 발생하는등 까다로운 제조 방법이 문제로 남아있었다. Triaryl phosphates, such as triphenylphosphate (TPP), a typical organophosphorus flame retardant, have had a bad effect on the physical properties of the resin composition by forming bridges with resins during processing, and have poor heat resistance. Due to the non-uniform distribution, undesirable physical properties such as a drop in impact strength were pointed out as problems. In order to overcome this problem, cyclic phosphonate ester (cyclic phosphonate ester) form was synthesized. In US Patent No. 3,141,032, pentaerythritol is reacted with a phosphite compound to synthesize cyclic phosphate ester. It was used as a flame retardant, but due to structural problems, there was a limit to the application to various types of polymer resins. U.S. Patent No. 3,789,091 proposes the structure of cyclic phosphate esters such as the following formulas (I) and (II), and U.S. Patent No. 3,849,368 proposes a resin composition comprising an organophosphorus flame retardant of this structure. Until now, it has been evaluated as a preferable organophosphorus flame retardant that can replace Br-based flame retardant because of its excellent heat resistance and hydrolysis resistance.However, in order to synthesize this material, it must be reacted for a long time in a high temperature nitrogen atmosphere and yellowing phenomenon of product appearance Frequent and difficult manufacturing methods remained a problem.
상기식에서 R1, R2 및 R3는 가각 수소원자 또는 C1 ~ C22의 알킬기, 알케닐기를 나타낸다.Wherein R 1, R 2 and R 3 represents a gagak a hydrogen atom or an alkyl group C 1 ~ C 22, alkenyl.
이와 유사한 종류의 사이클릭 인산에스터의 제조방법이 많이 알려져 있다. 미국 특허 제 3,801.677호 에서는 다음과 같이 치환이 용이한 페놀기를 가지고 있는 triphenyl phosphite에 다른 알콜로 치환반응을 시행하여 중간체를 형성시키고, 이 중간체에 펜타에리스리톨을 반응시켜 또 다른 중간체를 얻은 후, 이것을 Arbusov rearrangement반응을 시행하여 목적화합물을 얻고 있는데, 이 방법은 반응단계가 길뿐만 아니라 부산물로 생성되는 페놀을 진공증류 제거해야 하는등 산업적 적용성은 한계가 있는 방법이다.Many methods for producing cyclic phosphate esters of a similar kind are known. In US Patent No. 3,801.677, an intermediate is formed by performing a substitution reaction with another alcohol on triphenyl phosphite having a phenol group which is easily substituted as follows, and pentaerythritol is reacted with another intermediate to obtain another intermediate, which is then Arbusov. The rearrangement reaction is used to obtain the target compound. This method has a long industrial stage and has limited industrial applicability, such as distillation of phenol produced as a byproduct in vacuum.
미국특허 제 3,984,502호 에서는 펜타에리스리톨과 PCl3를 반응시켜 링을 형성시킨 후,이것을 에틸렌옥사이드와 반응시켜 중간체를 얻고, 다시 이것을 Arbusov rearrangement반응을 시켜 사이클릭 인산에스터를 얻고 있는데, 역시 반응단계가 길뿐만 아니라 부산물로서 발생하는 유독성의 염화수소(HCl)를 세척해 주어야하는 어려움이 있다. 미국특허 제 4,207,271호 에서는 다음과 같이 트리페닐포스파이트에 메탄올을 반응시켜 얻은 중간체를 Arbusov rearrangement를 먼저 시행하여 diphenyl methylphosphonate를 얻은 후, 이것을 펜타에리스리톨과 반응시켜 사이클릭 인산에스터를 얻고 있는데 이 방법 역시 반응단계가 길고 부산물로 생성되는 페놀을 진공증류로 제거해야 하는 어려움이 있다.In US Pat. No. 3,984,502, a ring is formed by reacting pentaerythritol with PCl 3 , which is then reacted with ethylene oxide to obtain an intermediate, which is then subjected to Arbusov rearrangement to obtain a cyclic phosphate ester. In addition, there is a difficulty in cleaning the toxic hydrogen chloride (HCl) generated as a by-product. In US Pat. No. 4,207,271, an intermediate obtained by reacting methanol with triphenylphosphite was first subjected to Arbusov rearrangement to obtain diphenyl methylphosphonate, which was then reacted with pentaerythritol to obtain a cyclic phosphate ester. The step is long and there is a difficulty in removing the by-product phenols by vacuum distillation.
