WO2019006774A1 - 一种DiDOPO类化合物的制备方法 - Google Patents

一种DiDOPO类化合物的制备方法 Download PDF

Info

Publication number
WO2019006774A1
WO2019006774A1 PCT/CN2017/092574 CN2017092574W WO2019006774A1 WO 2019006774 A1 WO2019006774 A1 WO 2019006774A1 CN 2017092574 W CN2017092574 W CN 2017092574W WO 2019006774 A1 WO2019006774 A1 WO 2019006774A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
group
acid
ketone
chloroorganophosphine
Prior art date
Application number
PCT/CN2017/092574
Other languages
English (en)
French (fr)
Inventor
姚强
赵月英
曹微虹
刘正西
邓永源
唐倩
Original Assignee
中国科学院宁波材料技术与工程研究所
贵州源翼磷系新材料股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院宁波材料技术与工程研究所, 贵州源翼磷系新材料股份有限公司 filed Critical 中国科学院宁波材料技术与工程研究所
Publication of WO2019006774A1 publication Critical patent/WO2019006774A1/zh

Links

Images

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
    • C07F9/657172—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 the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)

Definitions

  • the present application relates to a method for preparing a DiDOPO-based compound, and belongs to the field of halogen-free flame retardants.
  • Polymer materials are widely used in electronics, automotive, construction, textile and other industries. However, since the polymer material is flammable, it is necessary to add a flame retardant in actual use to meet the requirements of fire safety. Phosphonates, especially 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative flame retardants have received attention due to their high flame retardant efficiency and environmental friendliness.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • U.S. Patent No. 9522927 discloses DiDOPO having a vinylidene bridge structure, which is prepared by using an expensive strong base as a reactant, and has a low yield, resulting in high cost.
  • Chinese patent application CN104086593 uses the DiDOPO method for preparing an aromatic substituted vinylidene bridge structure by the action of DOPO and an arylalkyl ketone under the action of a catalyst such as phosphorus oxychloride.
  • the method is simple and convenient, but the DOPO needs to be prepared first.
  • the phosphorus oxychloride is not safe and increases the cost.
  • the preparation method of the compound I characterized in that the ketone compound II and the chloroorganophosphine compound III in the presence of an oxygenate to prepare the compound I;
  • the compound I is selected from at least one of the compounds having a structural formula represented by the formula (I):
  • the ketone compound II is selected from at least one selected from the group consisting of compounds of the formula (II);
  • the chloroorganophosphine compound III is selected from at least one selected from the group consisting of compounds of the formula (III);
  • Ar is selected from a C 3 -C 18 heteroaryl group or a C 6 -C 18 aryl group;
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, a C 1 -C 18 alkyl group, a C 3 -C 18 heteroaryl group, and a C 6 -C 18 aryl group;
  • R 3 , R 4 , R 5 and R 6 are independently selected from hydrogen, C 1 -C 18 alkyl, C 3 -C 18 heteroaryl, C 6 -C 18 aryl;
  • n, k and p are independently selected from 0, 1, 2, 3, 4;
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, a C 1 -C 18 alkyl group, a C 3 -C 18 heteroaryl group, and a C 6 -C 18 aryl group;
  • q and j are independently selected from 0, 1, 2, 3, 4;
  • Any hydrogen atom on the aryl or heteroaryl aromatic ring may be independently substituted with any C 1 -C 18 alkyl group.
  • R 1 is hydrogen
  • R 2 is aryl
  • R 1 is hydrogen
  • R 2 is alkyl
  • Common heteroaryl groups are furyl, benzofuranyl, isobenzofuranyl, pyrrolyl, indolyl, isodecyl, thienyl, benzo[b]thienyl, benzo[c]thienyl Imidazole Benzomidazolyl, fluorenyl, pyrazolyl, oxazolyl, oxazolyl, benzoxazolyl, isoxazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, pyridyl , quinolyl, isoquinolyl, pyrazinyl, quinoxalinyl, acridinyl, pyrimidinyl, quinazolinyl, pyridazinyl, pyridazinyl and porphyrinyl.
  • Common aryl groups are phenyl, naphthyl, anthracenyl, phenanthryl.
  • the heteroaryl group is selected from at least one of a furyl group and a benzofuranyl group.
  • the aryl group is selected from the group consisting of phenyl, naphthyl, anthracenyl, fluorenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, dimethylphenyl, isopropyl At least one of a phenyl group, an isobutylphenyl group, and a t-butylphenyl group.
  • the oxygenate contains active oxygen and provides an oxygen atom to the product having the structure of formula (I).
  • the oxygen-containing compound can promote the reaction of the ketone compound II with the chloroorganophosphine compound III to form the compound I having the structure of the formula (I), and the oxygen-containing compound contains active oxygen, and provides an oxygen atom to have the formula (I) Structure of Compound I.
  • the ketone compound II and the chloroorganophosphine compound III cannot form the compound I having the structure of the formula (I) without the presence of the active oxygen-containing compound.
  • the oxygen-containing compound is at least one selected from the group consisting of water, an oxo acid, a fatty alcohol, and an acid anhydride.
  • the oxyacid includes an inorganic oxyacid and an organic oxyacid.
  • the inorganic oxyacid is at least one selected from the group consisting of nitrous acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid, and metaphosphoric acid. Further preferably, the inorganic oxyacid is phosphoric acid.
  • the organic oxyacid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, benzoic acid, phenylphosphonic acid, diphenylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, At least one of the benzenesulfonic acids.
  • the organic oxyacid is formic acid.
  • the fatty alcohol is at least one selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol. Further preferably, the fatty alcohol is methanol.
  • the acid anhydride is at least one selected from the group consisting of acetic anhydride, benzoic anhydride, and phosphorus pentoxide.
  • the oxygenate is water and/or phosphoric acid.
  • the chloroorganophosphine compound III having the structural formula represented by the formula (III) is converted into a formula.
