CN107400144B

CN107400144B - Acylphosphine (oxy) compounds, process for their preparation and their use

Info

Publication number: CN107400144B
Application number: CN201710667166.2A
Authority: CN
Inventors: 王智刚; 郑成; 赵新阳
Original assignee: Shenzhen Youwei Technology Holding Co Ltd
Current assignee: Shenzhen Youwei Technology Holding Co Ltd
Priority date: 2017-08-03
Filing date: 2017-08-03
Publication date: 2020-04-14
Anticipated expiration: 2037-08-03
Also published as: CN107400144A

Abstract

The invention relates to the technical field of new materials and organic chemicals, in particular to a new acyl phosphine oxide type compound shown in a formula (I), a chemical preparation process technology, application of the new acyl phosphine oxide type compound as a radiation curing photoinitiator, and application of the new acyl phosphine oxide type compound in radiation curing formula products, especially in aqueous UV-LED photocuring paint or ink and other occasions.

Description

Acylphosphine (oxy) compounds, process for their preparation and their use

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of new materials, organic chemicals, in particular to a new acyl phosphine oxide type structure compound, a chemical preparation process technology, application of the compound as a radiation curing photoinitiator, and application of the compound in radiation curing formula products, especially aqueous UV-LED photocuring paint or ink and the like.

[ background of the invention ]

Photoinitiator compounds are an important class of fine organic chemical materials. In the field of radiation curing technology using ultraviolet Light or visible (UV) Light or LED (Light-Emitting Diode) as a Light source, a photoinitiator compound capable of generating radical active species under a Light irradiation condition is a key species for inducing an ethylenically unsaturated system to perform efficient photopolymerization, and thus is one of important radiation curing formulation components. Of the numerous photoinitiator products which have been commercially used, the phosphonyl compounds have taken an outstanding position, and representative products thereof are monoacylphosphine oxide compounds "2, 4, 6-trimethylbenzoyldiphenylphosphine oxide" (trade name TPO) and "2, 4, 6-trimethylbenzoylethoxyphenylphosphine oxide" (TPO-L), and bisacylphosphine oxide compounds "bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide" (BAPO, or Irgacure819), and aqueous dispersions of 819 (Irgacure 819-DW, basf corporation). Such compounds are finding increasingly widespread use due to a combination of high initiating activity, photobleaching, long wavelength absorption, and broad spectrum applicability to UV-LEDs, as described in, for example, US4292154, US4737593, US6399805, EP495752, and others. Furthermore, there are also a considerable number of examples in the technical literature disclosing the use of the above acylphosphine oxide photoinitiators in combination with other types of photoinitiators, for example the patents US8507726 and US 6777459.

On the other hand, the water-based light-cured coating and ink product conforms to the new strategic trend of the development of the world energy-saving and environment-friendly industry, so that the light-cured coating and ink product is increasingly and widely regarded and rapidly developed in recent years, particularly in the fields of water-based spraying materials with wide universality, water-based ink-jet printing materials and other water-based UV-LED light-cured materials, because the problems of environmental pollution and artificial health protection are completely avoided in the construction process and two stages after light curing, the energy consumption and ozone generation are greatly reduced by the application of the LED light-cured technology, and the industry is continuously and powerfully increased. From technical considerations, the formulation of aqueous photocurable coatings or inks requires two key materials, namely aqueous photocurable resin (water resin) and aqueous photoinitiator (water photo-initiators); for curing of the water-based LED system, a photoinitiator which has sensitive absorption for the long-wave emission wavelength (365-. Therefore, the design, development, and industrialization of novel water-soluble or water-dispersible photoinitiator compounds are currently the key technical challenges facing the field. Known acylphosphine oxide-type compounds, including the oil soluble TPO, TPO-L, 819, or 819-DW products mentioned above, are difficult to formulate with aqueous resin systems to form storage stable coating or ink products due to the highly hydrophobic nature, none of which possess sufficient water solubility or water-dispersing characteristics.

[ summary of the invention ]

Aiming at the technical problems, the invention provides a novel acylphosphine (oxy) compound which has better water solubility or water dispersibility, can be effectively compatible with water-based light-cured resin and can be compounded to form water-based light-cured ink or coating with stable storage, and a preparation method and application thereof.

The first object of the present invention is to provide an acylphosphine (oxy) compound represented by the general formula (I):

in the general formula (I):

R₀is a compound containing R₃、R₄、R₅、R₆、R₇Substituted aryl, or R₈、R₉、R₁₀Substituted tertiary alkyl, wherein R₃、R₄、R₅、R₆、R₇Independently of one another are hydrogen, halogen atoms, R, OR, NRR', CH₂OH、CH₂OR, OR CH₂NRR ', wherein R or R' are independently of each other selected from the group consisting of linear or branched alkyl containing 1 to 24 carbon atoms, -C₆-C₁₂Aryl, straight or branched chain alkyl containing 1-24 carbon atoms containing 1-6 non-consecutive A elements, -C containing 1-6 non-consecutive A elements₆-C₁₂One of aryl, wherein, the element A is selected from one or more of oxygen, nitrogen and sulfur; r and R' are independently present or are connected to form a 3-6 membered ring system structure; r₈、R₉、R₁₀Independently of one another are R, R₈、R₉、 R₁₀Either alone or in combination to form a 3-6 membered carbocyclic ring structure;

x is oxygen or sulfur, or X is absent:

n is an integer between 1 and 1000; r₁Is R or-C (O) -R₀；

When n is 1, R₂-Q is selected from hydrogen, C containing 0-4 substituents₆-C₂₄Aryl radical, CH₂OH、 CH₂OR、CH₂OC(O)R、CH₂NRR’、CHR(OH)、CRR’(OH)、CCH₃(CH₂OH)OH、 C(CH₂OH)₂OH、CH₂CH₂OH、CH₂CHMeOH、CHMeCH₂OH、CH₂CHPhOH、 CH₂C(O)R、CH₂CO₂H or its metal or amine salt, CH₂CH₂CO₂H or its metal or amine salt, CH₂CH₂C(O)OCH₂CH₂OH、CH₂CHMeC(O)OCH₂CH₂OH、 CH₂CH₂C(O)OCH₂CH₂OCH₂CH₂OH、CH₂CH₂C(O)OY、CH₂OC(O)-NHY、 CH₂CH₂One of oc (o) NHY, Y being a-C containing 2-6C ═ C double bonds₂-C₃₆The radical(s) is (are),

when n is 2 or an integer greater than 2, -R₂-Q is an n-membered linking group; -R₂-is selected from-CH₂-、-CH₂CH₂-、-CH₂CH(OH)CH₂-、-CH₂CH(OR)CH₂-、- CH₂CH(OC(O)R)CH₂-、-CH₂CH₂C(O)OCH₂CH₂-、-CH₂CH(Me)C(O)OCH₂CH₂-、 -CH₂CH₂C(O)OCH₂CH₂OCH₂CH₂-、-CH₂CH₂C(O)OCH₂CH₂CH₂-、- CH₂CH₂C(O)OCH₂CH₂CH₂CH₂-one of the above; q is a small molecule or polymer group having 2 or more-NHC (O) O-units; or, Q is a small molecule or polymer group having 2 or more-C (O) O-units;

or, when n takes the value 2 or an integer greater than 2 and when R₁When is R, -R₂-Q is a radical containing an n-membered-CH₂CH₂C(O)O-、-CH₂CH(Me)C(O)O-、-CH₂CH₂C(O)C(O)O-、- CH₂CH(Me)C(O)C(O)O-、-CH₂CH₂C(O)C(O)-、-CH₂CH(Me)C(O)C(O)-、- CH₂CH₂C(O)C(O)NH-、-CH₂CH(Me)C(O)C(O)NH-、-CH₂CH₂C(O)-、-CH₂CH(Me)C(O)-、-CH₂CH₂C(O)NH-、-CH₂CH(Me)C(O)NH-、- CH₂CH₂C(O)NR-、-CH₂CH(Me)C(O)NR-、-CH₂CH₂8O₂-、-CH₂CH(Me)SO₂-、- CH₂CH₂S (O) R-, or-CH₂CH (Me) S (O) R-units,

or, -R when n is 2 or an integer greater than 2₂-Q is a radical containing an n-membered-CH₂CH (OH) -, or-CH₂CH (OR) -units or polymer groups.

Preferably, R₃＝R₅＝R₇＝CH₃And R₄＝R₆H; or R₃＝R₇(ii) Cl and R₄＝R₅＝R₆H; or R₃＝R₇＝OCH₃And R₄＝R₅＝R₆H; or R₃＝R₅＝R₇＝CH₃And R₄＝R₆＝ CH₂OH; or R₃＝R₅＝R₇＝CH₃And R₄＝R₆＝CH₂OC (O) R; or R₃＝R₅＝R₇＝CH₃And R₄＝CH₂OH and R₆H; or R₃＝R₅＝R₇＝CH₃And R₄＝R₆＝CH₂OR; or R₃＝ R₅＝R₇＝CH₃And R₄＝R₆＝CH₂NRR'; or R₃＝R₅＝R₇＝CH₃And R₄＝CH₂OH and R₆＝CH₂NRR’。

Preferably, R₈＝R₉＝R₁₀＝CH₃(ii) a Or R₈＝R₉＝R₁₀＝CH₂CH₃(ii) a Or R₈＝CH₃、R₉- R₁₀Is a cyclohexane structure.

Preferably, n is an integer between 1 and 100; more preferably, n is an integer of 1 to 10.

Preferably, R₁Is selected from C₆H₅、p-CH₃OC₆H₄、CH₃、CH₂CH₃、CH₂CH＝CH₂、CH₂Ph、 C(O)CEt₃、C(O)CMe₃Biphenyl, 2,4,6-trimethylbenzoyl, 2, 6-dimethoxybenzoyl or 2, 6-dichlorobenzoyl.

Preferably, C₆-C₂₄The aryl is selected from one of phenyl, biphenyl and naphthyl.