독일 공개특허공보 제 3,432,574호 에서는 다음과 같이 치환이 가능한 인산에스터를 출발물질로 하여 다가 알콜기를 갖는 화합물을 반응시켜 사이클릭 인산에스터를 얻고 있는데, 이 방법 역시 부산물로 생성되는 알콜을 제거해 주어야 하고 치환되는 알콜이 페놀이 아닌 경우 반응이 완결되지 않거나 재현성이 떨어지는 방법으로 산업적 이용에는 한계가 있는 방법이다.German Patent Publication No. 3,432,574 discloses a cyclic phosphate ester by reacting a compound having a polyhydric alcohol group with starting phosphate ester which can be substituted as follows, and this method also needs to remove alcohol produced as a by-product. If the alcohol is not a phenol, the reaction is not complete, or the reproducibility is a method of limiting industrial use.
한편, 대한민국 공개특허공보 10-2005-0011394호 에서는 일반식 (I) 및 (II)의 사이클릭 인산에스터를 합성하는 방법으로 다음과 같이 트리메틸올알칸을 출발물질로 하여 첫단계에서 3개의 히드록시기중 2개를 보호한 중간체를 얻은 후, 2단계 반응에서 이것을 치환이 가능한 인산에스터와 trans esterification반응으로 또 다른 중간체를 얻고, 3 단계 반응에서 보호된 히드록시기를 치환 반응에 참여할 수 있도록 비보호시킨 후, 4 단계 반응에서 이것을 다시 치환 반응이 가능한 인산에스터와 반응 시킴으로써 목적화합물을 얻고 있는데, 지금까지 알려진 제조방법중 가장 반응단계가 길뿐만 아니라 이전의 방법들에 비해 반응용매를 사용하여 중간체를 제조하기 때문에 용매를 제거하는 시간이 길어지고, 2단계와 4단계에서 발생하는 알콜부산물을 제거해야하는 번거로움이 있어 산업적 이용가능성은 불투명하다.On the other hand, the Republic of Korea Patent Publication No. 10-2005-0011394 is a method for synthesizing the cyclic phosphate ester of the general formula (I) and (II) as a starting material in the three hydroxy groups in the first step as a starting material After the two protected intermediates were obtained, another intermediate was obtained by trans esterification with a phosphate ester which can be substituted in a two-step reaction, and the unprotected hydroxyl group in the three-step reaction was allowed to participate in the substitution reaction. In the step reaction, the target compound is obtained by reacting it with phosphate ester, which is capable of substitution reaction. The solvent is not only the longest reaction step known so far but also the intermediate is prepared using the reaction solvent compared to the previous methods. The longer it takes to remove, the more times you need to remove the alcohol byproducts that occur in steps 2 and 4 The hassle has made industrial applicability opaque.