  • the ketone compound II having the structural formula represented by the formula (II) is reacted with the chloroorganophosphine compound III having the structural formula represented by the formula (III) to form the compound I having the structural formula represented by the formula (I) in the presence of an oxygen-containing compound,
  • oxygenate is an organic oxoacid, such as formic acid
  • the oxygenate is a mineral acid, such as phosphoric acid
  • the phosphoric acid provides an oxygen atom and the remainder is converted to ((HO) 2 P(O)Cl)).
  • the by-product can be self-condensed to form polyphosphoric acid, and can continue to provide oxygen.
  • the atom, even the resulting polyphosphoric acid, can also provide an oxygen atom to the structural formula (I), see reaction equation (VI).
  • the oxygenate is a fatty alcohol
  • Product, the ideal reaction equation is shown in formula (VII).
  • the oxygenate is an anhydride
  • the anhydride provides an oxygen atom and the remainder is converted to other products, the other products being determined by the structure of the anhydride.
  • the anhydride is acetic anhydride
  • the ideal reaction equation is shown in formula (VIII).
  • the reaction system of the reaction includes an acidic catalyst.
  • the acidic catalyst is selected from at least one of non-oxyacids. Further preferably, the acidic catalyst is selected from at least one of hydrochloric acid and hydrobromic acid.
  • the ketone compound II is at least selected from the group consisting of acetophenone, 2-naphthylethyl ketone, furan ethyl ketone, 1-naphthyl ethyl ketone, propiophenone, acetophenone, acetophenone, and phenyl benzyl ketone.
  • acetophenone 2-naphthylethyl ketone
  • furan ethyl ketone furan ethyl ketone
  • 1-naphthyl ethyl ketone propiophenone
  • acetophenone acetophenone
  • acetophenone acetophenone
  • phenyl benzyl ketone phenyl benzyl ketone
  • the reaction temperature of the reaction is from 0 to 250 °C.
  • the reaction rate is slow; when the temperature is higher than 250 ° C, the by-products are greatly increased.
  • the reaction temperature of the reaction is from 80 to 200 °C.
  • the reaction for preparing the compound I can be carried out under normal pressure, positive pressure or under negative pressure.
  • the reaction time of the reaction is from 0.5 to 16 hours.
  • the molar ratio of the ketone compound II to the chloroorganophosphine compound III is:
  • the molar ratio of the ketone compound II to the halogenated organophosphine compound III is:
  • the molar ratio of the ketone compound II to the chloroorganophosphine compound III is a theoretical value or very close to the theoretical value:
  • the amount of oxygenate can be such that the ketone compound II having the structural formula represented by the formula (II) and the chloroorganophosphine compound III having the structural formula represented by the formula (III) are reacted to form a structural formula represented by the formula (I).
  • Compound I can be.
  • the oxygenate is water
  • the molar ratio of water to the chloroorganophosphine compound III is theoretical or close to the theoretical value of 0.5:1.
  • the chlorinated organophosphine compound III, the ketone compound II and the oxygen-containing compound may be mixed in any order, for example, all or part of any two may be mixed first, and then the remaining part and the third component may be added.
  • a mixture containing a chloroorganophosphine compound III and a ketone compound II is first obtained, and then an oxygen-containing compound is added dropwise to the mixture.
  • the reaction system of the reaction contains an inert solvent.
  • the inert solvent is at least one selected from the group consisting of cyclohexane, methylcyclohexane, toluene, benzene, xylene, hexane, heptane, octane, cumene, and t-butylbenzene.
  • the reaction is carried out under an inert atmosphere.
  • the inert atmosphere is selected from at least one of nitrogen gas and inert gas.
  • the inert atmosphere is selected from at least one of nitrogen, helium, and argon.
  • the chemical name of the chloroorganophosphine compound III is 6-chloro-(6H)dibenzo-(c,e)(1,2). - oxyphosphorus heterocycle.
  • the benzene ring in the chemical structural formula of the chlorinated organophosphine compound III of the present application has a hydrogen atom substituted by another substituent, and the common substituents are a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a chloro group, etc. .
  • the chloroorganophosphine compound III can be prepared according to a known method, for example, from the method of U.S. Patent No. 3,702,878, which is prepared by catalyzing the oxidation of zinc phthalate and phosphorus trichloride.
  • the chloroorganophosphine compound III is prepared from a raw material containing o-phenylphenol and phosphorus trichloride in the presence of a catalyst;
  • the catalyst is selected from at least one of the metal chlorides.
  • the catalyst is zinc chloride.
  • o-phenylphenol and phosphorus trichloride form a chloroorganophosphine compound III under the action of a catalyst, and the chlorinated organophosphine compound III is not separated or purified, and directly with the ketone compound II in water, The reaction is carried out in the presence of an oxo acid, an acid anhydride or a mixture thereof, and finally the product is purified by a conventional means such as washing, recrystallization, or the like.
  • the chloroorganophosphine compound III is first purified by distillation or the like, and then the pure chloroorganophosphine compound III and the ketone compound II are used in the presence of water, an oxo acid, an acid anhydride or a mixture thereof. The reaction is carried out, and finally the product is purified by a conventional means such as washing, recrystallization, or the like.
  • the aryl group and the heteroaryl group are groups formed after the loss of any one of the hydrogen atoms in the aromatic ring in the aromatic compound molecule.
  • the group formed is an aryl group; when the aromatic ring contains a hetero atom such as N, O or S, the group formed is a heteroaryl group.
  • the aromatic compound forming an aryl group or a heteroaryl group may have no substituent or a substituent on the aromatic ring, and a typical substituent such as an alkyl group, a carboxyl group, a hydroxyl group, a halogen group or the like.