Preferably, Y is a-C radical containing 2 to 6 acrylate units₂-C₃₆The radical, preferably, Y is one of the radicals indicated below:

preferably, when n is 2 or an integer greater than 2, Q is one of the groups shown below:

or Q is one of the groups shown below:

，

wherein R is₁₁Is hydrogen or R.

Or preferably, when n takes the value 2 or an integer greater than 2 and when R₁When R is, Q is as followsOne of the groups shown:

。

or preferably, -R when n is 2 or an integer greater than 2₂The structure-Q is a structure containing an n-membered-CH₂CH (OH) -, or-CH₂A small molecule or polymer group of CH (OR) -units, Q is one of the groups shown below:

it is a second object of the present invention to provide a process for preparing acylphosphine (oxy) compounds of the general formula (I): organic halogenated phosphine R₁PHal₂Starting from, organic phosphine R is prepared₁PH₂Organic phosphine hydrogen R₁PH₂Under the action of alkali and acyl halide R₀C (O) Hal or anhydride R₀C(O)OC(O)R₀Reacting to obtain an intermediate in the form of A or B, and reacting the intermediate with formaldehyde and an oxidant to obtain an acylphosphine (oxy) compound shown in a general formula (I), wherein Hal is halogen; or carrying out a first reaction between the intermediate A or B and a substance represented by the general formula C in the presence of an oxidant to obtain an acylphosphine (oxy) compound represented by the general formula (I); wherein Q represents a structure described by the chemical characteristics of Q and is a small molecule compound or polymer resin compound containing a polyepoxy, polyisocyanate, polyunsaturated carbonyl compound, polycarboxylic acid, polybasic acyl halide or polybasic anhydride functional group; the base is inorganic metal hydroxide or alkoxide or carbonate or carboxylate compound, or organic tertiary amine compound; the oxidant is selected from one of oxygen, air-metal salt compound, metal hypochlorite, oxygen-metal salt compound, hydrogen peroxide, peroxide in the form of ROOH, peroxyacid or sulfur; q is an integer between 1 and n; the substance represented by the general formula C is selected fromOne of polyepoxy C1, polybasic isocyanate C2, polybasic unsaturated carbonyl compound C3, polybasic carboxylic acid C4, polybasic acyl halide C5 and polybasic acid anhydride C6;

or, intermediate A or B and alkyl halide or alkyl pseudohalogen compound marked as R-Hal are subjected to nucleophilic substitution reaction in the presence of second base to prepare acylphosphine (oxygen) compound shown as general formula (I),

or, a starting phosphono starting material D is subjected to a Blanc reaction under the combined action of an acid and formaldehyde to obtain a halide intermediate E, wherein r is 1 or 2, the acid is Lewis or protonic acid, and Hal represents a halogen atom; the intermediate E is subjected to nucleophilic substitution reaction under the action of a nucleophilic reagent HNu to prepare an acylphosphine (oxygen) compound shown in a general formula (I),

or, bisacylphosphine oxide (BAPO) in acid and electrophilic reagent E⁺Under the action of the reaction, generating monophosphoryl group pair E⁺To prepare an acylphosphine (oxy) compound shown in the general formula (I); the acid is a lewis acid or a protic acid; electrophilic reagent E⁺Is C₁-C₄₈Or a branched or straight chain aliphatic or aromatic aldehyde or ketone, or α -unsaturated aldehyde, ketone, ester, nitrile, or amide, or a nitroalkene, or an alkenyl sulfone or sulfoxide,

or, the phosphonic acyl intermediate sodium bis (2,4, 6-trimethyloyl) phosphine of structure F or structure G phosphonic dimethyl bis (mesitylmethane), or the enol resonance isomers thereof react with formaldehyde or C reagent and react with oxidant to obtain acyl phosphine (oxygen) compound shown in general formula (I); the reagent C is one of polyepoxy C1, polyisocyanate C2, polyunsaturated carbonyl compound C3, polycarboxylic acid C4, polybasic acyl halide C5 and polybasic acid anhydride C6,

。

preferably, the first reaction is selected from one of an epoxy ring-opening reaction, an isocyanate addition reaction, a michael conjugate addition reaction, and an esterification reaction.

Preferably, the second base is an inorganic metal hydroxide or alkoxide or carbonate or carboxylate compound, or an organic tertiary amine-type compound.

Preferably, the acid is selected from one or more of aluminum trichloride, zinc chloride, ferric trichloride, aluminum tribromide, hydrochloric acid, hydrobromic acid and acetic acid; further preferably, the acid is aluminum trichloride or hydrochloric acid.

Preferably, said Hal is chlorine.

Preferably, the nucleophile HNu is a substance containing an oxygen, nitrogen, sulfur, or phosphorus atom, and more preferably, the nucleophile HNu is water or NR₃、HNRR’、H₂NR, HSR, RSSR ', HP (O) RR', or a heterocycle containing an oxygen, nitrogen, sulfur, or phosphorus atom.

Preferably, the electrophile E⁺Is formaldehyde, acrylic acid, acrolein, or a mono-or poly-acrylate monomer or acrylate polymer resin; further preferably, the acid is aluminum trichloride or hydrochloric acid, and the electrophile E⁺Is formaldehyde.

The third purpose of the invention is to provide the application of the acyl phosphine (oxygen) compound shown in the general formula (I) as a photoinitiator or other functional additive components in a photocuring formula system; or as intermediates or starting materials or reagents in chemical synthesis.

A fourth object of the present invention is to provide a mixture curable by actinic radiation containing a compound of the above general formula (I).

Preferably, the mixture contains at least one compound of the formula (I) as photoinitiator or one of the photoinitiator components; and at least one ethylenically unsaturated compound.

Preferably, the compound of the formula (I) is contained in an amount of 0.01 to 30 parts by weight per 100 parts by weight of the total amount of the ethylenically unsaturated compounds; preferably, the compound of formula (I) is contained in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the total amount of the ethylenically unsaturated compounds.

Preferably, the ethylenically unsaturated compound is a compound or mixture which is crosslinked by free radical polymerization of double bonds, the ethylenically unsaturated compound being a monomer, oligomer or prepolymer, or a mixture or copolymer thereof, or an aqueous dispersion thereof.

It is a fifth object of the present invention to provide the above mixture for use as a photocurable coating or ink.

Preferably, the photocureable coating or ink is applied to the fields of ink-jet printing, paper printing, adhesives, woodware coating, plastic coating, automobile coating, packaging materials, display technology, building materials, flexible electronic or photovoltaic materials.

The present inventors have surprisingly found that acylphosphine (oxy) compounds containing suitable polar functional groups, obtained via the synthesis method of the present invention, possess suitable water solubility or water dispersibility. We further prove that the novel water-based photoinitiator can be effectively compatible with water-based light-cured resin and compounded to form water-based light-cured ink or paint with stable storage, particularly, the water-based photoinitiator enables a water-based energy-saving environment-friendly LED light-cured technology to be realized for the first time, and the technology has profound influence on the fields of woodware green coating, environment-friendly printing, ink-jet printing, energy-saving materials and the like.

[ description of the drawings ]

FIG. 1 is a diagram of UV-Vis absorption spectrum (ultraviolet absorption spectrum) of a compound prepared in the first example of the present invention;

FIG. 2 is a diagram showing a UV-Vis absorption spectrum (ultraviolet absorption spectrum) of a compound prepared in example thirteen of the present invention.

[ detailed description ] embodiments

The present application discloses novel acylphosphine (oxy) compounds of the general formula (I):

in the structure of the compound of the above general formula (I):

R₀is a compound containing R₃、R₄、R₅、R₆、R₇Substituted aryl, or R₈、R₉、R₁₀Substituted tertiary alkyl (as shown in the figure), wherein R₃、R₄、R₅、R₆、R₇Independently of one another are hydrogen, halogen atoms, R, OR, NRR', CH₂OH、CH₂OR, OR CH₂NRR 'wherein R or R' independently of one another are radicals containing from 1 to 24 carbon atoms (marked as-C)₁-C₂₄The same applies hereinafter) straight-chain or branched alkyl or-C₆-C₁₂The aryl, R or R ' structure can contain 1-6 discontinuous oxygen, nitrogen or sulfur elements, and when R and R ' exist simultaneously, a 3-6-membered ring system structure can be formed between the R and R '. R₈，R₉，R₁₀Independently of one another, R, any two of which may also form a 3-to 6-membered carbocyclic ring structure. Preferably, R₃＝R₅＝R₇＝CH₃And R₄＝R₆H, or R₃＝R₇(ii) Cl and R₄＝R₅＝R₆H, or R₃＝R₇＝OCH₃And R₄＝R₅＝R₆H, or R₃＝R₅＝R₇＝CH₃And R₄＝R₆＝CH₂OH, or R₃＝R₅＝R₇＝CH₃And R₄＝R₆＝CH₂OC (O) R, or R₃＝R₅＝R₇＝CH₃And R₄＝CH₂OH and R₆H, or R₃＝ R₅＝R₇＝CH₃And R₄＝R₆＝CH₂OR, OR R₃＝R₅＝R₇＝CH₃And R₄＝R₆＝CH₂NRR', or R₃＝R₅＝R₇＝CH₃And R₄＝CH₂OH and R₆＝CH₂NRR'. Preferably, R₈＝R₉＝R₁₀＝CH₃Or R is₈＝R₉＝R₁₀＝CH₂CH₃Or R is₈＝CH₃And R₉-R₁₀Is a cyclohexane structure:

x is oxygen or sulfur, or X is absent (i.e., the compound of formula I is a phosphinane);

n is an integer between 1 and 1000, preferably n is an integer between 1 and 100, more preferably n is an integer between 1 and 10;