이상과 같이 난연제로 유용한 유기인계 난연제로서의 사이클릭 인산에스터의 산업적 요구는 크지만 합당한 제조방법이 원할치 못했던 점을 예의 주시해온 본 발명자들은, 앞에서 기술한 이전의 방법들이 가지고 있는 사이클릭 인산에스터의 제조법상의 문제점들, 즉 반응단계가 길어서 이전의 할로겐계 난연제를 대체할 경쟁력이 미흡하여 산업적 적용성이 어려웠던 점이나, 염화수소와 같은 유독성 부산물이 발생하여 이것을 제거하기위해 세척제로서의 또 다른 염기를 사용해야 하는 번거로움, 그리고 페놀이나 기타 알콜류의 부산물이 발생하여 진공증류 공정을 거쳐야하는 문제점 및 고온 반응으로부터 수반되는 제품 외형의 황변현상등의 반응재현성 문제등을 종합적으로 고려하여 좀더 온화한 조건에서 부산물 생성없이 간편하게 사이클릭 인산에스터를 제조할 수 있는 방법을 연구한 결과 특수한 촉매구성을 통해 보다 온화한 조건에서 사이클릭 인산에스터를 제조할 수 있을뿐만 아니라, 사이클릭 인산에스터 구조에서 사이클(링)수를 사용하는 촉매 구성에 따라 조절 가능한 방법을 확립함으로써 본 발명을 완성하게 되었다.As described above, the inventors of the present invention have made a careful observation that the industrial needs of cyclic phosphate esters as organophosphorus flame retardants useful as flame retardants are great, but proper manufacturing methods are not desired. It was difficult to replace the previous halogen-based flame retardants due to the problems in the phase, ie, the lack of competitiveness to replace the previous halogen-based flame retardants, and the toxic by-products such as hydrogen chloride were generated, and the need to use another base as a cleaning agent to remove them. And the reaction reproducibility problem such as yellowing of the product appearance resulting from high temperature reaction due to the generation of by-products of phenol or other alcohols, and the vacuum distillation process. Click-in As a result of studying how to prepare esters, it is not only possible to prepare cyclic phosphate esters under milder conditions through special catalyst composition, but also according to the catalyst composition using cycle (ring) water in cyclic phosphate ester structure. By establishing an adjustable method, the present invention has been completed.
본 발명은 다음의 일반식 (I) 및 (II)로 표시되는 사이클릭 인산에스터를 제조하는 방법으로서, 하기 일반식 (III)의 bicyclic phosphite를 하기 일반식 (IV)의 인산에스터와 특수한 촉매 존재하에서 rearrangement반응을 유도하여 목적화합물을 얻는 제조법으로서, 단일단계 반응의 용매없이 반응시킬 수 있는 간결한 방법으로 황변현상이 없는 제품외형을 유지 시킬 수 있는 재현성있는 제조방법을 제공한다.The present invention provides a method for producing a cyclic phosphate ester represented by the following general formulas (I) and (II), wherein bicyclic phosphite of the general formula (III) is present with a phosphate ester of the general formula (IV) It is a manufacturing method to obtain the target compound by inducing rearrangement reaction under the simple method, which provides a reproducible manufacturing method that can maintain the appearance of the product without yellowing as a concise method that can be reacted without solvent of a single step reaction.
상기식에서 R1, R2 및 R3는 가각 수소원자 또는 C1 ~ C22의 알킬기, 알케닐기를 나타낸다.Wherein R 1, R 2 and R 3 represents a gagak a hydrogen atom or an alkyl group C 1 ~ C 22, alkenyl.
본 발명에서 출발물질로 사용하는 일반식 (III)의 bicyclic phosphite는 미국특허 제 3,155,703호 에서 제시한 방법처럼 저 분자량의 트리알킬 포스파이트로부터 트리메틸올알칸과 치환반응으로 간단히 합성하거나 미국특허 제 3,755,270호에서 처럼 PCl3와 트리메틸올알칸을 반응시켜 합성할 수 있고 상업화 되어 있으며 일반식 (IV)의 인산에스터는 대량공급이 가능한 화학제품이다.Bicyclic phosphite of the general formula (III) used as a starting material in the present invention can be synthesized simply by substitution reaction with trimethylolalkane from trialkyl phosphite of low molecular weight, as described in US Pat. No. 3,155,703, or US Pat. No. 3,755,270. It is synthesized and commercialized by reacting PCl 3 with trimethylol alkanes, and the phosphate ester of formula (IV) is a chemical that can be supplied in large quantities.