  • the C 3 -C 18 heteroaryl group is a group formed by an aromatic compound molecule having a heterocyclic aromatic ring having 3 to 18 carbon atoms and having an arbitrary hydrogen atom lost on the aromatic ring.
  • C 3 to C 18 mean that the number of carbon atoms in the heterocyclic aromatic ring in the heteroaryl group is from 3 to 18.
  • the heterocyclic aromatic ring is an aromatic ring containing a hetero atom such as N, O or S.
  • An aromatic compound containing a heterocyclic aromatic ring which comprises a fused ring aromatic ring compound formed by a heterocyclic ring and a benzene ring, such as benzofuran, a group formed by the loss of any one of the hydrogen atoms on the benzene ring or the furan ring, all of which are heteroaryl base.
  • the C 6 -C 18 aryl group is formed by an aromatic compound having an aromatic ring having 6 to 18 carbon atoms and having no hetero atom in the aromatic ring, and losing any hydrogen atom on the aromatic ring.
  • Group. C 6 to C 18 mean that the number of carbon atoms in the aromatic ring which does not contain a hetero atom in the aryl group is from 6 to 18.
  • the aromatic compound which does not contain a hetero atom aromatic ring means that a conjugated aromatic ring system does not contain a hetero atom such as N, O or S.
  • the C 1 -C 18 alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms or an alkyl group having an aromatic ring.
  • the alkyl group containing an aromatic ring is an aromatic compound having an alkyl substituent on the aromatic ring, and a group formed by losing any hydrogen atom in the molecule in the molecule.
  • the alkyl group is a saturated hydrocarbon group, that is, a hydrocarbon group in which an alkane molecule loses one hydrogen atom, and contains a linear alkyl group and a branched alkyl group.
  • the alkyl group is selected from the group consisting of methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, isobutyl, pentyl or hexyl.
  • the aromatic ring may be a monocyclic aromatic ring, a polycyclic aromatic ring or a fused ring aromatic ring.
  • the monocyclic aromatic ring may be a benzene ring or a five- or six-membered heterocyclic ring containing a hetero atom such as N, O or S.
  • the polycyclic aromatic ring contains a plurality of benzene rings and/or heterocyclic rings, and between the benzene ring and the benzene ring, between the benzene ring and the hetero ring, and between the hetero ring and the hetero ring, does not share a carbon atom, such as Benzene ring.
  • the fused ring aromatic ring contains a plurality of benzene rings and/or heterocyclic rings, and a common carbon atom exists between the benzene ring and the benzene ring, between the benzene ring and the hetero ring, and between the hetero ring and the hetero ring.
  • the method provided by the present application is compared to the reaction from DOPO and ketone compounds
  • the method for preparing DiDOPO from the reaction of the chlorinated organophosphine compound III and the ketone compound II produces less non-volatile by-products, and the purification of the product is easier and the yield is higher.
  • Figure 1 is a nuclear magnetic resonance spectrum of the product of Example 1.
  • the product obtained in the examples was characterized by 1 H-NMR and 31 P-NMR using a Bruker 400 MHz AVANCE III type magnetic resonance apparatus without special explanation.
  • the yield was calculated as: (product weight / product theoretical weight) x 100%.
  • the theoretical weight of the product is calculated based on the amount of ketone compound in the raw material.
  • DOP-Cl was characterized by a P spectrum on a magnetic resonance apparatus, and its phosphorus spectrum is shown in Fig. 1.
  • the DOP-Cl was prepared in several batches by the above method. After the combination, the DOP-Cl was divided into two parts, one part was distilled to obtain pure DOP-Cl, and the other part was not subjected to other treatments for use.
  • the untreated DOP-Cl (33.41 g, 142.5 mmol) obtained in Example 1 and 14 ml of xylene were placed in a three-necked flask equipped with a thermometer, a water separator, a magnetic stirrer and a constant pressure dropping funnel. Under a nitrogen atmosphere, the mixture was heated to 160 ° C, and 8.56 g of acetophenone (71.25 mmol) was added dropwise while 2.16 g of an aqueous phosphoric acid solution (mass concentration: 64.5%) was added dropwise to the system. The acetophenone solution was dropped in 2 hours. After 1 hour, the phosphoric acid solution was also dropped.
  • Example 2 The procedure and the ratio of the raw materials were referred to Example 2, but without using phosphoric acid, the yield of the final product was 55%.
  • Untreated DOP-Cl (19.13g, 81.58mmol), acetophenone (4.90g, 40.78mmol) and 10ml of xylene were added to the thermometer, water separator, magnetic stirrer and constant pressure dropping funnel In a three-necked flask. Under a nitrogen atmosphere, the mixture was heated to 154 ° C, and 0.58 g of concentrated hydrochloric acid was added dropwise to the system, and the mixture was dropped in 0.5 hour. The internal temperature of the system was maintained at 152 ° C to 160 ° C for 8.5 hours. 0.5 g of hydrochloric acid was added and the temperature was raised to 170 ° C to 180 ° C to continue the reaction for 14.5 hours.
  • Untreated DOP-Cl (31.89 g, 136 mmol) and 14 ml of xylene were placed in a three-necked flask equipped with a thermometer, a water separator, a mechanical stirring and a constant pressure dropping funnel. Under a nitrogen atmosphere, the mixture was heated to 158 ° C, and a mixture of 11.57 g of naphthyl ethyl ketone (68 mmol) and 9 ml of xylene was added dropwise while 2.068 g of an aqueous phosphoric acid solution (mass concentration: 64.5%) was added dropwise to the system. The naphthyl ethyl ketone solution was dropped in 2 hours.
  • acetophenone (4.81g, 40mmol), 0.05g H 3 PO 4 and 30 ml of xylene were added into a reactor equipped with a thermometer, water separator, mechanical stirrer and constant A three-necked flask of a pressure funnel. Under nitrogen protection, the reaction was carried out at an internal temperature of 152 ° C to 160 ° C for 15.5 hours, and 0.35 g of H 3 PO 4 was added to the system in four portions during the reaction.
  • the untreated DOP-Cl of Example 2 was replaced with DOP-Cl obtained by distillation, and the other conditions were unchanged, and the yield of the final product was 90%.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