R₁is R or-C (O) -R₀Preferred is R₁Is C₆H₅，p-CH₃OC₆H₄，CH₃，CH₂CH₃， CH₂CH＝CH₂，CH₂Ph，C(O)CEt₃，C(O)CMe₃Biphenyl, 2,4,6-trimethylbenzoyl, 2, 6-dimethoxybenzoyl, or 2, 6-dichlorobenzoyl;

when n is 1, R₂-Q is hydrogen, C having 0 to 4 substituents₆-C₂₄Aryl (preferably phenyl, biphenyl, naphthyl), CH₂OH，CH₂OR，CH₂OC(O)R，CH₂NRR’，CHR(OH)， CRR’(OH)，CCH₃(CH₂OH)OH，C(CH₂OH)₂OH，CH₂CH₂OH，CH₂CHMeOH， CHMeCH₂OH，CH₂CHPhOH，CH₂C(O)R，CH₂CO₂H or a metal or amine salt thereof, CH₂CH₂CO₂H or a metal or amine salt thereof, CH₂CH₂C(O)OCH₂CH₂OH， CH₂CHMeC(O)OCH₂CH₂OH，CH₂CH₂C(O)OCH₂CH₂OCH₂CH₂OH， CH₂CH₂C(O)OY，CH₂OC (O) -NHY, or CH₂CH₂OC (O) NHY, where Y is a-C group containing 2-6C ═ C double bonds₂-C₃₆The radical, preferably Y, is a radical-C containing 2 to 6 acrylate units₂-C₃₆The radical, more preferably Y, is one of the radicals indicated below:

when n is 2 or an integer greater than 2, -R₂-the structure Q is an n-membered linking group; -R₂-is preferably-CH₂-，-CH₂CH₂-，-CH₂CH(OH)CH₂-，-CH₂CH(OR)CH₂-，- CH₂CH(OC(O)R)CH₂-，-CH₂CH₂C(O)OCH₂CH₂-，-CH₂CH(Me)C(O)OCH₂CH₂-， -CH₂CH₂C(O)OCH₂CH₂OCH₂CH₂-，-CH₂CH₂C(O)OCH₂CH₂CH₂-，- CH₂CH₂C(O)OCH₂CH₂CH₂CH₂And Q is a small molecule or polymer group having 2 or more-NHC (O) O-units, and Q is preferably the following group:

alternatively, Q is a small molecule or polymer group having 2 or more-C (O) O-units, and Q is preferably the following group (wherein R is₁₁Is hydrogen or R):

it will be apparent to those skilled in the art that the polyisocyanate in the above-described Q structure is readily apparentThe ester [ NHC (O) O ] unit or polybasic ester [ C (O) O ] unit is derived from R₂The hydroxyl group OH in the structure is obtained by esterification reaction with the corresponding polyurethane polyol NCO group or polybasic acid anhydride or polybasic acid halide, therefore, the above-mentioned preferred Q structure is only an exemplary but non-limiting structure, and all Q structures conforming to the essence of the above-mentioned chemical reaction are within the scope of the present disclosure.

Or, when n takes the value 2 or an integer greater than 2 and when R₁When is R, -R₂The structure-Q is a structure containing an n-membered-CH₂CH₂C(O)O-，-CH₂CH(Me)C(O)O-，-CH₂CH₂C(O)C(O)O-，- CH₂CH(Me)C(O)C(O)O-，-CH₂CH₂C(O)C(O)-，-CH₂CH(Me)C(O)C(O)-，- CH₂CH₂C(O)C(O)NH-，-CH₂CH(Me)C(O)C(O)NH-，-CH₂CH₂C(O)-，- CH₂CH(Me)C(O)-，-CH₂CH₂C(O)NH-，-CH₂CH(Me)C(O)NH-，- CH₂CH₂C(O)NR-，-CH₂CH(Me)C(O)NR-，-CH₂CH₂SO₂-，-CH₂CH(Me)SO₂-，- CH₂CH₂S (O) R-, or-CH₂CH (Me) S (O) R-units, preferably Q is the following:

it will be apparent to those skilled in the art that the structure of Q as described above is-CH₂CH₂C(O)O-，-CH₂CH(Me)C(O)O-，-CH₂CH₂C(O)C(O)O-，- CH₂CH(Me)C(O)C(O)O-，-CH₂CH₂C(O)C(O)-，-CH₂CH(Me)C(O)C(O)-，- CH₂CH₂C(O)C(O)NH-，-CH₂CH(Me)C(O)C(O)NH-，-CH₂CH₂C(O)-，-CH₂CH(Me)C(O)-，-CH₂CH₂C(O)NH-，-CH₂CH(Me)C(O)NH-，- CH₂CH₂C(O)NR-，-CH₂CH(Me)C(O)NR-，-CH₂CH₂SO₂-，-CH₂CH(Me)SO₂-，- CH₂CH₂S (O) R-, or-CH₂The CH (Me) S (O) R-units are derived from intermediates of nucleophilic (nucleophilicity) character of one of the following chemical structures (wherein Metal represents a Metal cation or a silane group, preferably sodium, potassium, lithium, SiR₃Etc.) to the corresponding unsaturated ester, unsaturated amide, unsaturated sulfone or sulfoxide, etc. Thus the above-mentioned preferred radicals-R₂The structure of-Q is merely exemplary and not limiting, as is the case for the small molecule or polymeric-R according to the essential significance of the chemical reaction described above₂the-Q structure is within the scope of the present disclosure.

Or, -R when n is 2 or an integer greater than 2₂The structure-Q is a structure containing an n-membered-CH₂CH (OH) -, or-CH₂A small molecule or polymer group of ch (or) -units, preferably Q is the following group:

it will be apparent to those skilled in the art that the structure of Q as described above is-CH₂CH (OH) -or-CH₂The ch (or) -units are derived from the ring-opening reaction of an intermediate of nucleophilic (nucleophilicity) character of one of the following chemical structures with the corresponding epoxide. Thus the above-mentioned preferred group-R₂The structure of-Q is merely exemplary and not limiting, as is the case for the small molecule or polymeric-R according to the essential significance of the chemical reaction described above₂the-Q structure is within the scope of the present disclosure.

One general method for the preparation of the compounds of the general formula (I) is shown by the following equation, starting from an organic phosphine halide R₁PHal₂(Hal is halogen), the organic phosphine hydrogen R can be prepared in situ or separated and purified to obtain the organic phosphine hydrogen R by a known literature method [ CN201510020417.9 ]₁PH₂Organic phosphine hydrogen R₁PH₂Under the action of proper Base and equivalent acyl halide R₀C (O) Hal or anhydride R₀C(O)OC(O)R₀Reacting to obtain an intermediate in the form of A or B, and obtaining a product of a general formula of a partial general formula (I) under the action of the intermediate, formaldehyde and an oxidant [ O ];

or, the intermediate A or B and the poly epoxy C1, the poly isocyanate C2, the poly unsaturated carbonyl compound C3, the poly carboxylic acid C4, the poly acyl halide C5, the poly acid anhydride C6 and the like represented by the general formula C are subjected to corresponding epoxy ring-opening reaction, isocyanate addition reaction (esterification reaction), Michael conjugate addition reaction, esterification reaction and the like in the presence of an oxidant [ O ], so as to obtain another part of the product of the general formula (I): the ring Q herein represents a structure described by the chemical characteristics of Q, i.e., a small molecule compound or polymer resin compound containing polyepoxide, polyisocyante, polyatomic unsaturated carboxylate, polycarboxylic acid, polyacyl halide, or polyanhydride functional groups.

Oxidant [ O ] represents oxygen, air, an air-metal salt complex, a metal hypochlorite (preferably sodium hypochlorite), an oxygen-metal salt complex, hydrogen peroxide, a peroxide in the form of ROOH, a peroxy acid, or sulfur; q is an integer between 1 and n.

Meanwhile, in view of the chemical nature of the Nucleophilic (nucleophilical) species of intermediate a or B, in association, a or B may be reacted with a series of alkyl halides (chlorides, bromides, or iodides) or alkyl pseudohalides (sulfonates, etc.) labeled R-Hal, preferably, in the presence of a suitable base, Nucleophilic substitution reaction produces a portion of the target compound of formula (I). The Base is an inorganic metal oxide or alkoxide or carbonate or carboxylate compound, or an organic tertiary amine type compound.

The preparation of the compounds of the general formula (I) as described above is further illustrated by the examples.

Another part of the compounds satisfying the above general formula (I) is prepared by the so-called Blanc reaction of a starting phosphono starting material D under the co-action of an acid and formaldehyde to give the corresponding halide intermediate E (where r has the value 1 or 2), where the acid is Lewis or protic, preferably the acid is aluminium trichloride, zinc chloride, ferric trichloride, aluminium tribromide, hydrochloric acid, hydrobromic acid, acetic acid, or a suitable mixture of the above acids; hal represents a halogen atom, and preferred Hal is chlorine. The key intermediate E is subjected to nucleophilic substitution reaction under the action of a suitable nucleophilic reagent HNu, and the target compound (I) is prepared. Preferred nucleophiles HNu are species containing oxygen, nitrogen, sulfur, or phosphorus atoms, and particularly preferred HNu is water, NR₃， HNRR’，H₂NR, HSR, RSSR ', HP (O) RR', or a heterocycle containing an oxygen, nitrogen, sulfur, or phosphorus atom. The above-mentioned novel chemical preparation techniques are disclosed in detail in our earlier patent application No. CN103172770, and the novel unexpected and beneficial finding of the present invention is that the novel acylphosphine oxide compounds with good water dispersibility or water solubility can be prepared by using the above-mentioned techniques through selecting the appropriate HNu reagent.

Another method for preparing a portion of the compounds of formula (I) is to subject a bisacylphosphine oxide compound (BAPO), such as the commercially available BAPO-819 to an acid and an electrophile E as shown in the following equation⁺Under the action of the reaction, generating monophosphoryl group pair E⁺Thereby conveniently carrying out an addition reaction ofOne or both of the following products are prepared for co-production. Where the acid is as defined above, electrophile E⁺Is C₁-C₄₈Or α -unsaturated aldehyde, ketone, ester, nitrile, or amide, or nitroalkene, or alkenyl sulfone or sulfoxide, preferably an electrophile E⁺Is formaldehyde, acrylic acid, acrolein, or a mono-or poly-acrylate monomer or acrylate polymer resin; particularly preferred acids are aluminum trichloride or hydrochloric acid, particularly preferred electrophiles E⁺Is formaldehyde, in the presence of a reagent of "aluminium trichloride or hydrochloric acid-formaldehyde", the E ═ CH in the following products₂OH or CH₂Cl。

Another method for preparing a portion of the compounds of formula (I) is to synthesize the intermediates sodinun bis (2,4,6-trimethylbenzoyl) phosphine (structure F) or phosphinyldimethylethane (structure G), or their enolic resonance isomers, as shown in the following equation, according to the method described in ETH-Z ü rich supra of Coenraus Johannes Hendrikus Hendriksen, page 124.