본 발명에서는 rearrangement가 유도되는 반응메카니즘(mechanism)을 고려하여 사이클릭 인산에스터 구조에서 사이클(링)수를 조절할 수 있는 방법을 확립하였는데 rearrangement 반응의 촉매조성을 달리 함으로써 명확하게 그 목적을 달성할 수 있었다. 사용하는 촉매는 2가지로 구성되어지고 각각의 촉매는 서로다른 역할을 하는데, 하나는 황변현상이 일어나지 않도록 하여 제품의 외형을 안정적으로 유지시키는 역할을 하고, 다른 하나는 사용하는 종류에따라 사이클릭 인산에스터 구조에서 사이클(링)수를 조절하는 역할을 수행하게된다. 반응매카니즘은 다음의 단계로 설명이 가능하며, bicyclic phosphite의 인에 있는 비공유전자쌍이 또 다른 출발물질중의 하나인 인산에스터의 알콕시의 알킬기를 공격하는 것을 시작으로 설명가능하다.In the present invention, the method of controlling the number of cycles in the cyclic phosphate structure is established in consideration of the reaction mechanism in which rearrangement is induced. However, the purpose of the rearrangement reaction can be clearly achieved by changing the catalyst composition of the rearrangement reaction. . Two catalysts are used, and each catalyst plays a different role. One catalyst plays a role of maintaining the appearance of the product stably by preventing yellowing, and the other cyclic according to the type used. In the phosphate ester structure, the number of cycles (ring) is controlled. The reaction mechanism can be explained by the following steps, beginning with the attack of the alkoxy alkyl group of the phosphate ester, one of the other starting materials, by the non-covalent pair of electrons in the phosphorus of bicyclic phosphite.
<모노사이클릭 인산에스터 합성 Mechanism><Monocyclic Phosphate Ester Synthesis Mechanism>
<바이사이클릭 인산에스터 합성 Mechanism><Bicyclic Phosphate Synthesis Mechanism>
상기식에서 R1, R2, R3는 앞에서 정의한 바와 같다.In the above formula, R 1 , R 2 , R 3 are as defined above.
앞에서 기술한 반응메카니즘에서 속도 결정단계는 모노 사이클릭이나 바이사이클릭 인산에스터의 경우 모두 첫 번째단계 인의 비공유 전자쌍이 인산에스터의 알킬기를 공격하며 인과 산소에 각각 +와 -의 전하를 갖는 불안정한 중간단계를 형성 시키는 단계로 추정할 수 있으며, 본 발명자들은 이 메카니즘상의 속도 결정단계에 이론적으로 접근하여, 크기와 성질이 다른 여러 촉매를 적용시키며 반응들을 추적한 결과 촉매의 종류에 따라 모노사이클릭 인산에스터와 바이사이클릭 인산에스터를 선택적으로 조절하며 합성할 수 있는 방법을 확립하였다.In the reaction mechanism described above, the rate determining step is the first step in both monocyclic and bicyclic phosphate esters.The unstable intermediate step in which the unpaired electron pair of phosphorus attacks the alkyl group of the phosphate ester and has a charge of + and-to phosphorus and oxygen, respectively Theoretic approach to the rate-determining phase of this mechanism is applied, and the present inventors apply various catalysts of different sizes and properties, and trace the reactions to determine the monocyclic phosphate ester according to the type of catalyst. We have established a method to selectively control and synthesize bicyclic phosphate esters.
촉매로서 일반적인 루이스산 대부분이 모노사이클릭 인산에스터 합성반응을 촉매 없이 반응시키는 경우에 비해 더 온화한 조건에서 반응을 진행시킬 수 있다. 이때 사용가능한 루이스산으로는 AlCl3, AlBr3, MgCl2, CuCl2, CuBr2, ZnCl2, ZnBr2, FeCl3, FeCl2,CoCl2, CoCl3, NiCl2등을 사용가능하며, 사용량은 전체반응중 무게비 0.01 내지 0.5%의 사용이 바람직하며 반응온도는 150 내지 210 oC, 바람직하게는 170 내지 190oC가 적합한 반응온도이다. 이들은 앞에 기술한 메카니즘의 첫단계에서 인의 비공유 전자쌍이 인산에스터의 알킬기를 공격할 때 반응성을 증대시키는 역할을 하는 것으로 추정된다.Most of Lewis's acids as catalysts can proceed under milder conditions than when monocyclic phosphate ester synthesis is carried out without a catalyst. At this time, the available Lewis acid may be AlCl 3 , AlBr 3 , MgCl 2 , CuCl 2 , CuBr 2 , ZnCl 2 , ZnBr 2 , FeCl 3 , FeCl 2 , CoCl 2 , CoCl 3 , NiCl 2, etc. The use of a weight ratio of 0.01 to 0.5% during the whole reaction is preferred and the reaction temperature is 150 to 210 ° C., preferably 170 to 190 ° C., is a suitable reaction temperature. They are believed to play a role in increasing the reactivity when unpaired electron pairs of phosphorus attack the alkyl group of the phosphate ester in the first step of the mechanism described above.
