- A simple straightforward synthesis of phenylphosphane and the photoinitiator bis(mesitoyl)phenylphosphane oxide (IRGACURE 819)
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A straightforward high-yield synthesis for the photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphane oxide (16, IRGACURE 819) involves: i) the reaction of phenyldichlorophosphane, PhPCl2, with sodium to give [Na2(P2Ph2)(tmeda)]6 (5); ii) protonation of 5 with tert-butanol to give 1,2-diphenyldiphosphane, PhHP-PHPh (12); iii) reduction of 12 by sodium to yield [Na(PHPh)x (13); iv) protonation of 13 with tert-butanol to give phenylphosphane PhPH2 (14) in excellent yields; v) reaction of 14 with 2,4,6-trimethylbenzoylchloride (MesCOCI) in presence of the NaOt-Bu formed in steps ii and iv to give bis(2,4,6-trimethylbenzoyl)phenylphosphane 7; vi) oxygenation of 7 with 30% aqueous hydrogen peroxide to give the final product 16. This reaction can be performed in toluene with about 4 vol-% of tmeda as an activator in a one-pot synthesis without changing the solvent. The structures determined by X-ray diffraction of the unique hexameric aggregate 5 and 16 are reported. Schweizerische Chemische Gesellschaft.
- Gruetzmacher, Hansjoerg,Geier, Jens,Stein, Daniel,Ott, Timo,Schoenberg, Hartmut,Sommerlade, Reinhard H.,Boulmaaz, Souad,Wolf, Jean-Pierre,Murer, Peter,Ulrich, Thomas
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- Preparation method of bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide
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The invention provides a preparation method of bis (2,4,6-trimethylbenzoyl)phenyl phosphine oxide, which comprises the following steps: adding a specific ether compound as a complexing agent in the reaction of sodium sand and phenyl phosphine dichloride, and adding the complexing agent to effectively inhibit the formation of phenyl phosphine sodium polyphosphide and promote the generation of phenyl phosphine sodium; a phenyl phosphine hydrogen process is not needed, so that the process cost is reduced, and the safety of the process is improved; besides, the complexing agent is a polar aproticsolvent, is low in dosage, can reduce the content of organic matters in the wastewater compared with a traditional method adopting a protic solvent as an activating agent or a proton source, has certain environmental benefits and saves the cost.
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Paragraph 0100-0102; 0107-0109; 0115-0117; 0122-0193
(2021/01/11)
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- Process for preparation of phosphorane and phosphonyl compounds
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The invention relates to the field of new materials of fine chemicals, in particular to a new safe, convenient, mild, efficient, environment-friendly and economical preparation process technology of phosphorane and phosphonyl compounds.
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Paragraph 0028-0030
(2021/06/06)
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- Co-production preparation of monoacylphosphine and bisacylphosphine and oxides thereof
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The invention relates to the field of photocuring functional new material chemicals, discloses co-production preparation of a series of monoacylphosphine and diacylphosphine, and oxides thereof, namely monoacylphosphine oxide and diacylphosphine oxide for the first time, wherein one-pot preparation of the compounds in the same flow process and the same reactor is achieved for the first time. The process technology has the characteristics of outstanding low-cost economic competitiveness and environmental friendliness. The compounds are important olefinic bond (C=C)-containing unsaturated photoinitiator for a radiation polymerization system.
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Paragraph 0058-0060
(2021/11/19)
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- Preparation method of photoinitiator
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The invention provides a preparation method of a photoinitiator phenyl bis(2, 4, 6-trimethylbenzoyl) phosphine oxide, which is characterized by comprising the following steps of (1) reacting water serving as a solvent, phenyl phosphine oxide and 2, 4, 6-trimethylbenzaldehyde serving as raw materials and tert-butyl alcohol salt and pyridinium serving as catalysts to obtain an intermediate compoundshown as a formula I, wherein the equation is as described in the specification, (2) oxidizing the formula I under the action of an oxidizing agent to obtain the target product photoinitiator phenyl bis(2, 4, 6-trimethylbenzoyl) phosphine oxide, wherein the equation is as described in the specification. Tert-butyl alcohol salt and pyridinium are used as catalysts, and the pyridinium has the effectof a phase transfer catalyst, therefore, water can be directly used as a reaction solvent, the use of an organic solvent with toxicity and relatively high price is avoided, and compared with the prior art, the method is more economical and environment-friendly.
