KR880002005B1 - Process for the preparation of phosphine compounds - Google Patents
Process for the preparation of phosphine compounds Download PDFInfo
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- KR880002005B1 KR880002005B1 KR1019850002785A KR850002785A KR880002005B1 KR 880002005 B1 KR880002005 B1 KR 880002005B1 KR 1019850002785 A KR1019850002785 A KR 1019850002785A KR 850002785 A KR850002785 A KR 850002785A KR 880002005 B1 KR880002005 B1 KR 880002005B1
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- 238000000034 method Methods 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 4
- 150000003003 phosphines Chemical class 0.000 title 1
- -1 malonic acid diester Chemical class 0.000 claims abstract description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001361 adipic acid Substances 0.000 claims abstract description 3
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- 239000001384 succinic acid Substances 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims 1
- 235000013922 glutamic acid Nutrition 0.000 claims 1
- 239000004220 glutamic acid Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- SNKAWJBJQDLSFF-NVKMUCNASA-N 1,2-dioleoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/CCCCCCCC SNKAWJBJQDLSFF-NVKMUCNASA-N 0.000 abstract description 5
- 239000010408 film Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical group 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 229960002989 glutamic acid Drugs 0.000 abstract 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 C1C=C(**C2=CC=CCC22)C2=CC1 Chemical compound C1C=C(**C2=CC=CCC22)C2=CC1 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VSOYJNRFGMJBAV-UHFFFAOYSA-N N.[Mo+4] Chemical compound N.[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- UANQBSLQFDXBAX-UHFFFAOYSA-N diethyl butanedioate;sodium Chemical compound [Na].CCOC(=O)CCC(=O)OCC UANQBSLQFDXBAX-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition 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
- 239000003039 volatile agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- C07F9/547—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
- C07F9/6574—Esters of oxyacids of phosphorus
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Description
본 발명은 내염성을 가진 섬유, 필름, 수지등의 제조원료로 이용될 수 있는 유기인 화합물로서 다음의 구조식으로 표시되는 신규인 포스핀 화합물의 제조방법에 관한 것이다.The present invention relates to a method for producing a novel phosphine compound represented by the following structural formula as an organophosphorus compound that can be used as a raw material for flame retardant fibers, films, resins and the like.
식중, R은 탄소수 1-4의 알킬기이며 ; R1은 -COOC2H5, -COOCH3, -COOCH2CH2OH이며, R2는 할로겐 또는 1-4의 알킬이며, n1은 2의 정수이며, n2는 0-2의 정수를 나타낸다.In the formula, R is an alkyl group having 1 to 4 carbon atoms; R 1 is -COOC 2 H 5 , -COOCH 3 , -COOCH 2 CH 2 OH, R 2 is halogen or 1-4 alkyl, n 1 is an integer of 2 , n 2 is an integer of 0-2 Indicates.
n2와 n3눈 같거나 다르며, 각각 0-4의 정수를 나타낸다.n 2 and n 3 are the same or different and each represents an integer of 0-4.
최근 세계적 추세에 따라 난연화 기술에 대한 관심이 높아지고 소방법에 의한 방화규제가 강화됨에 따라 섬유, 필름, 수지, 도료 등의 일상품에 대한 난연화 기술개발에 활기를 띠게 되었다.In recent years, as the interest in flame retardant technology has increased according to the global trend, and fire protection regulations have been strengthened by fire fighting methods, the development of flame retardant technology for textiles, films, resins, paints, and other commodities has been invigorated.
종래에 내염성을 부여하는 방법으로는 브롬등의 할로겐계 단분자 화합물 또는 인산 트리페닐과 같은 인산 에스테르류나 벤젠, 포스폰산유도체와 같은 포스폰산류 등을 성형물의 제조시에 첨가하는 방법이 사용되어 왔다.Conventionally, as a method of imparting flame resistance, a method of adding halogen-based monomolecular compounds such as bromine or phosphate esters such as triphenyl phosphate or phosphonic acids such as benzene and phosphonic acid derivatives in the production of moldings has been used. .
그러나 이와 같은 화합물을 이용하는 경우에는 성형물 제조에 사용되는 촉매의 활성이 떨어지고 폴리머의 융점이 저하되거나 겔화현상등으로 내염성이 우수한 폴리머를 얻을 수 없을 뿐만 아니라. 성형물을 지속적으로 사용하는 경우인 화합물이 유리되어 영구 난연성을 기대할 수 없는 문제점이 있었다.However, when such a compound is used, it is not only possible to obtain a polymer having excellent flame resistance due to a decrease in the activity of the catalyst used in the production of the molding, a low melting point of the polymer, or gelation. There is a problem that the compound is released when the molding is used continuously can not expect permanent flame retardancy.