Exemplary compounds conforming to the structure of formula (I) are listed below:

the invention further discloses a mixture which contains the compound of the general formula (I) and can be cured by light (ultraviolet or visible light or LED light or an equivalent light source) radiation, in particular an aqueous photocuring formula mixture system, and application of the formula material system in the fields of ink-jet printing, paper printing, adhesives, woodenware coating, plastic coating, automobile coating, packaging materials, flexible electronics, photovoltaic materials and the like.

Such photoradiation curing formulation systems are characterized by:

(1) containing at least one compound described by the general formula (I) as a photoinitiator or one of its components;

(2) contains at least one ethylenically (C ═ C) unsaturated compound.

The compound of the formula (I) is suitably contained in an amount of 0.01 to 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the total amount of the ethylenically unsaturated components in the system. Suitable radiation-curable systems disclosed herein comprise polymerizable ethylenically unsaturated-containing components which are compounds or mixtures that can be crosslinked by free-radical polymerization of the double bond, which ethylenically unsaturated-containing components can be monomers, oligomers or prepolymers, or mixtures or copolymers thereof, or aqueous dispersions of the above components.

The above-mentioned suitable radiation-curing systems may contain any of inorganic or organic fillers and/or colorants (e.g., pigments or dyes, etc.), and other additives (e.g., ultraviolet absorbers, light stabilizers, flame retardants, leveling agents, defoamers, etc.) and solvents, which may be added as necessary.

Suitable free radically polymerizable monomers are, for example, ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, (meth) acrylic acid derivatives such as (meth) acrylamide, vinyl halides, vinylidene halides, and the like.

Suitable ethylenic-containing prepolymers and oligomers include, but are not limited to, (meth) acryloyl-functional (meth) acrylic copolymers, urethane (meth) acrylates, polyester (meth) acrylates, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylates, epoxy (meth) acrylates, and the like, as well as water-soluble or water-dispersible analogs of the foregoing.

The above-mentioned monomers, oligomers, prepolymers, or copolymers, whether containing olefins, are well known to those skilled in the art and are not particularly limited.

For the gist of the present invention, we will further describe it in connection with the following series of examples.

Example zero: 2- (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) acetic acid

Sodium tert-butoxide (13.8 g) was added to a toluene-ethylene glycol dimethyl ether (300 ml, 1/1 vol.) solution of phenylphosphine (12.5 g, 114 mmol) under nitrogen at room temperature, followed by 2 hours of dropwise addition of 2,4, 6-trimesoyl chloride (24.8 g), stirring was continued for half an hour, then 16.2 g of chloroacetic acid was added slowly, and after addition, stirring was carried out at room temperature overnight. Adjusting the pH value of a reaction system to 2-3 by using 0.5N hydrochloric acid, slowly dropwise adding 30% aqueous hydrogen peroxide (17 g), reacting for 1 hour at about 40 ℃ after adding, then adding 100 ml of water into the reaction system, stirring, layering, mixing an organic phase with 80 ml of saturated aqueous sodium bicarbonate solution, washing with 80 ml of water twice, washing with dilute saline water once, drying with sodium sulfate, evaporating the solvent under reduced pressure at 60 ℃, adding 100 ml of N-heptane into the residue, pulping, filtering to obtain 24.7 g of light yellow solid, and taking part of the solid to perform gradient elution on silica gel column chromatography by using ethyl acetate-hexane to obtain an analytically pure sample. HRMS (M + H) for C₁₈H₂₀O₄P：331.1099(calculated)，331.1017(experimental)； (M+Na)for C₁₈H₁₉NaO₄P：353.0919(calculated)，353.0922(experimental)。

The first embodiment is as follows: ((hydroxymethyl) (phenyl) phosphoryl) (mesityl) methanone

Under the protection of nitrogen, sodium tert-butoxide (13.8 g) was added to a toluene (300 ml) solution containing phenylphosphine (114 mmol) at room temperature, then 2,4, 6-trimesoyl chloride (24.8 g) was slowly added dropwise over 2 hours, concentrated sulfuric acid (5.7 g) was added dropwise over 30 minutes while cooling in a cold water bath after the completion of the addition, and after stirring for 30 minutes, 37% paraformaldehyde aqueous solution (11.0 g) was added dropwise, and after the completion of the addition, the mixture was stirred at room temperature for 3 hours. Slowly dropwise adding 30% aqueous hydrogen peroxide (17 g), reacting at about 40 ℃ for 1 hour after the addition is finished, then adding 50 ml of water into the reaction system, stirring, layering, mixing the organic phase with 20 ml of saturated sodium bicarbonate aqueous solution, washing with 40 ml of water twice, washing with dilute saline once, drying with sodium sulfate, evaporating the solvent under reduced pressure at 60 ℃, adding 70 ml of n-heptane for beating, and filtering to obtain 26.5 g of a light yellow solid powder product.¹H-NMR(CDCl₃)：δ＝7.87-7.84(m，2H)，7.60-7.57(m，1H)，7.52-7.48(m， 2H)，6.75(s，2H)，5.55(br，1H)，4.55(dd，1H)，4.10(dd，1H)，2.24(s，3H)，2.05(s， 6H)；¹³C-NMR(CDCl₃)：δ＝＞220(C＝Osignal)，140.7，135.7，135.4，135.2，132.7， 131.4，128.9，128.8，126.9，126.3，608(d)，21.1，19.4ppm；³¹P-NMR(CDCl₃)：δ＝ 23.5ppm。HRMS(M+H)for C₁₇H₂₀O₃P：303.1150(calculated)，303.1140 (experimental)；(M+Na)for C₁₇H₁₉NaO₃P：325.0970(calculated)，325.0948 (experimental)。

The UV-Vis absorption spectrum of the compound is shown in figure 1 (the solvent is acetonitrile, and the mass percentage concentration), and the compound has remarkable absorption in the UV-LED emission wavelength region as shown in the figure:

example two: (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) methyl 2,4, 6-trimethyi-benzoate

The two compounds of this example were isolated simultaneously in the synthesis of the first example.¹H-NMR (CDCl₃)：δ＝7.96-7.92(m，2H)，7.62-7.60(m，1H)，7.55-7.27(m，2H)，6.81(s，2H)， 6.78(s，2H)，5.15(d，2H)，2.27(s，3H)，2.24(s，3H)，2.20(s，6H)，2.02(s，6H)；¹³C- NMR(CDCl₃)：δ＝＞220(C＝O signal)，139.7，135.7，135.3，133.1，131.6，131.5， 129.1，128.9，128.3ppm；³¹P-NMR(CDCl₃)：δ＝18.1ppm。HRMS(M+H)for C₂₇H₃₀O₄P：449.1882(calculated)，449.1890(experimental)；(M+Na)for C₂₇H₂₉NaO₄P：471.1701(calculated)，471.1714(experimental)。

Example three: ((chloromethyl) (phenyl) phosphonyl) (mesityl) methanone

Under the protection of nitrogen, 418 mg of Irgacure819 photoinitiator, 142 mg of anhydrous aluminum trichloride and 72 mg of paraformaldehyde are placed in 10 ml of chloroform, the system is heated to 75 ℃ for reaction for 45 minutes, the mixture is poured into ice water, liquid separation, drying and filtration are carried out, and after concentration, the residue is subjected to gradient elution by ethyl acetate on silica gel column chromatography to obtain 112 mg of example compound and 92 mg of target product of the example.¹H-NMR(CDCl₃)：δ＝7.92-7.88(m，2H)，7.62-7.60(m，1H)，7.54-7.51(m，2H)， 6.82(s，2H)，4.98(dd，1H)，4.81(dd，1H)，2.26(s，3H)，2.10(s，6H)；HRMS(M+H) for C₁₇H₁₉ClO₂P：321.0811(calculated)，321.0809(experiental)；(M+Na)for C₁₇H₁₈NaClO₂P：343.0631(calculated)，343.0644(experimental)。

Example four: ((2-hydroxyethenyl) (phenyl) phosphoryl) (mesityl) methanone

Under nitrogen protection, after sodium tert-butoxide (464 mg) was added to a toluene (20 ml) solution containing phenylphosphine (2.36 mmol) at room temperature, 2,4, 6-trimesoyl chloride (431 mg) was slowly added dropwise over 40 minutes, after the addition of the reaction system, the reaction system was stirred for 2 hours, and then transferred to a Sealed pressure-resistant tube (Sealed tube), ethylene oxide was introduced into the Sealed tube and then stirred for 2 hours, and the reaction mixture was treated with 0.86 ml of 28% hydrogen peroxide at a pH of 2 to 3 with sulfuric acid for 1 hour. The organic phase was washed with a 1% aqueous solution of sodium hydrogencarbonate and saturated brine in this order, separated, dried over sodium sulfate, filtered, and the resulting clear solution was concentrated to remove toluene, and the residue was subjected to silica gel column chromatography with a gradient elution of hexane-ethyl acetate to give 402 mg of the objective compound as a pale yellow viscous wax. HRMS (M + H) for C_i8H₂₂O₃P：317.1307 (calculated)，317.1326(experimental)；(M+Na)for C₁₈H₂₁NaO₃P：339.1126 (calculated)，339.1141(experimental)。

Example five: 3- (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) propanoic acid