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Paragraph 0053-0060
(2021/03/24)
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- Preparation method of bis(2, 4, 6-trimethylbenzoyl)phenylphosphine oxide
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The invention provides a preparation method of bis(2, 4, 6-trimethylbenzoyl)phenylphosphine oxide, which comprises the following steps of (1) mixing sodium sand, phenylphosphine dichloride and urotropine in a non-polar solvent to react to obtain a reactant, and (2) adding mesitylene formyl chloride into the reactant obtained in the step (1), reacting, and oxidizing to obtain bis(2, 4, 6-trimethylbenzoyl)phenylphosphine oxide. According to the method, urotropine is used as an activating agent, sodium phenylphosphine can be effectively prevented from being agglomerated to form sodium phenylphosphine polyphosphide, generation of sodium phenylphosphine is promoted, the hydrogen phenylphosphine process is not needed, and the reaction safety is greatly improved; and the preparation process can be realized by only needing a small amount of activating agent, so that the economical efficiency of industrial production is facilitated, the content of organic matters in the wastewater can be reduced, certain environmental benefits are achieved, and the cost is saved.
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Page/Page column 6-14
(2020/12/30)
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- Double-benzoyl phenyl phosphine oxide and benzoyl diphenyl phosphine oxide of the preparation method
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The invention relates to a preparation method of di (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide used in the technical field of radiation polymerization curing new materials, hydrogen phosphide as a raw material is reacted with chlorobenzene or bromobenzene and 2,4,6-trimethylbenzoyl chloride, and an acyl oxygen phosphonic compound is obtained by oxidizing with an oxidant. By adjusting the feed ratio, the di (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and the (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide are respectively obtained, and the purpose for simultaneously producing the two target products of di (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and the (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide can be achieved by use of same material and device, and compared with known technology paths reported in literatures, the preparation method has the significant advantages of novelty of the chemical reaction technology, cost economic competitiveness and environmental friendliness.
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Paragraph 0045-0050
(2019/03/21)
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- Preparation method of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide
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The invention provides a preparation method of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide. The preparation method comprises the following steps: using phenyl phosphorus dichloride as an initial raw material, under the protection of nitrogen, adopting a catalyst (the catalyst is a mixture of potassium tert-butoxide and serine) to replace chlorine with powdery metal sodium, carrying out reduction under a weak alkaline condition, and carrying out condensation and oxidation reaction with 2,4,6-trimethylbenzoyl chloride to prepare a phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide product. The preparation method of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide has better catalytic effect and higher yield; and the metal sodium is prepared into powder in a toluene solvent, and all reaction processes are carried out under the protection of nitrogen, so that the safety is high.
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Paragraph 0032; 0037-0039; 0043-0045; 0049-0050
(2019/10/01)
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- Preparation method of photoinitiator phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide
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The invention belongs to the technical field of photoinitiator preparation synthesis, particularly relates to a preparation method of organophosphorus photoinitiator phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and provides a preparation method of the phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide. The preparation method is characterized by comprising the steps: phenyl phosphine metallide and CO2 are directly constructed to form phosphenyl phthalate, then carboxyl of the phosphenyl phthalate is subjected to in-situ activation through N,O-dimethylhydroxylamine hydrochloride (DMHA) toprepare Weinreb amide, then a Grignard reagent or an organic lithium reagent of trimethylphenyl is used for attacking, an addition reaction is conducted to obtain a main skeleton, and finally throughoxidation, the phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide is obtained. A process technology route is novel, the raw materials are cheap and easy to obtain, the cost is economical, environmental friendliness is achieved, and compared with an existing process, significant advantages are achieved.