公开了一种化合物I的制备方法，其特征在于，酮类化合物II与氯代有机膦化合物III在含氧化合物的存在下反应，制备得到所述化合物I。该方法相比于已有从DOPO和芳基烷基酮在三氯氧磷等催化下反应制备DiDOPO的合成方法，缩短了反应步骤，有效地降低了成本，提高了工艺的可操作性以及安全性，产物的提纯更容易，产率更高。

Description

一种DiDOPO类化合物的制备方法 技术领域
本申请涉及一种DiDOPO类化合物的制备方法，属于无卤阻燃剂领域。
背景技术
高分子材料广泛用于电子电器，汽车，建筑，纺织等行业。但由于高分子材料具有可燃性，实际使用时需要添加阻燃剂，以达到防火安全的要求。膦酸酯特别是9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)衍生物阻燃剂由于阻燃效率高和对环境友好受到了重视。
美国专利9522927报道了亚乙烯基桥链结构的DiDOPO，其制备过程使用了昂贵的强碱作为反应物，且产率低，导致成本高昂。
美国专利9562063报道了使用DOPO和二元醇来制备DiDOPO的方法，但其只适合于简单的直链脂肪族二元醇。
中国专利申请CN104086593使用了DOPO和芳基烷基酮在三氯氧磷等催化剂作用下制备芳香基取代亚乙烯基桥链结构的DiDOPO方法，该方法简单方便，但需要先制备DOPO，同时所使用的三氯氧磷不安全，提高了成本。
发明内容
根据本申请的一个方面，提供一种芳香基取代亚乙烯基桥链结构DiDOPO化合物(即本申请中所述化合物I)的制备方法，该方法简单方便、低成本、环保性好。
所述化合物I的制备方法，其特征在于，酮类化合物II与氯代有机膦化合物III在含氧化合物的存在下反应，制备得到所述化合物I；
所述化合物I选自具有如式(I)所示结构式的化合物中的至少一种：
Figure PCTCN2017092574-appb-000001
所述酮类化合物II选自具有如式(II)所示结构式的化合物中的至少一种；
Figure PCTCN2017092574-appb-000002
所述氯代有机膦化合物III选自具有如式(III)所示结构式的化合物中的至少一种；
Figure PCTCN2017092574-appb-000003
其中，Ar任选自C3～C18的杂芳基或C6～C18的芳基；
R1和R2独立地任选自氢、C1～C18的烷基、C3～C18的杂芳基、C6～C18的芳基；
R3，R4，R5和R6独立地任选自氢、C1～C18的烷基、C3～C18的杂芳基、C6～C18的芳基；
m，n，k和p独立地任选自0，1，2，3，4；
R7和R8独立地任选自氢、C1～C18的烷基、C3～C18的杂芳基、C6～C18的芳基；
q和j独立地任选自0，1，2，3，4；
所述芳基或杂芳基芳香环上的任意氢原子可以独立被任意C1-C18的烷基取代。
优选地，R1和R2均为氢，m＝n＝k＝p＝0。
优选地，R1为氢，R2为芳基，m＝n＝k＝p＝0。
优选地，R1为氢，R2为烷基，m＝n＝k＝p＝0。
常见的杂芳基有呋喃基、苯并呋喃基、异苯并呋喃基、吡咯基、吲哚基、异吲哚基、噻吩基、苯并[b]噻吩基、苯并[c]噻吩基、咪唑 基、苯并咪唑基、嘌呤基、吡唑基、吲唑基、恶唑基、苯并恶唑基、异恶唑基、苯并异恶唑基、噻唑基、苯并噻唑基、吡啶基、喹啉基、异喹啉基、吡嗪基、喹喔啉基、吖啶基、嘧啶基、喹唑啉基、哒嗪基、酞嗪基和噌啉基。常见的芳基有苯基、萘基、蒽基、菲基。
优选地，所述杂芳基选自呋喃基、苯并呋喃基中的至少一种。
优选地，所述芳基选自苯基、萘基、茚基、芴基、甲基苯基、乙基苯基、丙基苯基、丁基苯基、二甲基苯基、异丙基苯基、异丁基苯基、叔丁基苯基种的至少一种。
所述含氧化合物中含有活泼氧，提供氧原子给具有式(I)结构的产物。所述该含氧化合物能促使酮类化合物II和氯代有机膦化合物III反应生成具有式(I)结构的化合物I，同时该含氧化合物中含有活泼氧，提供氧原子给具有式(I)结构的化合物I。若无含活泼氧化合物的存在，酮类化合物II和氯代有机膦化合物III不能生成具有式(I)结构的化合物I。
优选地，所述含氧化合物选自水、含氧酸、脂肪醇、酸酐中的至少一种。所述含氧酸包括无机含氧酸和有机含氧酸。
优选地，所述无机含氧酸选自亚硝酸、硝酸、硫酸、亚硫酸、磷酸、多聚磷酸、亚磷酸、次磷酸、偏磷酸中的至少一种。进一步优选地，所述无机含氧酸为磷酸。
优选地，所述有机含氧酸选自甲酸、乙酸、丙酸、丁酸、己酸、辛酸、苯甲酸、苯基磷酸、二苯基磷酸、苯基膦酸、二苯基膦酸、甲基苯磺酸中的至少一种。进一步优选地，所述有机含氧酸为甲酸。
优选地，所述脂肪醇选自甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇中的至少一种。进一步优选地，所述脂肪醇为甲醇。
优选地，所述酸酐选自乙酸酐、苯甲酸酐、五氧化二磷中的至少一种。
作为一种优选的实施方式，所述含氧化合物为水和/或磷酸。
由于化合物I的结构式中含有P＝O基团，而氯代有机膦化合物III的结构式中不含有P＝O基团，具有式(III)所示结构式的氯代有机膦化合物III转化为具有式(I)所示结构式的化合物I时，需要由 含活泼氧的含氧化合物来提供O原子，生成P＝O基团。理想情况下，含活泼氧的含氧化合物提供氧原子生成一半的P＝O，另外一半的P＝O基团中的O可以来自结构式II中C＝O的氧。
具有式(II)所示结构式的酮类化合物II和具有式(III)所示结构式的氯代有机膦化合物III反应，在含氧化合物存在下生成具有式(I)所示结构式的化合物I，含氧化合物提供氧原子转化成式(I)结构P＝O中的氧原子，非含氧部分转化为其他产物，其他产物由含氧化合物决定。
当含氧化合物为水时，理想情况下，水分子提供氧原子以生成式(I)结构中的一半的P＝O，结构式(II)中C＝O提供氧原子生成结构式(I)中另一半的P＝O，见反应式(IV)。
Figure PCTCN2017092574-appb-000004
当含氧化合物为有机含氧酸，譬如甲酸，其提供O原子以生成式(I)结构中一部分的P＝O，甲酸其它部分转化成CO和HCl，理想的反应式见(V)。
Figure PCTCN2017092574-appb-000005
当含氧化合物为无机酸，譬如磷酸，则磷酸提供氧原子，剩余部分转化成((HO)2P(O)Cl)),该副产物可以自缩聚生成多聚磷酸，也可以继续提供氧原子，甚至生成的多聚磷酸也可以提供氧原子给结构式(I)，见反应方程式(VI)。
Figure PCTCN2017092574-appb-000006
当含氧化合物为脂肪醇，脂肪醇提供O原子以生成式(I)结构中的一部分P＝O,其它部分转化为HCl和脂肪族氯代物，即脂肪族醇当中的羟基被氯原子取代的产物，理想的反应方程式见式(VII)。
Figure PCTCN2017092574-appb-000007