Under the protection of nitrogen, after sodium tert-butoxide (214 mg) was added to a toluene (20 ml) solution containing phenylphosphine (2.19 mmol) at room temperature, 2,4, 6-trimesoyl chloride (400 mg) was slowly added dropwise over 40 minutes, after the addition of the reaction system, acrylic acid (205 mmol) was added and the reaction system was heated at 60-70 ℃ for 1 hour with stirring. The reaction solution is adjusted by 0.52 ml of 28 percent hydrogen peroxide solution and sulfuric acidAnd (5) treating for 1 hour under the condition of adjusting the pH to 2-3. The organic phase was washed with a 1% ammonium chloride aqueous solution and a saturated sodium chloride aqueous solution in this order, separated, dried over sodium sulfate, filtered, and the resulting clear solution was concentrated to remove toluene, and the residue was subjected to silica gel column chromatography and gradient elution with hexane-ethyl acetate to obtain 286 mg of the objective compound as a pale yellow solid powder. HRMS (M + H) for C₁₉H₂₂O₄P：345.1256(calculated)，345.1277(experimental)；(M+Na)for C₁₉H₂₁NaO₄P：367.1075(calculated)，367.1082(experimental)。

Example six:

160 mg of the example compound and 222 mg of the diisocyanate IPDI were placed in 8 ml of dry toluene solvent under nitrogen, 6 mg of dibutyltin dilaurate catalyst were added to the system, the mixture was heated at 80 ℃ for 1 hour, the reaction system was concentrated to remove toluene, and the residue was subjected to silica gel column chromatography and gradient elution with hexane-ethyl acetate to obtain 334 mg of a pale yellow viscous waxy target compound. HRMS (M + H) for C₄₆H₅₇N₂O₈P₂：827.3590(calculated)，827.358(experimental)； (M+Na)for C₄₆H₅₆N₂O₈NaP₂：849.3410(calculated)，849.3423(experimental)。

Example seven: tris ((2, 4,6-trimethylbenzoyl) phosphoryl) methyl) bezene-1, 3, 5-tricarboxylate

302 mg of the example compound, 88 mg of toluoyl chloride, 138 ml of triethylamine and 12 mg of 4-Dimethylaminopyridine (DMAP) are placed in 25 ml of dry dichloroethane solvent under nitrogen protection and stirred overnight at room temperature. The mixture was washed with an equal volume of half-saturated brine 3 times and the organic phase was washed with sulfurThe sodium salt was dried, filtered, concentrated to remove the solvent and the residue was subjected to silica gel column chromatography with a hexane-ethyl acetate gradient to give 267 mg of the title compound as a pale yellow solid. HRMS (M + H) for C₆₀H₅₈O₁₂P₃：1063.3141(calculated)，1063.3166(experimental)；(M+Na)for C₆₀H₅₇O₁₂NaP₃：1085.2961(calculated)，1085.2961(experimental)。

Example eight: 2- ((acryloxy) methyl) -2-ethyl propane-1, 3-diyl bis (3- (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) propane)

Under the protection of nitrogen, after sodium tert-butoxide (464 mg) is added to a toluene (20 ml) solution containing phenylphosphine (2.36 mmol) at room temperature, 2,4, 6-trimesoyl chloride (431 mg) is slowly added dropwise over 40 minutes, after the reaction system is stirred for 2 hours, 219 mg of Sartomer SR 351 monomer is slowly added, after that, 0.90 ml of 28% hydrogen peroxide (adjusted to pH 2-3 with sulfuric acid in advance) is added dropwise to the reaction system, after the reaction is stirred for 1 hour, the organic phase is washed with 1% sodium bicarbonate aqueous solution and saturated saline solution in turn, separated, dried with sodium sulfate, filtered, and the obtained clear solution is concentrated to remove the demethylbenzene, and the residual solution is eluted on a silica gel column by a hexane-ethyl acetate gradient to obtain 417 mg of light yellow viscous liquid target compound. HRMS (M + H) for C₆₃H₇₂O₁₂P₃：1113.4237(calculated)， 1113.4256(experimental)；(M+Na)for C₆₃H₇₁NaO₁₂P₃：1135.4056(calculated)， 1135.4063(experimental)。

Example nine: 2, 2-bis (((3- (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) oxy) methyl) propane-1, 3-diyl bis (3- (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) propanoate)

In a manner completely analogous to example eight, after addition of sodium tert-butoxide (464 mg) to a solution of phenylphosphine (2.36 mmol) in toluene (20 ml) at room temperature under nitrogen, then slowly dropwise adding 2,4, 6-trimesoyl chloride (431 mg) within 40 minutes, continuously stirring the reaction system for 2 hours after the addition is finished, 207 mg of pentaerythritol tetraacrylate monomer was slowly added, and then 0.95 ml of 28% hydrogen peroxide (previously adjusted to pH 2-3 with sulfuric acid) was added dropwise to the reaction system, and after further stirring and reacting for 1 hour, the organic phase was washed with a 1% aqueous solution of sodium hydrogencarbonate and saturated brine in this order, separated, dried with sodium sulfate, filtered, and the resulting clear solution was concentrated to remove toluene, and then the residue was subjected to gradient elution with hexane-ethyl acetate on silica gel column chromatography to obtain 466 mg of the objective compound as a pale yellow viscous liquid. HRMS (M + H) for C₈₁H₈₉O₁₆P₄：1441.5101(calculated)，1441.5129(experimental)；(M+Na)for C₈₁H₈₈NaO₁₆P₄：1463.4921(calculated)，1463.4954(experimental)。

Example ten: ((dimethyl) methyl) (phenyl) phosphoryl) (mesityl) methanone

Under the protection of nitrogen, adding sodium tert-butoxide (557 mg) into a toluene (30 ml) solution containing phenylphosphine (2.83 mmol) at room temperature, then slowly adding 2,4, 6-sym-tricarboxychloride (520 mg) dropwise within 40 minutes, continuing to stir the reaction system for 2 hours after the addition is finished, transferring the reaction system into a pressure-resistant tube (Sealed tube), and adding Eschenmoser Salt CH into the tube₂＝NMe₂After stirring for 1 hour after I (524 mg), the reaction was treated with 0.34 ml of 28% hydrogen peroxide solution for half an hour with sulfuric acid to pH 2-3. Washing the organic phase with 1% sodium bicarbonate water solution and saturated saline solution, separating, drying with sodium sulfate, filtering, concentrating the obtained clear solution to remove toluene, and subjecting the residual solution to silica gel column chromatographyThe crude product was eluted with a hexane-ethyl acetate gradient to give 484 mg of the title compound as a pale yellow viscous wax. HRMS (M + H) for C₁₉H₂₅NO₂P：330.1623(calculated)，330.1629(experimental)；(M+Na) forC₁₉H₂₄NaNO₂P：352.1442(calculated)，352.1459(experimental)。

Example eleven: 1, 3, 5-tris (2-hydroxy-3- (phenyl (2,4, 6-trimethylbenzol) phosphoryl) propyl) -1, 3, 5-triazanine-2, 4, 6-trione

Under the protection of nitrogen, after sodium tert-butoxide (464 mg) was added to a toluene (20 ml) solution containing phenylphosphine (2.36 mmol) at room temperature, 2,4, 6-trimesoyl chloride (431 mg) was slowly added dropwise over 40 minutes, after the addition of the reaction system was stirred for 2 hours, the reaction system was transferred to a Sealed pressure-resistant tube (Sealed tube), 233 mg of ternary epoxy (NRC (O)) was added to the Sealed tube₃(where R is propylene oxide) was stirred overnight and the reaction was treated with 1.12 ml of 28% hydrogen peroxide adjusted to pH 2-3 with sulfuric acid for 5 hours. The organic phase was washed with a 1% aqueous solution of sodium hydrogencarbonate and saturated brine in this order, separated, dried over sodium sulfate, filtered, and the resulting clear solution was concentrated to remove toluene, and the residue was subjected to silica gel column chromatography with a gradient elution of hexane-ethyl acetate-methanol to give 276 mg of the objective compound as a pale yellow viscous wax. HRMS (M + H) for C₆₀H₆₇N₃O₂P₃：1114.3938(calculated)，1114.3948(experimental)； (M+Na)forC₆₀H₆₆N₃NaO₁₂P₃：1136.3757(calculated)，1136.3762(experimental)。

Example twelve: (3, 5-bis (chloromethyl) -2, 4, 6-trimethylphenyl) (diphenylphosphonyl) methanone

Under the protection of nitrogen and at room temperature, 1.5 g of paraformaldehyde solid and 5.65 g of aluminum trichloride powder are dispersed in 120 ml of dry dichloroethane, when the temperature of the system is raised to 45 ℃, a solution of 3.48 g of photoinitiator TPO in 80 ml of dichloroethane is slowly dripped into the system, the reaction is maintained to be lower than the reflux temperature, after half a hour of dripping, the reaction liquid is poured onto ice water, liquid separation, drying and concentration are carried out, and the solid is recrystallized by ethyl acetate to obtain 3.43 g of light yellow target product which can be directly used for the next reaction.