<루이스산의 역할>Role of Lewis
루이스산의 사용은 사이클릭 인산에스터의 합성을 용이하게 하지만 제품외관에 영향을 미치는 황변현상까지 방지하지는 못한다. 황변 현상을 방지하는 방법도 본 발명의 주요부분이며 본 발명에서는 루이스산과 더불어 황변현상을 방지할 수 있는 또 다른 촉매를 혼합으로 사용하며 반응결과를 추적한 결과 알칼리금속을 함유하는 염기를 루이스산과 혼합사용하여 황변현상을 억제하는 방법을 확립함으로써 본 발명을 완성하게 되었다. 본 발명에서 사용하는 알칼리금속 함유 염기는 LiOH, NaOH, KOH, MeONa, EtONa 등이 가능하고, 그 사용량은 무게비로 0.01 내지 0.5% 사용이 바람직하다. 이하 본 발명을 실시예에 의거 더욱 상세히 설명한다. 그러나, 본 발명이 실시예에 명시된 방법들에 국한되는 것은 아니다.The use of Lewis acids facilitates the synthesis of cyclic phosphate esters but does not prevent yellowing which affects the appearance of the product. The method of preventing yellowing is also an important part of the present invention, and in the present invention, a mixture of Lewis acid and another catalyst capable of preventing yellowing is mixed, and the base of the reaction is mixed with a base containing alkali metal with Lewis acid. The present invention has been completed by establishing a method of suppressing yellowing by using the method. The alkali metal-containing base used in the present invention may be LiOH, NaOH, KOH, MeONa, EtONa and the like, and the amount of the alkali metal-containing base is preferably 0.01 to 0.5% by weight. Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the methods specified in the Examples.
실시예 1Example 1
250 mL 플라스크에 bicyclic phosphite 64.9g(0.40 mol)과 methyl dimethylphosphonate 49.6g(0.40 mol), NaOH 0.05g 및 ZnCl2 0.08g을 넣고 질소기류하에서 서서히 가열하여 내부 온도를 180 oC로 상승시키며 교반한다. 180 내지 190 oC에서 12시간 교반하여 반응을 완결시키면 전체 반응 혼합물이 투명한 무색 용액이 되며 Gas Chromatography분석에서 출발 물질인 bicyclic phosphite와 methyl dimethylphosphonate가 소량 남지만 모노사이클릭 인산에스터가 85%이상이고 바이사이클릭 인산에스터가 소량 생성되어 있다.In a 250 mL flask, 64.9 g (0.40 mol) of bicyclic phosphite, 49.6 g (0.40 mol) of methyl dimethylphosphonate, 0.05 g of NaOH, and 0.08 g of ZnCl 2 were slowly heated under a nitrogen stream to raise the internal temperature to 180 ° C. and stirred. After completion of the reaction by stirring at 180 to 190 o C for 12 hours, the entire reaction mixture becomes a clear colorless solution.In the gas chromatography analysis, small amounts of bicyclic phosphite and methyl dimethylphosphonate, which are starting materials, remain above 85% of monocyclic phosphate and A small amount of click phosphate ester is produced.