当含氧化合物为酸酐，酸酐提供氧原子，其余部分转化为其他产物，其他产物决定于酸酐的结构。譬如酸酐为乙酸酐时，乙酸酐提供O原子以生成式(I)结构中的一部分P＝O，其余部分转化为乙酰氯，理想的反应方程式见式(VIII)。
Figure PCTCN2017092574-appb-000008
可选择地，所述含氧化合物为水时，所述反应的反应体系中包括酸性催化剂。
优选地，所述酸性催化剂选自非含氧酸中的至少一种。进一步优选地，所述酸性催化剂选自盐酸、氢溴酸中的至少一种。
优选地，所述酮类化合物II选自苯乙酮、2-萘乙酮、呋喃乙酮、1-萘乙酮、苯丙酮、茚乙酮、芴乙酮、苯基苄基酮中的至少一种。
优选地，所述反应的反应温度为0～250℃。温度低于0℃，反应速度缓慢；温度高于250℃，副产物大量增多。进一步优选地，所述反应的反应温度为80～200℃。
所述制备化合物I的反应可以在常压、正压或负压条件下进行。
优选地，所述反应的反应时间为0.5-16小时。
优选地，所述酮类化合物II与氯代有机膦化合物III的摩尔比例为：
酮类化合物II：卤代有机膦化合物III＝1：1～5。
进一步优选地，所述酮类化合物II与卤代有机膦化合物III的摩尔比例为：
酮类化合物II：氯代有机膦化合物III＝1：2～5。
特别优选地，所述酮类化合物II与氯代有机膦化合物III的摩尔比例为理论值或者非常接近理论值：
酮类化合物II：氯代有机膦化合物III＝1：2。
本领域技术人员可以根据实际需要，如反应所需要进行的程度、具体选用的含氧化合物种类，选择含氧化合物的用量。原则上，含氧化合物的用量能够满足促使具有式(II)所示结构式的酮类化合物II和具有式(III)所示结构式的氯代有机膦化合物III反应生成具有式(I)所示结构式的化合物I即可。比如，当含氧化合物为水时，水和氯代有机膦化合物III的摩尔比例为理论值或者接近理论值0.5:1为佳。
氯代有机膦化合物III、酮类化合物II和含氧化合物可以以任意次序混合，比如可以先混合任意两个的全部或部分，然后加入剩余部分和第三组分。作为一种优选的实施方式，先获得含有氯代有机膦化合物III和酮类化合物II的混合物，然后再向混合物中滴加含氧化合物。
可选择地，所述反应的反应体系中含有惰性溶剂。优选地，所述惰性溶剂选自环己烷、甲基环己烷、甲苯、苯、二甲苯、己烷、庚烷、辛烷、异丙苯、叔丁基苯中的至少一种。
作为一种可选择的实施方式，所述反应在非活性气氛下进行。可选择地，所述非活性气氛选自氮气、惰性气体中的至少一种。可选择地，所述非活性气氛选自氮气、氦气、氩气中的至少一种。
根据本领域公知常识，当式(III)中q和j为0时，氯代有机膦化合物III的化学名称为6-氯-(6H)二苯并-(c,e)(1,2)-氧磷杂己环。本申请所述氯代有机膦化合物III化学结构式中的苯环上，有氢原子被其他取代基取代，常见的取代基有甲基、乙基、异丙基、叔丁基、氯代基等。
氯代有机膦化合物III可以根据已知的方法制备得到，譬如美国专利US3702878中的方法，从邻苯基苯酚和三氯化磷在氯化锌催化下制备而得。
作为一种实施方式，所述氯代有机膦化合物III由含有邻苯基苯酚和三氯化磷的原料在催化剂的存在下制备得到；
所述催化剂选自金属氯化物中的至少一种。
优选地，所述催化剂为氯化锌。
作为一种具体的实施方式，邻苯基苯酚和三氯化磷在催化剂作用下生成氯代有机膦化合物III，氯代有机膦化合物III不经过分离或提纯，直接和酮类化合物II在水、含氧酸、酸酐或者它们的混合物存在下进行反应，最后通过常规的手段譬如洗涤，重结晶等方法将产物提纯。
作为一种具体的实施方式，首先通过蒸馏等方法提纯氯代有机膦化合物III，然后用纯的氯代有机膦化合物III和酮类化合物II在水、含氧酸、酸酐或者它们的混合物存在下进行反应，最后通过常规的手段譬如洗涤，重结晶等方法将产物提纯。
氯代有机膦化合物III和酮类化合物II反应的机理如下：氯代有机膦化合物III和酮类化合物II的碳基先络合生成5价的磷中间体，该中间体和水等反应生成α-OH膦酸酯或者α-X膦酸酯,该中间体脱水或脱HX，生成α-C＝C。第二份子氯代有机膦化合物III跟水或者酸等反应生成DOPO，DOPO再加成到上述的α-C＝C上，生成具有式(I)结构式的化合物I。或者α-OH膦酸酯跟化合物III反应，脱氯化氢，再消除生成DOPO和α-C＝C中间体，加成生成具有式(I)结构式的化合物I。
本申请中，所述芳基和杂芳基为芳香族化合物分子中失去芳香环上任意一个氢原子后形成的基团。当芳香环上不包含N、O、S等杂原子时，形成的基团为芳基；当芳香环上包含N、O、S等杂原子时，形成的基团为杂芳基。形成芳基或杂芳基的芳香族化合物，芳香环上可以没有取代基也可以有取代基，典型的取代基如烷基、羧基、羟基、卤代基等。
本申请中，所述C3～C18的杂芳基是含有碳原子数为3～18杂环芳香环的芳香族化合物分子中，芳香环上失去任意一个氢原子后形成的基团。C3～C18指的是杂芳基中杂环芳香环上的碳原子数为3～18。杂环芳香环为含有N、O、S等杂原子的芳香环。含有杂环芳香环的芳香族化合物，包含杂环与苯环形成的稠环芳香环化合物，如苯并呋喃，其苯环或者呋喃环上失去任意一个氢原子形成的基团，均为杂芳基。
本申请中，所述C6～C18的芳基是芳香环碳原子数为6～18且芳香环上不含有杂原子的芳香族化合物分子中，芳香环上失去任意一个氢原子后形成的基团。C6～C18指的是芳基中不含杂原子的芳香环上的碳原子数为6～18。不含有杂原子芳香环的芳香族化合物，指共轭的芳香环体系中，不包含N、O、S等杂原子。
所述C1～C18的烷基为碳原子数为1～18的直链烷基、碳原子数为1～18的带有支链的烷基或者含有芳香环的烷基。所述含有芳香环的烷基，为芳香环上存在烷基取代基的芳香族化合物，分子中失去烷基上任意一个氢原子后形成的基团。
优选地，所述烷基为饱和烃基，即烷烃分子失去一个氢原子而成的烃基，包含直链烷基和带有支链的烷基。进一步优选的，所述烷基任选自甲基、乙基、丙基、丁基、异丙基、叔丁基、异丁基、戊基或己基。
本申请中，所述芳香环可以为单环芳香环、多环芳香环或者稠环芳香环。其中，所述单环芳香环可以为苯环，也可以为含有N、O、S等杂原子的五元或者六元杂环。所述多环芳香环，含有多个苯环和/或杂环，且苯环与苯环之间、苯环与杂环之间、杂环与杂环之间，不共用碳原子，如联苯环。所述稠环芳香环，含有多个苯环和/或杂环，且苯环与苯环之间、苯环与杂环之间、杂环与杂环之间，存在共用的碳原子，如萘环、苯并呋喃环等。
本申请的有益效果包括但不限于：
(1)本申请所提供的方法，相比于已有从DOPO和酮类化合物在三氯氧磷等催化下反应制备DiDOPO的合成方法，使用氯代有机膦化合物III作为反应原料，不必经过全部转化为或者分离出DOPO,不仅减少了在传统制备DOPO中需要等当量的水，而且缩短了反应步骤，有效地降低了成本。