Example thirteen: (3, 5-bis (2-hydroxyethenyl) methyl) -2, 4, 6-trimethylphenyl (diphenylphosphonyl) methanone

Under nitrogen protection at room temperature, 2.28 g of the compound of example twelve, 1.24 g of diethanolamine HN (CH)₂CH₂OH)₂And 1.32 g of triethylamine were dispersed in 120 ml (volume ratio: 1: 6) of a mixed solvent of DMF and acetonitrile, the system was reacted at 80 ℃ for 4 hours, after most of acetonitrile was removed by concentration under reduced pressure, the residue was poured into 100 ml of water under rapid stirring, and 2.66 g of a pale yellow solid powder target product was obtained by suction filtration.¹H-NMR(CDCl₃)：δ＝8.00-7.96(m，4H)，7.59-7.57(m，2H)，7.54-7.50(m， 4H)，3.73(s，4H)，3.50(s，8H)，2.60(s，8H)，2.52(s，4H)，2.04(s，3H)，2.00(s，6H)；¹³C-NMR(CDCl₃)：δ＝＞220(C＝Osignal)，132.6，131.7，131.6，128.9，128.8，59.7， 55.7，53.4，17.8，16.7ppm；HRMS(M+H)for C₃₂H₄₄N₂O₆P：583.2937(calculated)， 583.2951(experimental)；(M+Na)for C₃₂H₄₃NaN₂O₆P：605.2756(calculated)， 605.2774(experimental)。

The UV-Vis absorption spectrum of the compound is shown in figure 2 (the solvent is acetonitrile, and the mass percentage concentration), and the compound has remarkable absorption in the UV-LED emission wavelength region as shown in the figure:

example fourteen: (3, 5-bis (hydroxymethy) -2, 4, 6-trimethylphenyl) (diphenylphoryl) methanone

Under the protection of nitrogen and at room temperature, 1.7 g of the compound of example twelve was placed in 10 ml of DMF and 10 ml of acetic acid-sodium acetate buffer solution (pH 8), the reaction was stirred at room temperature overnight and poured onto ice water, and the mixture was separated, dried, concentrated, and the solid was gradient-eluted with ethyl acetate-hexane on silica gel column chromatography to give 0.68 g of the objective product as a pale yellow solid. HRMS (M + H) for C₂₄H₂₆O₄P：409.1569(calculated)， 409.1571(experimental)；(M+Na)forC₂₄H₂₅NaO₄P：431.1388(calculated)， 431.1395(experimental)。

Example fifteen: ((3- (hydroxymethy) -2, 4, 6-trimethyibenzoyl) (phenyl) phosphonyl) (mesityl) methanone

Under the protection of nitrogen, 2 g of paraformaldehyde and 2.67 g of aluminum trichloride are dissolved in a minimum amount of chloroform and heated to 75 ℃ for 45 minutes of reaction, 8.4 g of a saturated solution of Irgacure819 photoinitiator in chloroform is added, the reaction is continued for 35 minutes after the addition, then 2.67 g of aluminum trichloride is added, the reaction is continued for 10 minutes (note that the TLC tracking reaction process is carried out by using a mixed solvent of hexane and ethyl acetate in a volume ratio of 2 to 1 as a developing agent), the reaction solution is poured into ice water, liquid separation is carried out, extraction is carried out, drying is carried out, filtration is carried out, and the residue after concentration is subjected to silica gel column chromatography and gradient elution by using a hexane-dichloromethane eluent, so that 2.9 g of a yellow powder solid target compound is obtained (meanwhile, 1.7 g of an example compound is obtained).¹H-NMR(CDCl₃)：δ＝7.97-7.91(m，2H)，7.59-7.62(m，1H)，7.56-7.26(m，2H)，6.81(s，2H)，6.78(s，2H)，5.15(s，2H)，2.30(s， 1H)，2.26(s，3H)，2.24(s，3H)，2.20(s，6H)，2.02(s，6H)；¹³C-NMR(CDCl₃)：δ ＝218.8，217.9，169.1，169.0，141.0，139.7，135.7，135.4，135.2，134.9，133.1，131.7， 131.6，131.5，129.3，129.2，128.9，128.3，126.8，125.7，73.4，61.3，60.2，21.1，21.0， 19.8，19.4ppm；³¹P-NMR(CDCl₃)：δ＝18.2ppm。HRMS(M+H)for C₂₇H₃₀O₄P： 449.1882(calculated)，449.1888(experimental)；(M+Na)for C₂₇H₂₉NaO₄P： 471.1701(calculated)，471.1644(experimental)。

Example sixteen: 2- (2-hydroxyethoxy) ethyl 3- (bis (2,4, 6-trimethylbenzoxy) phosphoryl) propanoate

Synthesis of intermediate sodium bis (2,4,6-trimethylbenzoyl) phosphine, a pale yellow solid powder, was carried out under nitrogen protection at room temperature according to the method described in the paper of the Coenrus Johannes Hendrikus Hendriksen ETH-Z ü Rich Ph.M.P.124, 3.48 g of this compound was placed in 100 ml of a 50: 50 THF-water mixed solvent, and 0.062 g of glacial acetic acid and 1.65 g of acrylate monomer CH were added in this order₂＝CHC(O)OCH₂CH₂OCH₂CH₂And (2) reacting the OH post-reaction system for 30 minutes under microwave irradiation without separation, adding 1.6 ml of 28% hydrogen peroxide, continuously stirring and reacting overnight, pouring the reaction solution into an ethyl acetate-saturated ammonium chloride mixed solution, separating an organic phase, washing the saturated ammonium chloride solution and a salt solution once respectively, drying, filtering and concentrating, and performing gradient elution on the residue on silica gel column chromatography by using an ethyl acetate-hexane eluent to obtain 2.03 g of a yellow solid target product. HRMS (M + H) for C₂₇H₃₆O₇P：503.2199(calculated)，503.2207(experimental)；(M+Na)for C₂₇H₃₅NaO₇P： 525.2018(calculated)，525.2034(experimental)。

Example seventeen: ((hydroxymethyl) phosphoryl) bis (mesitylmethane)

Under nitrogen protection and at room temperature, the intermediate sodium bis (2,4,6-trimethylbenzoyl) phosphanide was synthesized according to the method described in the paper of ETH-Z ü Rich Ph.D. of Coenrus Johannes Hendrikus Hendriksen at page 124, light yellow solid powder 3.48 g of this compound was placed in 80 ml of a 50: 50 THF-water mixed solvent, 0.62 g of glacial acetic acid and 5 times equivalent of aqueous formaldehyde solution were added in order, the reaction system was reacted for 30 minutes under microwave irradiation without separation, 1.4 ml of 28% hydrogen peroxide was added and the reaction was stirred overnight, the reaction solution was poured into 200 ml of an ethyl acetate-saturated ammonium chloride mixed solution, the organic phase was separated, the saturated ammonium chloride solution and the saline solution were washed once, dried, filtered, concentrated, and the residue was eluted on a silica gel column chromatography with an ethyl acetate-hexane eluent gradient to give 1.88 g of a yellow viscous target product HRMS (M + H) for C₂₁H₂₆O₄P：373.1569(calculated)，373.1574(experimental)；(M+Na)for C₂₁H₂₅NaO₄P：395.1388(calculated)， 395.1392(experimental)。

Example eighteen: ((2-hydroxythienyl) phosphoryl) bis (methiylmethane)

Under the protection of nitrogen and at room temperature, synthesizing an intermediate sodion bis (2,4,6-trimethylbenzoyl) phosphamide and light yellow solid powder according to the method described in page 124 of ETH-Z ü Rich Ph-Ph paper of Coenrus Johannes Hendrikus Hendriksen, putting 3.48 g of the compound into 60 ml of THF, adding 0.62 g of glacial acetic acid, stirring for half an hour, centrifugally separating the generated solid, transferring clear liquid into a pressure-resistant tube, introducing 3 atm of ethylene oxide, sealing the pressure-resistant tube, stirring for reacting for 4 hours at room temperature, adding 1.4 ml of 28% hydrogen peroxide, continuing stirring for reacting overnight, pouring 200 ml of the reaction liquid into a mixture of ethyl acetate and saturated ammonium chloride, and mixingIn the solution, the organic phase was separated, washed once with saturated ammonium chloride solution and once with brine, dried, filtered, concentrated and the residue was subjected to silica gel column chromatography with ethyl acetate-hexane eluent gradient to give 1.42 g of the desired product as a yellow viscous wax. HRMS (M + H) for C₂₂H₂₈O₄P：387.1725(calculated)，387.1740(experimental)；(M+Na)for C₂₂H₂₇NaO₄P：409.1545(calculated)，409.1566(experimental)。

Example nineteenth: bis (2,4,6-trimethylbenzoyl) methyl) hexane-1, 6-dimethyldicarbamate

227 mg of the seventeen-compound of example and 51 mg of hexamethylene diisocyanate HDI were placed in 20 ml of a dry toluene solvent under nitrogen protection, 8 mg of dibutyltin dilaurate catalyst was added to the system, the mixture was heated at 80 ℃ for 1 hour, the reaction system was concentrated to remove toluene, and the residue was subjected to silica gel column chromatography and gradient elution with hexane-ethyl acetate to obtain 203 mg of a pale yellow viscous waxy target compound. HRMS (M + H) for C₅₀H₆₃N₂O₁₀P₂：913.3958(calculated)，913.3977(experimental)； (M+Na)for C₅₀H₆₂N₂O₁₀NaP₂：935.3777(calculated)，935.3789(experimental)。

Example twenty: bis ((2, 4,6-trimethylbenzoyl) phosphoryl) methyl) tert-pthalate

740 mg of the seventeen-compound of example, 202 mg of terephthaloyl chloride, 245 ml of triethylamine and 24 mg of 4-Dimethylaminopyridine (DMAP) were placed in 60 ml of dry dichloroethane solvent under nitrogen protection and stirred at room temperature overnight. The mixture was washed 3 times with an equal volume of half-saturated brine, containingThe organic phase is dried over sodium sulfate, filtered and concentrated to remove the solvent, and the residue is chromatographed on a silica gel column with a hexane-ethyl acetate gradient to give 604 mg of the yellow title compound. HRMS (M + H) for C₅₀H₅₃O₁₀P₂：875.3114(calculated)，875.3140(experimental)；(M+Na)forC₅₀H₅₂O₁₀NaP₂：897.2933(calculated)，897.2928(experimental)。

Example twenty one: UV light curing test

Sample systems containing ethylenic (acrylate) bonds were prepared according to the following formulation (in weight percent):

bisphenol a epoxy acrylate (Ebecryl 605): 30 percent; aminoacrylate (Ebecryl 7100): 8 percent; propoxylated glycerol triacrylate: 30 percent; hexanediol diacrylate: 24 percent; polysiloxane acrylate: 0.5 percent; ethoxy pentaerythritol tetraacrylate: 3.5 percent; photoinitiator (2): 2% of the photoinitiator in the embodiment and 2% of Shenzhen are the photoinitiators APi-180 of the chemical company [ the structure is 2-hydroxy-1- (3- (hydroxymethyl) phenyl) -2-methyl propan-1-one ].

Comparative example system one: the formulation was the same as above except that the photoinitiator used was 2% TPO and 2% Irgacure 184.

Comparative example system two: the formulation was the same as above except that the photoinitiator used was 4% Irgacure 184.

The above formulation examples and comparative examples were coated on cardboard to form a coating of about 30-35 microns using a 2-pin 80 watt mercury-in-the-middle lamp as the light source and a variable speed conveyor test. The criterion for completing photopolymerization curing is that repeated nail scratching and scratching can not generate marks.