본 발명자들은 종래의 이러한 난연화 방법의 문제점을 해결하기 위하여 오랜 연구를 행한 결과, 에스테르 형성기인 2개의 카르복실기를 가지는 상기 구조식(I)의 신규 화합물을 폴리에스테르 제조시에 첨가하여 공중합시킴으로서 내염성이 우수하고 가교화 반응이 없는 성형품을 제조활 수 있는 사실을 발견하여 본 발명을 완성하게 되었다.The present inventors conducted a long study to solve the problems of the conventional flame retardant method, and as a result, by adding a new compound of the above formula (I) having two carboxyl groups as ester forming group in the preparation of polyester to copolymerize excellent flame resistance The present invention was completed by discovering the fact that a molded article without crosslinking reaction can be produced.
따라서 본 발명의 목적은 신규의 상기 구조식(I)화합물을 제공하는 것이다.It is therefore an object of the present invention to provide novel compounds of formula (I).
상기인 화합물의 구체적인 제조예는 다음과 같은 방법에 의하여 제조가능하다. 즉, 9,10-디하이드로-9-옥사-10-포스퍼펜안트렌-10-클로라이드(9,10-디하이드로-9-옥사-10-포스퍼펜안트렌-10-클로라이드 ; 이하 DOPC라 함), 또는 그의 벤젠핵 치환체와 카르보 음이온(carbanion)을 가진 금속(Na, Zn, Li, Mg) 카르복실산 에스테르와 반응시키는 것에 의해 제조될 수 있고, 또 상기 반응후 디올과 에스테르화하여 제조하는것이 가능하다. 상기 카르복실 화합물로서는, 말론산, 숙신산, 글루탄산, 아디프산 등의 디카르복실산의 에스테르화 물이 선택된다.Specific preparation examples of the compound may be prepared by the following method. That is, 9,10-dihydro-9-oxa-10-phosphorphenanthren-10-chloride (9,10-dihydro-9-oxa-10-phosphorphenanthren-10-chloride; hereinafter referred to as DOPC ), Or by reacting a benzene-nuclear substituent thereof with a metal (Na, Zn, Li, Mg) carboxylic acid ester having a carbanion, followed by esterification with a diol after the reaction. It is possible to do As said carboxyl compound, esterified products of dicarboxylic acids, such as malonic acid, succinic acid, glutanoic acid, and adipic acid, are selected.
또 상기 DOPC 또는 그의 벤젠핵 치환체는 2-하이드록시-비페닐 또는 그의 핵 치환체와 염화인 또는 산화염화인의 븐응에서 얻어지는 중간체이다.The DOPC or its benzene-nuclear substituent is an intermediate obtained from the reaction of 2-hydroxy-biphenyl or its nuclear substituent and phosphorus chloride or phosphorus oxychloride.
상기 일반식(I)로 표시되는 인화합물의 구체적인 예로서 다음과 같은 것들을 열거할 수 있다.Specific examples of the phosphorus compound represented by the general formula (I) include the following ones.
상기 인화합물(I)의 인 함유율은 시료를 황산, 질산, 과염소산으로 가열 분해하여 몰리브텐 암모늄 및 황산하이드라진으로 발색하여 비색 측정하여, 적외선 흡수펙트럼은 브롬화칼륨과 혼합 판상으로 만들어 측정하고 핵자기 공명스펙트럼(NMR)은 증수소화 클로로포름을 용매로 사용하고, BRUKER WP 80 SY로 1사이클/초의 필터폭, 250초의 스위프시간 500사이클/초의 스위프 폭의 조건하에서 TMS를 내부 기준으로 측정하였다.The phosphorus content of the phosphorus compound (I) was measured by color decomposition by thermal decomposition of the sample with sulfuric acid, nitric acid, and perchloric acid, followed by color development with molybdenum ammonium and hydrazine sulfate. Resonance Spectrum (NMR) measured the TMS as an internal reference using distilled chloroform as a solvent and under the conditions of a filter width of 1 cycle / sec and a sweep width of 250 seconds and a sweep width of 250 seconds with a BRUKER WP 80 SY.
이하 본 발멸을 실시예에 의거 상세히 설명하면 다음과 같다.Hereinafter will be described in detail based on the present utterance as follows.
[실시예 1]Example 1
교반기, 냉각콘덴사, 온도계를 갖춘 1ℓ의 4구플라스크에 234g의 9,10-디하이드로-9-옥소-10-포스퍼펜안트렌-10-클로라이드(DOPC), 182g의 나트륨말론산디에틸을 넣고 90℃로 유지한 중탕에서 10분간 교반한다.Into a 1 liter four-necked flask equipped with a stirrer, a cooling condenser, and a thermometer, 234 g of 9,10-dihydro-9-oxo-10-phosphorphenanthrene-10-chloride (DOPC) and 182 g of diethyl sodium malonate were added. Stir for 10 minutes in a hot water bath maintained at 90 ℃.
이때 90℃의 물 200ml를 혼합하고 강하게 교반하면서 상온으로 냉각시킨 후 여과된 고체를 물 100ml로 세척, 건조하여 백색 고체의 포스핀 화합물(a) 330g을 얻는다At this time, 200 ml of water at 90 ° C. were mixed, cooled to room temperature with vigorous stirring, and the filtered solid was washed with 100 ml of water and dried to obtain 330 g of a white solid phosphine compound (a).