(2)本申请所提供的方法，避免使用已知文献中有毒有害的三氯氧磷催化剂，提高了工艺的可操作性以及安全性。
(3)本申请所提供的方法，相比于从DOPO和酮类化合物反应 制备DiDOPO过程，本申请从氯代有机膦化合物III和酮类化合物II反应制备DiDOPO的方法生成的不挥发副产更少，产物的提纯更容易，产率更高。
应理解，在本申请披露的技术方案范围内，本申请的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
除非另行定义，文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本申请方法中。文中所述的较佳实施方法与材料仅作示范之用。
附图说明
图1是实施例1产物的核磁共振磷谱。
具体实施方式
本申请提到的上述特征，或实施例提到的特征可以任意组合。本案说明书所揭示的所有特征可与任何组合物形式并用，说明书中所揭示的各个特征，可以被任何提供相同、均等或相似目的的替代性特征取代。因此除有特别说明，所揭示的特征仅为均等或相似特征的一般性例子。
下面结合实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。除非另外说明，否则百分比按重量计算。
未做特殊说明的情况下，本申请所使用原料，均通过商业途径购买，不经特殊处理直接使用。
未做特殊说明的情况下，本申请使用Bruker 400MHz AVANCE Ⅲ型磁共振仪对实施例中所得产品进行1H-NMR和 31P-NMR表征。磷谱表征条件为氢去耦，预延期D1＝10秒，扫描次数大于16次，溶剂CDCl3，使用85％磷酸做定位标样。
实施例中，产率的计算方法为：(产物重量/产物理论重量)×100％。其中产物理论重量是基于原料中酮类化合物的量计算得到。
实施例1氯代有机膦化合物III样品的制备
将51.06g(0.30mol)邻苯基苯酚(简称OPP)和0.41g氯化锌投入到装有恒压滴液漏斗、克莱森管、冷凝管、温度计和磁力搅拌子的100ml三口瓶中，通氮气。当体系内温升至78℃变为透明液相，开始滴加45.33g PCl3。在滴加过程中，逐渐提高反应温度到165℃。PCl3在7.5h滴加完毕，升温至172℃并保温至无HCl产生。随后向体系中加入100g二甲苯，蒸馏去除多余的PCl3。最后得到产品粗品，所得产品记为DOP-Cl。在磁共振仪上对所得DOP-Cl进行P谱的表征，其磷谱详见图1。
用上述方法分几批制备了DOP-Cl，合并之后将DOP-Cl分为2部分，一部分经过蒸馏获得纯的DOP-Cl,另外一部分未经过其他处理待用。
实施例2以水和磷酸为含氧化合物，Ar＝苯基
将实施例1获得的未经处理的DOP-Cl(33.41g，142.5mmol)和14毫升二甲苯加入到装有温度计，分水器，磁搅拌子和恒压滴液漏斗的三口烧瓶中。在氮气保护下，混合液加热到160℃，开始滴加8.56g苯乙酮(71.25mmol)，同时滴加2.16g磷酸水溶液(质量浓度64.5％)至体系中。苯乙酮溶液2小时滴完，1小时后磷酸溶液也滴完，继续保温反应1.5小时后，向体系中滴加0.2g水，保持体系内温在155℃～160℃下继续反应1.5小时。核磁磷谱显示式(I)结构的产物(R1＝R2＝R3＝R4＝R5＝R6＝H,Ar＝Ph)为98.9％,DOPO为1.1％。随后慢慢滴加40g异丙醇，回流搅拌直至产物全部溶解，冷却，降温，待固体析出后，过滤、碱洗、水洗，干燥得产品，产率89％。
在磁共振仪器上对所得产品进行H谱和P谱的表征，其磷谱数 据为31PNMR(85％H3PO4＝0ppm)：34.2-37.0ppm(多峰)；其氢谱数据为1HNMR(CDCl3，TMS):6.2-8.0(多峰，21H)，3.3-3.8(多峰，1H)，2.5-3.0(多峰，2H)。
实施例3以水为含氧化合物，Ar＝苯基
步骤和原料配比参照实施例2,但是不使用磷酸，最后产物的产率为55％。
实施例4以水为含氧化合物，以盐酸为催化剂，Ar＝苯基
将未经处理的DOP-Cl(19.13g，81.58mmol)，苯乙酮(4.90g，40.78mmol)和10毫升二甲苯加入到装有温度计，分水器，磁搅拌子和恒压滴液漏斗的三口烧瓶中。在氮气保护下，混合液加热到154℃，开始滴加0.58g浓盐酸至体系中，0.5小时滴完。保持体系内温在152℃～160℃下继续反应8.5小时。补加0.5g盐酸并升温至170℃～180℃继续反应14.5小时。再补加0.15g盐酸反应4小时。核磁磷谱显示式(I)结构的产物(R1＝R2＝R3＝R4＝R5＝R6＝H,Ar＝苯基)为92％。随后降温慢慢滴入25g异丙醇，回流搅拌直至产物全部溶解，冷却，降温，待固体析出后，过滤、碱洗、水洗，干燥得产品。
实施例5以水和磷酸为含氧化合物，Ar＝萘基
将未经处理的DOP-Cl(31.89g，136mmol)和14毫升二甲苯加入到装有温度计，分水器，机械搅拌和恒压滴液漏斗的三口烧瓶中。在氮气保护下，混合液加热到158℃，开始滴加11.57g萘乙酮(68mmol)和9ml二甲苯的混合液，同时滴加2.068g磷酸水溶液(质量浓度64.5％)至体系中。萘乙酮溶液2小时滴完，2小时后磷酸溶液也滴完，继续保温反应2小时后向体系中滴加0.36g水，保持体系内温在155℃～160℃下继续反应8小时。核磁磷谱显示式(I)结构的产物(R1＝R2＝R3＝R4＝R5＝R6＝H,Ar＝萘基)为86.1％。随后降温，慢慢滴加38g异丙醇，回流搅拌直至产物全部溶解，冷却，降温，待固体析出后，过滤、碱洗、水洗，干燥得产品。
在磁共振仪器上对所得产品进行H谱和P谱的表征，其磷谱数据为31PNMR(85％H3PO4＝0ppm)：34.0-37.0ppm(多峰)；其氢谱数据为1HNMR(CDCl3):6.0-8.0(多峰，23H)，4.2-4.7(多峰，1H)，2.8-3.2(多峰，2H)。
实施例6以磷酸为含氧化合物，Ar＝苯基
将未经过处理的DOP-Cl(18.76g，80mmol)，苯乙酮(4.81g，40mmol)，0.05g H3PO4和30毫升二甲苯加入到装有温度计，分水器，机械搅拌和恒压漏斗的三口烧瓶中。在氮气保护下，在内温152℃～160℃下反应15.5小时，反应过程中分四次向体系中补加0.35g H3PO4。核磁磷谱显示式(I)结构的产物(R1＝R2＝R3＝R4＝R5＝R6＝H,Ar＝萘基)为54％，DOP-Cl 23％，DOPO 7％,其他为反应中间体。
实施例7以水和磷酸为含氧化合物，Ar＝苯基
用经过蒸馏获得的DOP-Cl替代实施例2中未经处理的DOP-Cl，其它条件不变，最后产物的收率为90％。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (14)