Residual odor test odor levels were evaluated independently for 5 persons, respectively, and the criteria for evaluation are indicated by the following numbers: level 0: no smell; level 1: very mild odor; and 2, stage: a slight odor; and 3, level: a clear odor; 4, level: a strong odor; and 5, stage: a very strong smell.

The results show that formulation systems containing the example compounds from zero to two, four to eleven, and thirteen to twenty all cure efficiently at speeds above 60 meters per minute with odor ratings of 0 or 0-1 grade; in contrast, comparative formulation system one has a photocuring speed of 45-50 m/min and an odor rating of 3-4 or 4; comparative example formulation system two exhibited a problem of insufficient bottom dry (through cure) at a rate of greater than 30 m/min and an odor rating of 4.

The above experimental results show that the photoinitiators prepared by the invention have good UV light curing efficiency performance and low odor characteristics.

Example twenty two: LED light curing test

bisphenol a epoxy acrylate (Ebecryl 605): 25 percent; aminoacrylate (Ebecryl 7100): 8 percent; propoxylated glycerol triacrylate: 25 percent; hexanediol diacrylate: 22 percent; polysiloxane acrylate: 0.5 percent; ethoxy pentaerythritol tetraacrylate: 3.5 percent; photoinitiator (2): 2% of the photoinitiator of this example; auxiliary initiator: 14% CYTEC LED-01 [ mercapto-modified photocurable resin ].

The mixture of the preparation examples is coated on a cardboard to form a coating of about 30-35 microns, and the unit power produced by 1 Shenzhen Shenri science and technology company is 16W/cm²LED light source (3 cm wide and 80 cm long LED area light source) with an emission wavelength of 395 nm, variable speed conveyor belt test. The criterion of photo-polymerization curing completion is that repeated nail scratching and pressing does not generate marks.

The results show that the formulation containing the example compounds one to eleven, and thirteen to twenty all cured efficiently at speeds above 45 meters per minute with odor ratings of 0 or 0-1.

The above experimental results show that the photoinitiators prepared according to the invention have both good LED photocuring efficiency properties and (neat) or low-odour characteristics.

Example twenty three: light curing experiment

the photocurable mixture system was prepared in the following weight percentages (total 100 parts), and the mixture was stirred, dispersed or dissolved and spray-coated on an aluminum plate (about 20 to 30 μm), and polymerization was initiated by irradiation using a 400 watt high-pressure mercury lamp as the light source. The embodiment uses the acylphosphine oxide photoinitiator and Shenzhen of the embodiment as chemical APi-1173. The curing efficiency was judged to be complete by finger pressure (i.e., repeated rubbing of the coating with a thumb nail press film did not break).

White woodenware coating: 77.2 parts of PEA, 5.9 parts of HDDA, 2.9 parts of TMPTA, 2.5 parts of example one photoinitiator, 1.5 parts of photoinitiator APi-1173 (the structure is 2-hydroxy-2-methyl-1-phenyl propan-1-one), 10 parts of TiO₂。

Floor matt finish: 14.78 parts of high-gloss UP (VP LS2100), 14.78 parts of Tromox R KB6, 7.39 parts of Banc-Fixe N, 1.18 parts of Lancemax HM 1666, 2.95 parts of TPGDA, ground to a particle size of less than 10 μm with mixing, and then 14.78 parts of high-gloss UP (VP LS2100), 5.91 parts of Gasil EBN, 35.47 parts of TPGDA, 0.06 part of BYK 300, 1 part of the example hexa photoinitiator, 1.7 parts of photoinitiator APi-1173.

Optical disk ink: 20 parts of PEA (EB525), 20 parts of EB1710, 15 parts of EO-TMPTA, 10 parts of TPGDA, 25 parts of TiO₂2.5 parts of example fifteen photoinitiator, 2.5 parts of APi-1173 photoinitiator, 3.0 parts of SiO₂2.0 parts of an antifoaming agent Airex 900.

Automobile coating: 19.4 parts of urethane acrylate (sartomer CN999), 19.4 parts of ethoxybisphenol a diacrylate (sartomer SR601), 31 parts of sartomer SR492, 24 parts of sartomer SR355, 0.32 part of the example seventeen photoinitiator, 2.60 parts of APi-180 photoinitiator, 3.28 parts of hydroxybenzotriazole light absorber (note: irradiation of this sample was performed under a nitrogen atmosphere).

The above formulation systems containing the photoinitiators of the examples all achieved sufficient curing, exhibiting excellent photopolymerization initiation activity.

Example twenty-four: water-based UV-LED photocuring experiment

example 23A: 78 parts of Shenzhen, namely a chemical company APi-313 aqueous polyurethane acrylate dispersion (with the solid content of 43 wt%), and 15 parts of 75% TiO₂The paint comprises 2 parts of auxiliary agent propylene glycol monomethyl ether, 1 part of deionized water, 2 parts of example one photoinitiator and 2 parts of hydroxy ketone photoinitiator APi-180.

Example 23B: 78 parts of Shenzhen, namely a chemical company APi-313 aqueous polyurethane acrylate dispersion (with the solid content of 43 wt%), and 15 parts of 75% TiO₂The pigment comprises 2 parts of auxiliary agent propylene glycol monomethyl ether, 1 part of deionized water, 2 parts of example hexa-photoinitiator and 2 parts of hydroxy ketone photoinitiator APi-180.

Example 23C: 96 parts of Shenzhen, namely a chemical company APi-313 aqueous polyurethane acrylate dispersion (solid content is 43 wt%), 2 parts of the first embodiment photoinitiator and 2 parts of the hydroxyketone photoinitiator APi-180.

Example 23D: 96 parts of UCECOAT 7699 aqueous polyurethane acrylate dispersion (35% wt solids) from Cyantride (now ALLNEX), 2 parts of the photoinitiator of example one, 2 parts of the photoinitiator of hydroxyketone APi-180.

Example 23E: 96 parts of an aqueous polyurethane acrylate dispersion UCECOAT 7177 from Cyantt (AllNEX) (35% by weight solids), 2 parts of the example undecane photoinitiator, 2 parts of the hydroxyketone photoinitiator APi-180.

Example 23F: 94 parts of UCECOAT 7856 aqueous polyurethane acrylate dispersion (the solid content is 35 wt%) of Cyanote (AllNEX), 2 parts of auxiliary agent propylene glycol monomethyl ether, 2 parts of example thirteen photoinitiator and 2 parts of hydroxy ketone photoinitiator APi-180.

Example 23G: 96 parts of UCECOAT 7856 aqueous polyurethane acrylate dispersion (35% by weight solids) from Cyanut (AllNEX), 2 parts of the pentadeca photoinitiator of example, 2 parts of the hydroxyketone photoinitiator APi-180.

Example 23H: 96 parts of UCECOAT 7699 aqueous polyurethane acrylate dispersion (35% by weight of solid content) from Cyanut (AllNEX), 1 part of auxiliary propylene glycol monomethyl ether, 2 parts of the seventeen photoinitiator of example.

Example 23I: 96 parts of Shenzhen, namely APi-313 water-based polyurethane acrylate dispersion (solid content is 43 wt%), 1 part of auxiliary agent propylene glycol monomethyl ether and 3 parts of example one photoinitiator.

Example 23J: 96 parts of Shenzhen, namely APi-313 aqueous polyurethane acrylate dispersion (solid content is 43 wt%), 1 part of auxiliary agent propylene glycol monomethyl ether and 3 parts of the seventeen photoinitiator of the example.

Example 23K: 96 parts of Shenzhen, namely APi-313 aqueous polyurethane acrylate dispersion (solid content is 43 wt%), 1 part of auxiliary agent propylene glycol monomethyl ether and 3 parts of example thirteen photoinitiator.

Example 23L: 81 parts of Shenzhen, namely a chemical company APi-313 aqueous polyurethane acrylate dispersion (with the solid content of 43 wt%), 12 parts of 50% carbon black pigment dispersion, 2 parts of auxiliary agent propylene glycol monomethyl ether, 1 part of deionized water and 4 parts of example one photoinitiator.

Example 23M: 83 parts of Shenzhen, namely APi-313 aqueous polyurethane acrylate dispersion (with the solid content of 43 wt%) of chemical company, 10 parts of aqueous red pigment dispersion, 2 parts of auxiliary agent propylene glycol monomethyl ether, 1 part of deionized water and 4 parts of example seventeen photoinitiator.

Comparative example 23N: 78 parts of Shenzhen, namely a chemical company APi-313 aqueous polyurethane acrylate dispersion (with the solid content of 43 wt%), and 15 parts of 75% TiO₂The paint comprises a pigment, 2 parts of auxiliary agent propylene glycol monomethyl ether, 1 part of deionized water, 2 parts of TPO photoinitiator and 2 parts of photoinitiator Irgacure 184.

Comparative example 23O: 94 parts of cyanote (now ALLNEX) UCECOAT 7699 aqueous polyurethane acrylate dispersion (35% by weight of solids content), 2 parts of auxiliary propylene glycol monomethyl ether, 2 parts of photoinitiator Irgacure 500 (50: 50 Irgacure184 and benzophenone BP liquid mixture).

Comparative example 23P: 96 parts of Shenzhen is APi-313 aqueous polyurethane acrylate dispersion (solid content is 43 wt%) of chemical company, and 4 parts of Irgacure 819-DW initiator.

Comparative example 23Q: 95 parts of Shenzhen is APi-313 aqueous polyurethane acrylate dispersion (solid content is 43 wt%), 1 part of Irgacure184 initiator and 4 parts of Irgacure 819-DW initiator.

The photocuring test method comprises the following steps: spraying the above formula system on substrate (glass, paper, plastic, or wood skin), removing water under 60 deg.C heating and air draft conditions, and forming 10-20 μm film body under UV (400W high pressure mercury lamp with substrate and light source spacing of 18 cm) or LED (16W/cm)²Unit power, 395 nm wavelength, 1 cm distance between substrate and light source) light source. All the substrates are placed on a belt conveyor, and the linear speed of the belt conveyor is set at 30 m/min. The hardness of the curing is indicated by pencil hardness.