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Paragraph 0040
(2019/10/29)
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- A acylphosphanes efficient photoinitiator and its preparation method
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The invention discloses an acylphosphine efficient photoinitiator and a preparation method thereof. The preparation method comprises the following steps of firstly in a solvent and in the presence of a catalyst, reacting organic phosphorus halide as a raw material with an alloy of active metal; reacting reaction product obtained from the former step with an aliphatic alcohol compound containing active hydrogen to product a phosphine hydride compound; reacting the phosphine hydride compound with acyl halide to obtain an acylphosphine compound; after the reaction is completed and under the condition of no separation, further adding an oxidant into a reaction container to prepare acylphosphine oxide. By the preparation method of the acylphosphine efficient photoinitiator designed by the invention, the separation of an intermediate is not needed, the yield and production efficiency of the product are increased and the needs of industrial production can be met.
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Paragraph 0037-0038
(2017/03/28)
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- Preparing method for acyl phosphate (oxide) or sulfonyl phosphate (oxide) compound
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The invention relates to the technical field of novel radiation-cured photo-polymerization materials, in particular to a synthesizing method for an acyl phosphate or acyl phosphate oxide (sulfur) or sulfonyl phosphate oxide (sulfur) photo-polymerization initiator of the structure shown in the formula (I) in the description.
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Paragraph 0079; 0080
(2017/01/02)
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- Preparation method of acyl phosphine (oxygen) or sulfonyl phosphine (oxygen) compounds
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The invention relates to the technical field of radiation-cured photo-polymerized novel materials and especially relates to synthesis methods for a photo-polymerization initiator in the types of acyl phosphine, acyl phosphine oxygen (sulfur) or sulfonyl phosphine oxygen (sulfur) represented as the formula (I).
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Paragraph 0043; 0044; 0048; 0049; 0065; 0066
(2018/02/04)
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- A photo initiator double (2, 4, 6-trimethyl benzoyl) method for preparing phenyl phosphine oxide
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The invention discloses a preparation method for a photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. The preparation method comprises the synthesis steps: under the protection of inert gas, carrying out a reaction of aluminium trichloride or tin tetrachloride and trimethylsilane in the temperature range of 0-100 DEG C to obtain aluminium dichloride ions, and rapidly acting with dichlorophenyl phosphine in the reaction system, to obtain a bis(aluminium trichloride or tin tetrachloride)phosphine salt intermediate; then carrying out a reaction of the intermediate and 2,4,6-trimethyl benzoyl chloride, to obtain bis(2,4,6-trimethylbenzoyl)phenyl phosphine; and under the condition of the temperature of 20-50 DEG C, oxidizing by nitrogen dioxide, to obtain the target product. The method avoids use of a dangerous active metal potassium or sodium, and adopts aluminium trichloride or tin tetrachloride with relatively low price and trimethylsilane for on-site generation of the active intermediate to achieve the reaction. The method has the characteristics of low preparation cost, simple and safe operation process, easy control of the reaction process, high product yield, good purity, easy realization of mass production and the like.
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Paragraph 0034; 0037; 0038; 0039
(2017/02/09)
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- Preparation method for phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide
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The invention discloses a preparation method for phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide. The preparation method comprises the following steps: selecting triphenylphosphine as a raw material for reactions with sodium metal and phosphorus halide in the presence of one or more catalysts; carrying out an acyl chloride reaction; carrying out oxidation to prepare phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide. The preparation method has the advantages of being easy in raw material obtaining, low in cost, easy to operate, environmentally friendly, and easy for industrialization.
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Paragraph 0022
(2016/10/09)
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- Preparation method of photoinitiator phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide
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The invention discloses a preparation method of a photoinitiator phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide, comprising the steps of enabling diethyl benzylphosphonate and an excessive vitride solution to react in argon under the temperature of 60-70 DEG C, so as to generate phenyl phosphine, enabling the phenyl phosphine and 2,4,6-trimethylbenzoyl chloride to react, so as to obtain a methylbenzene solution of diphenyl(2,4,6-trimethylbenzoyl)phosphine, and oxidizing the diphenyl(2,4,6-trimethylbenzoyl)phosphine into 2 phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide by hydrogen peroxide without separating. According to the process, dangerous metal sodium or potassium is not used, the process is advanced, the operation is simple and safe, the product yield is high, the quality is good, and large-scale production is easy.