  1. 一种化合物I的制备方法，其特征在于，酮类化合物II与氯代有机膦化合物III在含氧化合物的存在下反应，制备得到所述化合物I；
    所述化合物I选自具有如式(I)所示结构式的化合物中的至少一种：
    Figure PCTCN2017092574-appb-100001
    所述酮类化合物II选自具有如式(II)所示结构式的化合物中的至少一种；
    Figure PCTCN2017092574-appb-100002
    所述氯代有机膦化合物III选自具有如式(III)所示结构式的化 合物中的至少一种；
    Figure PCTCN2017092574-appb-100003
    其中，Ar任选自C3～C18的杂芳基或C6～C18的芳基；
    R1和R2独立地任选自氢、C1～C18的烷基、C3～C18的杂芳基、C6～C18的芳基；
    R3，R4，R5和R6独立地任选自氢、C1～C18的烷基、C3～C18的杂芳基、C6～C18的芳基；
    m，n，k和p独立地任选自0，1，2，3，4；
    R7和R8独立地任选自氢、C1～C18的烷基、C3～C18的杂芳基、C6～C18的芳基；
    q和j独立地任选自0，1，2，3，4；
    所述芳基或杂芳基芳香环上的任意氢原子可以独立被任意C1-C18的烷基取代。
  2. 根据权利要求1所述的方法，其特征在于，所述杂芳基选自呋喃基、苯并呋喃基中的至少一种；所述芳基选自苯基、萘基、茚基、芴基、甲基苯基、乙基苯基、丙基苯基、丁基苯基、二甲基苯基、异丙基苯基、异丁基苯基、叔丁基苯基种的至少一种。
  3. 根据权利要求1所述的方法，其特征在于，所述含氧化合物选自水、无机含氧酸、有机含氧酸、脂肪醇、酸酐中的至少一种。
  4. 根据权利要求3所述的方法，其特征在于，所述无机含氧酸选自亚硝酸、硝酸、硫酸、亚硫酸、磷酸、多聚磷酸、亚磷酸、次磷酸、偏磷酸中的至少一种；
    所述有机含氧酸选自甲酸、乙酸、丙酸、丁酸、己酸、辛酸、苯甲酸、苯基磷酸、二苯基磷酸、苯基膦酸、二苯基膦酸、甲基苯磺酸中的至少一种；
    所述脂肪醇选自甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇中的至少一种；
    所述酸酐选自乙酸酐、苯甲酸酐、五氧化二磷中的至少一种。
  5. 根据权利要求3所述的方法，其特征在于，所述含氧化合物为水时，所述反应的反应体系中包括酸性催化剂。
  6. 根据权利要求1所述的方法，其特征在于，所述酮类化合物II选自苯乙酮、2-萘乙酮、呋喃乙酮、1-萘乙酮、苯丙酮、茚乙酮、芴乙酮、苯基苄基酮中的至少一种。
  7. 根据权利要求1所述的方法，其特征在于，所述反应的反应温度为0～250℃。
  8. 根据权利要求1所述的方法，其特征在于，所述反应的反应温度为80～200℃。
  9. 根据权利要求1所述的方法，其特征在于，所述反应的反应时间为0.5～16小时。
  10. 根据权利要求1所述的方法，其特征在于，所述酮类化合物II与氯代有机膦化合物III的摩尔比例为：
    酮类化合物II：氯代有机膦化合物III＝1：1～5。
  11. 根据权利要求1所述的方法，其特征在于，所述酮类化合物II与氯代有机膦化合物III的摩尔比例为：
    酮类化合物II：氯代有机膦化合物III＝1：2～5。
  12. 根据权利要求1所述的方法，其特征在于，所述反应的反应体系中含有惰性溶剂；所述惰性溶剂选自环己烷、甲基环己烷、甲苯、苯、二甲苯、己烷、庚烷、辛烷、异丙苯、叔丁基苯中的至少一种。
  13. 根据权利要求1所述的方法，其特征在于，所述氯代有机膦化合物III由含有邻苯基苯酚和三氯化磷的原料在催化剂的存在下制备得到；
    所述催化剂选自金属氯化物中的至少一种。
  14. 根据权利要求13所述的方法，其特征在于，所制备得到的氯代有机膦化合物III不经提纯直接用于化合物I的制备；或者
    所制备得到的氯代有机膦化合物III经提纯后用于化合物I的制备。
PCT/CN2017/092574 2017-07-05 2017-07-12 一种DiDOPO类化合物的制备方法 WO2019006774A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710542673.3A CN107325128B (zh) 2017-07-05 2017-07-05 一种DiDOPO类化合物的制备方法
CN201710542673.3 2017-07-05