Investigation of storage stability: formulation Stability (Formulation & Storage Stability) study was measured by dynamic light scattering (UPA-EX150 instrument) and percent viscosity rise after 10 days of Formulation Storage at 60 degrees Celsius (NDJ-5S digital viscometer compared to the initial viscosity of a freshly prepared Formulation at room temperature). The formula stability expression method comprises the following steps: percent viscosity rise (number average particle diameter of the dispersion in nanometers; if particles of 10 microns or more are formed, the label is "sedimentation"). Typical values for the room temperature starting average particle size of the aqueous resin dispersion in the above formulation are in the range of 60 to 100 nm.

Evaluation of residual odor: the odor level was evaluated independently in 5 persons, and the evaluation criteria are indicated by the following numbers: level 0: no smell; level 1: very mild odor; and 2, stage: a slight odor; and 3, level: a noticeable odor; 4, level: a strong odor; and 5, stage: a very strong smell.

The test results are shown in Table 1.

TABLE 1

The experiments of the above examples and comparative examples clearly prove that the novel acylphosphine oxide photoinitiator disclosed by the invention, whether being an oily or aqueous photocuring system, whether being varnish or paint containing pigment, and whether being cured by a UV or LED light source, shows excellent and broad-spectrum photocuring practical application performance, and outstanding characteristics of environmental protection, health protection, smell elimination and the like, and is particularly important for industries such as green printing, furniture and wood lacquer; meanwhile, further, due to the technical shortage of photoinitiators with sufficient water solubility or water dispersion characteristics, the compounding and storage stability of aqueous UV-LED formula systems are long-standing puzzled problems in the industry, and the compounds disclosed by the invention firstly disclose mature solutions, so that the key technical challenge is effectively solved.

Example twenty-five: aqueous UV-LED inkjet (Ink-Jet) Ink

Samples of aqueous UV-LED inkjet ink were made according to the following formulation (in weight percent):

81 parts Shenzhen has a chemical company API-313 aqueous polyurethane acrylate dispersion (43% by weight of solid content), 8 parts of 50% carbon black pigment dispersion, 2 parts of propylene glycol monobutyl ether, 2 parts of anti-settling agent, 0.5 part of BYK-021 defoamer, 3 parts of deionized water, 3.5 parts of example one, or example five, or example six, or example eleven, or example fifteen, or example sixteen, or example seventeen photoinitiator.

Spraying the above formula system on copper plate paper substrate, removing water under 60 deg.C heating and air draft conditions to form 15 μm film body under UV (400W high pressure mercury lamp with substrate and light source spacing of 18 cm) or LED (16W/cm)²The unit power, the wavelength of 395 nm and the distance between the substrate and the light source being 1 cm) is adopted, the curing line speed is set at 50 m/min, the nail scraping method is adopted to judge the surface drying degree and the internal drying degree, and the result shows that all the water-based black ink-jet inks obtain satisfactory curing effect by using the UV or energy-saving LED light source.

It is emphasized that the above-described examples are merely exemplary tests and are not to be considered limiting tests or conditions. The scope of the innovation covered by this application is defined by the claims.

Claims

1. A compound of the general formula (I):

in the general formula (I):

R₀is a compound containing R₃、R₄、R₅、R₆、R₇Substituted aryl, or R₈、R₉、R₁₀Substituted tertiary alkyl, wherein R₃、R₄、R₅、R₆、R₇Independently of one another are hydrogen, halogen atoms, R, OR, NRR', CH₂OH、CH₂OR, OR CH₂NRR ', wherein R or R' are independently of each other selected from the group consisting of linear or branched alkyl groups containing 1 to 24 carbon atoms, C₆-C₁₂Aryl, straight or branched chain alkyl containing 1-24 carbon atoms containing 1-6 non-consecutive A elements, -C containing 1-6 non-consecutive A elements₆-C₁₂One of aryl, wherein, the element A is selected from one or more of oxygen, nitrogen and sulfur; r and R' are independently present or are connected to form a 3-6 membered ring system structure; r₈、R₉、R₁₀Independently of one another are R, R₈、R₉、R₁₀Either alone or in combination to form a 3-6 membered carbocyclic ring structure;

x is oxygen or sulfur, or X is absent;

n is an integer between 1 and 1000; r₁Is R or-C (O) -R₀；

The compound shown as the general formula (I) is

2. A process for the preparation of a compound of formula (I) as defined in claim 1:

organic halogenated phosphine R₁PHal₂Starting from, organic phosphine R is prepared₁PH₂Organic phosphine hydrogen R₁PH₂Under the action of alkali and acyl halide R₀C (O) Hal or anhydride R₀C(O)OC(O)R₀Reacting to obtain an intermediate in the form of A or B, and reacting the intermediate with formaldehyde and an oxidant to obtain a compound shown in a general formula (I), wherein Hal is halogen; or carrying out a first reaction on the intermediate A or B and a substance represented by the general formula C in the presence of an oxidant to obtain a compound represented by the general formula (I); wherein Q represents a structure described by the chemical characteristics of Q and is a compound containing polyepoxy, polyisocyanate and polyunsaturated carbonylA small molecule compound or polymer resin compound of a compound, polycarboxylic acid, polybasic acid halide, or polybasic acid anhydride functional group; the base is inorganic metal hydroxide or alkoxide or carbonate or carboxylate compound, or organic tertiary amine compound; the oxidant is selected from one of oxygen, air-metal salt compound, metal hypochlorite, oxygen-metal salt compound, hydrogen peroxide, peroxide in the form of ROOH, peroxy acid or sulfur; q is an integer between 1 and n; the substance represented by the general formula C is selected from one of polyepoxy C1, polyisocyanate C2, polyunsaturated carbonyl compound C3, polycarboxylic acid C4, polybasic acyl halide C5 and polybasic acid anhydride C6;

or, the intermediate A or B and alkyl halide or alkyl pseudohalogen compound marked as R-Hal are subjected to nucleophilic substitution reaction in the presence of second alkali to prepare the compound shown in the general formula (I),

or, a starting phosphonyl raw material D is subjected to Blanc reaction under the combined action of acid and formaldehyde to obtain a halide intermediate E, wherein r is 1 or 2, the acid is Lewis or protonic acid, and Hal represents a halogen atom; the intermediate E is subjected to nucleophilic substitution reaction under the action of a nucleophilic reagent HNu to prepare the compound shown in the general formula (I),

or, bisacylphosphine oxide (BAPO) in acid and electrophilic reagent E⁺Under the action of the reaction, generating monophosphoryl group pair E⁺To prepare the compound shown in the general formula (I); the acid is a lewis acid or a protic acid; electrophilic reagent E⁺Is C₁-C₄₈Branched or straight-chain aliphatic or aromatic aldehydes or ketonesOr α -unsaturated aldehydes, ketones, esters, nitriles or amides, or nitroenes, or alkenyl sulfones or sulfoxides,

or, the phosphonic intermediate sodium bis (2,4, 6-trimethyloylyl) phosphine of the structure F or the structure Gphosphinodiylidinylbis (methiylmethane), or the enol resonance isomers of the phosphonic intermediate sodium bis (2,4, 6-trimethyloylyl) phosphine react with formaldehyde or a reagent C and are acted by an oxidant to obtain the compound shown in the general formula (I); the reagent C is one of polyepoxy C1, polyisocyanate C2, polyunsaturated carbonyl compound C3, polycarboxylic acid C4, polybasic acyl halide C5 and polybasic acid anhydride C6,

3. the method of claim 2, wherein the first reaction is selected from one of an epoxy ring opening reaction, an isocyanate addition reaction, a michael conjugate addition reaction, and an esterification reaction;

and/or, the second base is an inorganic metal hydroxide or alkoxide or carbonate or carboxylate compound, or an organic tertiary amine-type compound;

and/or the acid is selected from one or more of aluminum trichloride, zinc chloride, ferric trichloride, aluminum tribromide, hydrochloric acid, hydrobromic acid and acetic acid;

and/or, said Hal is chloro;

and/or, the nucleophile HNu is a substance containing an oxygen, nitrogen, sulfur, or phosphorus atom;

and/or the electrophile E⁺Is formaldehyde, acrylic acid, acrolein, or a mono-or poly-acrylate monomer or acrylate polymer resin.

4. The method of claim 3, wherein said HNu is water, NR₃、HNRR’、H₂NR, HSR, RSSR ', HP (O) RR', or a heterocycle containing an oxygen, nitrogen, sulfur, or phosphorus atom;

the acid is aluminum trichloride or hydrochloric acid;

the electrophile E⁺Is formaldehyde.

5. Use of a compound of formula (I) according to claim 1 as photoinitiator or other functional additive component in a photocuring formulation system; or as intermediates or starting materials or reagents in chemical synthesis.

6. A mixture which is cured by means of actinic radiation and which contains a compound of the general formula (I) as claimed in claim 1.

7. The mixture according to claim 6, wherein the mixture comprises at least one compound of the general formula (I) as photoinitiator or one of the photoinitiator components; and at least one ethylenically unsaturated compound.

8. The mixture according to claim 7, wherein the compound of the formula (I) is contained in an amount of 0.01 to 30 parts by weight per 100 parts by weight of the total amount of the ethylenically unsaturated compounds.

9. The mixture according to claim 8, wherein the compound of the formula (I) is contained in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the total amount of the ethylenically unsaturated compounds.

10. The mixture according to claim 7, wherein the ethylenically unsaturated compound is a compound or mixture which is crosslinked by free radical polymerization of the double bond, and the ethylenically unsaturated compound is a monomer, oligomer or prepolymer, or a mixture or copolymer thereof, or an aqueous dispersion thereof.

11. Use of a mixture according to any of claims 6 to 10 as a cured coating or ink.

12. The use according to claim 11, wherein the photocurable coating or ink is used in the fields of inkjet printing, paper printing, adhesives, wood coating, plastic coating, automotive coating, packaging materials, display technology, building materials, flexible electronic or photovoltaic materials.