상술한 바와 같이, 제조된 화합물 (a)의 원소분석가는 P〓8.62, C〓63.72%, H〓5.34%로서 이론치 P〓8.66%, C〓63.69%, H〓5.31%와 잘 일치했다. 또 산가는 0.00meq/kg이었다. 적외선 흡수 스펙트럼은 진동수 3000-3050cm-1에서 페닐의 C-H, 1720cm-1에서 C〓0.1440cm-1에서 P-C, 1100cm-1에서 P-O 결합의 흡수띠를 나타내고, NMR에 의한 분석으로 부터 상기 구조식을 갖음이 확인되었다.As described above, the elemental analysts of the prepared compound (a) were well matched with the theoretical values of P8.66%, C633.69% and H5.31% as P'8.62, C'63.72% and H'5.34%. The acid value was 0.00 meq / kg. The infrared absorption spectrum shows the absorption band of the PO bond in the PC, 1100cm -1 in C〓0.1440cm -1 in the phenyl CH, 1720cm -1, at a frequency 3000-3050cm -1, the gateum the formula from the analyzes by NMR Confirmed.
[실시예 2]Example 2
교반기, 냉각콘덴서, 온도계를 갖춘 1ℓ의 4구플라스크에 234g의 DOPC, 195g의 나트륨 숙신산 디에틸 에스테르를 500ml의 클로로포름과 혼합하여 90℃의 중탕에서 10분간 교반후. 상온으로 냉각후 여과한다. 염이 제거된 여과액을 증류하여 화합물(d)를 얻는다.In a 1 L four-necked flask equipped with a stirrer, a cooling capacitor and a thermometer, 234 g of DOPC and 195 g of sodium succinic acid diethyl ester were mixed with 500 ml of chloroform and stirred for 10 minutes in a 90 ° C. hot water bath. After cooling to room temperature, it is filtered. The filtrate from which the salt was removed is distilled off to obtain compound (d).
[실시예 3]Example 3
교반기, 냉각콘덴서, 온도계를 갖춘 1ℓ의 4구 플라스크에 실시예(2)로 제조된 370g의 고체(d) 및 350g의 에틸렌글리콜을 넣고, 200℃로 유지된 오일 중탕에서 생성된 에탄올이 에틸렌글리콜과 함께 증류될때까지 3시간 동안 질소 분위기에서 교반한다. 최종적으로 0.1mmHg의 감압하 100℃에서 휘발물질을 제거한다. 얻어진 내용물은 무색 투명한 고농조액으로 이 액체(e)의 인 함유율은 7.69%, C〓59.6%, H〓5.11%로서, 이론치 P〓7.67%, C〓59.4%, H〓5.12%와 잘 일치했다. 또 산가 및 적외선 흡수스펙트럼, NMR 분석으로 하기 구조의 포스핀 화합물(e)를 확인했다.Into a 1 L four-necked flask equipped with a stirrer, a cooling capacitor, and a thermometer, 370 g of solid (d) and 350 g of ethylene glycol prepared in Example (2) were placed, and the ethanol produced in the oil bath maintained at 200 ° C was ethylene glycol. Stir in nitrogen atmosphere for 3 hours until distillation with. Finally, the volatiles were removed at 100 ° C. under a reduced pressure of 0.1 mmHg. The resulting content was a colorless, transparent, high-concentrate liquid with a phosphorus content of 7.69%, C〓59.6%, and H〓5.11%, which is in good agreement with theoretical values of P7.67%, C〓59.4%, and H〓5.12%. did. Moreover, the phosphine compound (e) of the following structure was confirmed by acid value, infrared absorption spectrum, and NMR analysis.
본 발명의 효과로는 유기인 화합물 폴리에스테르 제조시에 첨가하여 공중합시킨 결과 촉매 활성 저하 폴리머 융점저하, 겔화 현상으로 내염성저하와 같은 종래의 문제점이 해결되어 내염성이 우수하고 가교화 반응이 없는 성형품을 제조 가능하였다.The effect of the present invention is that in the preparation of the organophosphorus polyester, copolymerization is carried out. As a result, conventional problems such as lowering of the catalyst activity, lowering the melting point of the polymer, and lowering the flame resistance due to gelation are solved. It was possible to manufacture.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019850002785A KR880002005B1 (en) | 1985-04-25 | 1985-04-25 | Process for the preparation of phosphine compounds |
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| KR1019850002785A KR880002005B1 (en) | 1985-04-25 | 1985-04-25 | Process for the preparation of phosphine compounds |
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| KR880002005B1 true KR880002005B1 (en) | 1988-10-11 |
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| WO2014200147A1 (en) * | 2013-06-10 | 2014-12-18 | 제일모직 주식회사 | (meta)acrylic-based fine particle, preparation method therefor and thermoplastic resin composition including same |
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| WO2014200147A1 (en) * | 2013-06-10 | 2014-12-18 | 제일모직 주식회사 | (meta)acrylic-based fine particle, preparation method therefor and thermoplastic resin composition including same |
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