실시예 2Example 2
250 mL 플라스크에 bicyclic phosphite 64.9g(0.40 mol)과 methyl dimethylphosphonate 59.6g(0.48 mol), NaOH 0.05g 및 ZnCl2 0.08g을 넣고 질소기류하에서 서서히 가열하여 내부 온도를 180 oC로 상승시키며 교반한다. 180 내지 190 oC에서 12시간 교반하여 반응을 완결시키면 전체 반응 혼합물이 투명한 무색 용액이 되며 Gas Chromatography분석에서 bicyclic phosphite는 남아있지 않고 methyl dimethylphosphonate가 소량 남지만 모노사이클릭 인산에스터가 90%이상이고 바이사이클릭 인산에스터가 거의 생성되어 있지 않다. 소량 남아 있는 methyl dimethylphosphonate는 끓는 온도가 이 반응온도이므로 질소를 통과시켜 쉽게 제거 가능하고 소량이므로 그대로 난연제로 사용하는 경우에도 전체적인 물성에는 큰 영향이 없다.In a 250 mL flask, 64.9 g (0.40 mol) of bicyclic phosphite, 59.6 g (0.48 mol) of methyl dimethylphosphonate, 0.05 g of NaOH, and 0.08 g of ZnCl 2 were slowly heated under a nitrogen stream to raise the internal temperature to 180 ° C. and stirred. After completion of the reaction by stirring at 180 to 190 o C for 12 hours to complete the reaction, the entire reaction mixture becomes a clear, colorless solution. In gas chromatography analysis, bicyclic phosphite is not left, and methyl dimethylphosphonate is left in a small amount. There is almost no click phosphate ester. The remaining amount of methyl dimethylphosphonate can be easily removed by passing nitrogen because the boiling temperature is this reaction temperature, and even if used as a flame retardant, there is no significant effect on the overall physical properties.
실시예 3Example 3
250 mL 플라스크에 bicyclic phosphite 64.9g(0.40 mol)과 methyl dimethylphosphonate 49.6g(0.40 mol), NaOH 0.05g 및 AlCl3 0.07g을 넣고 질소기류하에서 서서히 가열하여 내부 온도를 175 oC로 상승시키며 교반한다. 175 내지 185 oC에서 12시간 교반하여 반응을 완결시키면 전체 반응 혼합물이 투명한 무색 용액이 되며 Gas Chromatography분석에서 bicyclic phosphite는 남아있지 않으며 methyl dimethylphosphonate가 소량 남지만 모노사이클릭 인산에스터가 30%이하이고 바이사이클릭 인산에스터가 60%이상 생성되어있다. 소량 남아 있는 methyl dimethylphosphonate는 질소를 통과시켜 쉽게 제거 가능하고 소량이므로 그대로 난연제로 사용하는 경우에도 전체적인 물성에는 큰 영향이 없다.In a 250 mL flask, add 64.9 g (0.40 mol) of bicyclic phosphite, 49.6 g (0.40 mol) of methyl dimethylphosphonate, 0.05 g of NaOH, and 0.07 g of AlCl 3 , and slowly heat it under nitrogen stream to raise the internal temperature to 175 ° C. and stir. When the reaction was completed by stirring for 12 hours at 175 to 185 o C, the entire reaction mixture became a clear colorless solution. In gas chromatography analysis, no bicyclic phosphite remained and a small amount of methyl dimethylphosphonate remained, but less than 30% of monocyclic phosphate ester, More than 60% of click phosphate esters are produced. The remaining amount of methyl dimethylphosphonate can be easily removed by passing nitrogen and small amount, so even when used as a flame retardant, there is no significant effect on the overall physical properties.