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Paragraph 0025; 0026; 0027
(2016/12/26)
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- ( benzoin phosphine oxygen radical ) (are three a phenyl) methanone and ( benzene phosphine oxygen radical ) double (are three a phenyl methanone) method for the preparation of
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The invention relates to the technical field of optical radiation free-radical polymerized new materials, especially to a novel synthesis technological process of commercial photoinitiator compounds of (diphenylphosphine oxide)(mesitylene)ketone and (phenylphosphine oxide)bis(mesitylene ketone). According to the invention, 1,3,5-trimethyl-2-(trichloromethyl)-benzene is used as a key raw material and is respectively subjected to a condensation reaction with corresponding organic phosphine precursors so as to prepare the target compounds. In comparison with a known technological route, the technology disclosed in the application has significant advantages such as novelty of the chemical reaction process, economical cost, competitiveness and environmental friendliness.
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Paragraph 0016; 0025; 0026
(2017/04/07)
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- The preparation method of compound acyl method
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The invention relates to the technical field of radiation polymerization curing novel materials, and especially relates to a chemical preparation novel process of an acyl phosphine (oxide) compound represented by the general formula (I). A core characteristic of the method is that: a Grignard reagent of an aromatic compound substituted by an appropriate trichloromethyl group is subjected to condensation with related (substituted) phosphorus halide, such that a critical phosphorus-carbon bond is obtained. The innovativeness, cost economic competitiveness, and environment-friendliness of the process and chemical reaction technology provided by the invention are substantially advantaged than those of literatures and existing process routes.
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- benzyl pair (2, 4, 6-trimethyl benzoyl) phosphine oxide of the preparation method
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The invention discloses a preparation method of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide as an efficient free radical photoinitiator. The preparation method of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide comprises the concrete steps of with 2,4,6-trimethylbenzaldehyde as a raw material, enabling 2,4,6-trimethylbenzaldehyde and phenylphosphine oxide to be subjected to condensation reaction in the existence of a catalyst, and then, carrying out oxidation reaction. Extraction and solvent replacement are not needed and continuous reaction can be realized in the reaction process. The preparation method of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, disclosed by the invention, is low in price, environment-friendly, easy to operate and suitable for realizing industrialization.
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Paragraph 0011; 0055; 0056
(2016/11/21)
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- Phase change inks containing amide gellant compounds with aromatic end groups
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Disclosed is a phase change ink comprising a colorant, an initiator, and a phase change ink carrier, said carrier comprising at least one radically curable monomer compound and a compound of the formula wherein R1 and R1′ are the same, and wherein R1 and R1′ are each an aromatic group; and wherein R2 and R2′ and R3 each, independently of the others, are alkylene groups, arylene groups, arylalkylene groups, or alkylarylene groups; or wherein, in embodiments, R1 and R1′ can be the same or different, and wherein R1 and R1′ each, independently of the other is an alkyl group having a least one ethylenic unsaturation, an arylalkyl group having at least one ethylenic unsaturation, an alkylaryl group having at least one ethylenic unsaturation, or an aromatic group, provided that at least one of R1 and R1′ is an aromatic group; and provided that neither of R1 or R1′ is a photoinitiator group. Also disclosed herein is a method of printing with the phase change ink.
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Page/Page column
(2013/08/28)
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- Method for producing acylphosphine oxide solids
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The present invention relates to a process for the preparation of solid acylphosphine oxides by converting an acylphosphine oxide which is in the form of a melt or in dispersed form into the solid state of aggregation with mechanical stress, shearing/internal agitation of the melt.