Publications (1)

Publication Number Publication Date
WO2019006774A1 true WO2019006774A1 (zh) 2019-01-10

Family

ID=60196778

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/092574 WO2019006774A1 (zh) 2017-07-05 2017-07-12 一种DiDOPO类化合物的制备方法

Country Status (2)

Country Link
CN (1) CN107325128B (zh)
WO (1) WO2019006774A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110885344B (zh) * 2018-09-07 2021-07-27 中国科学院宁波材料技术与工程研究所 Dopo亚乙烯基桥链衍生物制备方法、阻燃剂及阻燃高分子材料
CN110183726B (zh) * 2019-06-05 2020-06-09 中国科学院宁波材料技术与工程研究所 一种组合物及其制备方法、含有该组合物的阻燃高分子材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102428092A (zh) * 2009-05-19 2012-04-25 雅宝公司 Dopo衍生物阻燃剂
CN102971333A (zh) * 2010-03-31 2013-03-13 雅宝公司 制备dopo衍生的化合物及其组合物的方法
CN104086593A (zh) * 2014-07-14 2014-10-08 中国科学院宁波材料技术与工程研究所 一类dopo衍生物、其制备方法及应用
WO2014179688A1 (en) * 2013-05-03 2014-11-06 Albemarle Corporation Butadien2,3-diyl linked di-dopo derivatives as flame retardants

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104119673B (zh) * 2014-07-14 2018-04-27 中国科学院宁波材料技术与工程研究所 无卤阻燃高温尼龙
CN104592549A (zh) * 2015-02-03 2015-05-06 上海交通大学 一种含磷反应型阻燃剂、合成方法及其应用
CN106519296B (zh) * 2016-10-31 2018-11-27 贵州省材料产业技术研究院 一种透明无卤环氧树脂阻燃材料及其制备方法
CN106751471A (zh) * 2016-11-24 2017-05-31 贵阳学院 一种蒙脱土/dopo衍生物协效阻燃环氧树脂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102428092A (zh) * 2009-05-19 2012-04-25 雅宝公司 Dopo衍生物阻燃剂
CN102971333A (zh) * 2010-03-31 2013-03-13 雅宝公司 制备dopo衍生的化合物及其组合物的方法
WO2014179688A1 (en) * 2013-05-03 2014-11-06 Albemarle Corporation Butadien2,3-diyl linked di-dopo derivatives as flame retardants
CN104086593A (zh) * 2014-07-14 2014-10-08 中国科学院宁波材料技术与工程研究所 一类dopo衍生物、其制备方法及应用

Also Published As

Publication number Publication date
CN107325128A (zh) 2017-11-07
CN107325128B (zh) 2019-04-02

Similar Documents

Publication Publication Date Title
KR101665735B1 (ko) 감마-델타-불포화 케톤의 제조 방법
JP6101636B2 (ja) バナジウム錯体を用いたファルネサールの製造方法
Fu et al. Copper-catalyzed oxidative dehydrogenative coupling of carboxylic acids with H-phosphonates: an efficient and practical approach to acyl phosphate esters
WO2019006774A1 (zh) 一种DiDOPO类化合物的制备方法
JPH06192281A (ja) α−カルボニルホスフィンオキシドの製造方法および２−ヒドロキシベンジルホスフィンオキシド
CN112300072A (zh) 5-碘异喹啉类化合物的高收率合成方法
CN110156832A (zh) 双缩醛基苯基膦、它们的制备方法及在偶联反应中的用途
TWI668208B (zh) 醚類之烷氧羰基化方法
CN107628948B (zh) 醇的烷氧羰基化的方法
JP4592158B2 (ja) カルボン酸アリールエステルの製造方法
KR101638331B1 (ko) 호기성 산화법을 이용한 벤즈이미다졸의 합성방법
KR101522464B1 (ko) 아렌설포닉 에시드로부터 아렌설포닐 클로라이드를 얻는 새로운 방법
KR101061602B1 (ko) 난연성 포스파펜안트렌 화합물 및 이의 제조방법
JPS61129193A (ja) ビス‐ホスフインオキシド化合物の製造法
CN109180725B (zh) 一种炔基磷酸酯的制备方法
JP2012528122A (ja) 亜リン酸ジアルキルの製造のための方法
JP2012528128A (ja) 亜リン酸ジアルキルの製造のための方法
JPH0555494B2 (zh)
KR100565763B1 (ko) 케톤의 제조방법
JPS6023389A (ja) ビニルホスホン酸又はビニルピロホスホン酸の誘導体の製造法
US6215013B1 (en) Preparation of phosphonic acid derivatives
JP2017071556A (ja) オキソバナジウム錯体を用いたカルボン酸プレニル類及びプレノール類の製造方法
JP2759088B2 (ja) １，４―ジヒドロキシ―２―ナフトエ酸アリールエステルの製造法
CN110964060A (zh) 双-(α-羟基磷酸酯)的制备方法
JP2023176740A (ja) 有機リン化合物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17916612

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17916612

Country of ref document: EP

Kind code of ref document: A1