실시예 4Example 4
250 mL 플라스크에 bicyclic phosphite 129.8g(0.80 mol)과 methyl dimethylphosphonate 49.6g(0.40 mol), NaOH 0.05g 및 AlCl3 0.07g을 넣고 질소기류하에서 서서히 가열하여 내부 온도를 175 oC로 상승시키며 교반한다. 175 내지 185 oC에서 12시간 교반하여 반응을 완결시키고 실온으로 냉각하면 연한 노란색 고체가 생성 되며 Gas Chromatography분석에서 bicyclic phosphite와 methyl dimethylphosphonate는 남아 있지 않으며 모노사이클릭 인산에스터가 3%이하이고 바이사이클릭 인산에스터가 95%이상 생성되어있다.129.8 g (0.80 mol) of bicyclic phosphite, 49.6 g (0.40 mol) of methyl dimethylphosphonate, 0.05 g of NaOH, and 0.07 g of AlCl 3 were added to a 250 mL flask, and the mixture was heated slowly under a nitrogen stream to raise the internal temperature to 175 ° C. and stirred. Stirring at 175 to 185 o C for 12 hours to complete the reaction and cooling to room temperature yielded a pale yellow solid. Gas chromatographic analysis showed no bicyclic phosphite and methyl dimethylphosphonate, less than 3% of monocyclic phosphate and bicyclic More than 95% of phosphate esters are produced.
실시예 5Example 5
실시예 1에서 ZnCl2 대신 FeCl3를 사용하는 것을 제외하고는 실시예 1과 동일한 방법을 시행하여 실시예 1과 동일한 결과를 얻었다.Except for using FeCl 3 instead of ZnCl 2 in Example 1 The same method as in Example 1 was carried out to obtain the same results as in Example 1.
실시예 6Example 6
실시예 4에서 AlCl3 대신 AlBr3를 사용하는 것을 제외 하고는 실시예 4와 동일한 방법을 시행하여 실시예 4와 동일한 결과를 얻었다.Except for using AlBr 3 instead of AlCl 3 in Example 4 The same method as in Example 4 was carried out to obtain the same results as in Example 4.
실시예 7Example 7
실시예 2에서 NaOH대신 NaOMe를 사용하는 것을 제외 하고는 실시예 2와 동일한 방법을 시행하여 실시예 2와 동일한 결과를 얻었다.Except for using NaOMe instead of NaOH in Example 2, the same method as in Example 2 was carried out to obtain the same results as in Example 2.
본 발명에서는 그동안 우수한 물성을 확인 하고도 적절한 제조방법이 없어 원할한 공급이 어려웠던 사이클릭 인산에스터의 새로운 합성 방법을 제공함으로써 기존의 방법들이 안고 있던 문제점들, 즉 여러반응단계의 불합리한 합성방법과 격렬한 반응조건 및 부산물의 생성 및 부산물의 제거 공정을 획기적으로 개선한, 한단계 반응이면서 부산물생성이 없는 온화한 조건의 황변현상 없는 제조방법을 확립하였으며 기존의 사이클릭 인산에스터의 제조공정은 물론이고 향후 더 개선된 물성을 갖는 신규 구조의 사이클릭 인산에스터의 합성에도 응용가능하여 그 산업적 응용 범위가 더욱 넓어질 것으로 기대된다.The present invention provides a new method of synthesis of cyclic phosphate esters, which has been difficult to supply smoothly because there is no proper manufacturing method even after confirming excellent physical properties, that is, problems with existing methods, that is, unreasonable synthesis method of various reaction steps and violent Established a method of producing yellowing under mild conditions with one-step reaction and no by-products, which greatly improved the reaction conditions, by-products generation and removal of by-products, and further improved the manufacturing process of the existing cyclic phosphate esters as well as in the future. It is also expected to be applicable to the synthesis of cyclic phosphate esters of novel structure with improved physical properties, thereby broadening their industrial application.
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| KR20230024043A (en) | 2021-08-11 | 2023-02-20 | (주)에이론 | Organophosphate flame retardant composition for thermal reflective insulation panel and composition method thereof |
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| KR101814196B1 (en) | 2015-04-14 | 2018-01-30 | 주식회사 영주양행 | Novel phosphorus compound and the method for preparing thereof |
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| KR101085381B1 (en) * | 2009-12-10 | 2011-11-22 | (주)서진라이트 | Composition for flame retardant transparent light shaft board |
| KR20230024043A (en) | 2021-08-11 | 2023-02-20 | (주)에이론 | Organophosphate flame retardant composition for thermal reflective insulation panel and composition method thereof |
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