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- PROCESS FOR PREPARING ACYLPHOSPHANES AND DERIVATIVES THEREOF
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The invention relates to a process for the preparation of (bis)acylphosphanes of formula I, wherein n and m are each independently of the other 1 or 2; R1 if n = 1 , is e.g. unsubstituted or substituted C1-C18alkyl or C2-C18alkenyl, or phenyl, R1 if n = 2, is e.g. a divalent radical of the monovalent radical defined above; R2 is e.g. C1-C18alkyl, C3-C12cycloalkyl, C2-C18alkenyl, mesityl, phenyl, naphthyl; R3 is one of the radicals defined under R1; the process comprises the steps a) contacting e.g. elemental phosphorous [P]∞, P(Hal)3 with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH2; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV or, in case that in formula I m = 1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa, wherein R is the residue of an alcohol and R2 is as defined above; d) alkylation reaction subsequent reaction with an electrophilic agent R1Hal or other electrophilic agents to obtain the compounds of formula I. An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides, which are used as photoinitiators.
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Page/Page column 46
(2010/11/08)
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- PROCESS FOR PREPARING ACYLPHOSPHANES AND DERIVATIVES THEREOF
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The present invention relates to a new, selective process for the preparation of mono- and bisacylphosphanes of formula (I) n and m are each independently of the other 1 or 2; R1, if n = 1, is e.g. phenyl R1, if n = 2, is e.g. C1-C18alkylene or phenylene; R2 is e. g. C1-C18alkyl, phenyl or substituted phenyl; R3 is e. g. C1-C18alkyl, by (1) reacting a phosphorous halide of formula Ila or a phosphorous halide oxide of formula (Ilb) or a phosphorous halide sulfide of formula (IIc) with an alkali metal in a solvent in the presence of a proton source; (2) subsequent reaction with m acid halides of formula (III) An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono-and bisacylphosphane sulfides.
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Page/Page column 28
(2010/02/10)
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- A PROCESS FOR THE PREPARATION OF ACYLPHOSPHINES
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A process for the preparation of acylphosphines of formula (I) wherein m is 1 or 2; R1, R2, and R3 are organic residues derived from aliphatic or aromatic hydrocarbons; by (1) reacting organic phosphorus halides of formula (II) wherein Y is Br or Cl,with an alkali metal in a solvent in the presence of an activator, wherein the alkali metal is present in the form of a dispersion of alkali metal particles having a mean particle size of ≤ 500 μm in the solvent, (2) subsequent reaction with acid halides of formula (III) which process is carried out without isolation of the intermediates. Preferably, R1, R2 and R3 are independently from each other phenyl, naphthyl and bi-phenyl, being unsubstituted or substituted by one to five halogen, C1-C8 alky and/or C1-C8 alkoxy. Most preferably, R1 and R3 are phenyl and R2 is 2,4,6-trimethylphenyl. The alkali metal is preferably sodium, the activator is preferably chlorobenzene and/or n-butanol.
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Page/Page column 10-11
(2010/02/10)
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- Photo-curable reparative material for dental use
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A photocurable dental restorative comprising (i) 100 parts by weight of a polymerizable monomer, (ii) 0.01 to 5 parts by weight of a photopolymerization initiator of acylphosphine oxide, and (iii) 200 to 1900 parts by weight of an inorganic filler, wherein the inorganic filler (iii) is a mixed filler of: (A) irregular-shaped inorganic particles having an average particle size of not smaller than 0.1 μm but smaller than 1 μm; (B) spherical inorganic particles having an average primary particle size of not smaller than 0.1 μm but not larger than 5 μm; and (C) fine inorganic particles having an average primary particle size of not larger than 0.1 μm; which are so blended as to satisfy the following mass ratios {circle over (1)} to {circle over (3)}: mA/(mB+mC)=0.2 to 3??{circle over (1)} mB/(mB+mC)=0.5 to 0.99??{circle over (2)} mC/(mB+mC)=0.01 to 0.5??{circle over (3)} where mA, mB and mC are masses of the inorganic particles (A) to (C). The restorative features excellent handling property, and makes it possible to obtain a cured product having a high fracture toughness and excellently glossy surface.
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- Molecular complex compounds of acylphosphine oxide and α-hydroxy ketones as photoinitiators
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Molecular complex compounds comprising a mono-, bis- or trisacylphosphine oxide compound with an α-hydroxy ketone compound are suitable as photoinitiators for the photopolymerization of free-radically polymerizable compounds.
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