阅读说明：本技术 双酰基次膦酸的衍生物、其制备及其作为光敏引发剂的用途 (Derivatives of bisacylphosphinic acids, their preparation and their use as photoinitiators ) 是由 G·穆勒 H·格鲁特玛舍尔 K·迪耶特里克 于 2013-12-16 设计创作，主要内容包括：式(I)或(II)的双酰基氧化膦或双酰基硫化膦化合物是合适的光敏引发剂,其中R<Sub>1</Sub>、R<Sub>2</Sub>、R<Sub>3</Sub>、R<Sub>1a</Sub>、R<Sub>2a</Sub>和R<Sub>3a</Sub>相互独立地为C<Sub>1</Sub>-C<Sub>4</Sub>烷基、C<Sub>1</Sub>-C<Sub>4</Sub>烷氧基或卤素；X为O、NR<Sub>5</Sub>或S；或者若R<Sub>4</Sub>为Cl、F或Br,则X为直接键；Y为O或S；n为1或2；若n为1,则R<Sub>4</Sub>例如为氢、(CO)R<Sub>6</Sub>、(CO)OR<Sub>6</Sub>、(CO)NR<Sub>5</Sub>R<Sub>6</Sub>、(SO<Sub>2</Sub>)-R<Sub>6</Sub>、C<Sub>1</Sub>-C<Sub>28</Sub>烷基,若n＝2,则R<Sub>4</Sub>例如为C<Sub>1</Sub>-C<Sub>18</Sub>亚烷基；R<Sub>5</Sub>例如为氢或C<Sub>1</Sub>-C<Sub>12</Sub>烷基；R<Sub>6</Sub>例如为C<Sub>1</Sub>-C<Sub>12</Sub>烷基；R<Sub>7</Sub>、R<Sub>8</Sub>和R<Sub>9</Sub>相互独立地例如为C<Sub>1</Sub>-C<Sub>4</Sub>烷基；R<Sub>10</Sub>例如为C<Sub>2</Sub>-C<Sub>18</Sub>亚烷基；X<Sub>1</Sub>为O或S；m为1、2或3；Q表示一个或两个电荷为m<Sup>+</Sup>的无机或有机阳离子；这些化合物可以由所要求保护的方法得到。<Image he="267" wi="700" file="DDA0002270881280000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(Bisacylphosphine oxides or bisacylphosphine sulfide compounds of formula (I) or (II) wherein R is a suitable photoinitiator 1 、R 2 、R 3 、R 1a 、R 2a And R 3a Independently of one another are C 1 ‑C 4 Alkyl radical, C 1 ‑C 4 Alkoxy or halogen; x is O, NR 5 Or S; or if R is 4 Is Cl, F or Br, X is a direct bond; y is O or S; n is 1 or 2; if n is 1, then R 4 For example hydrogen, (CO) R 6 、(CO)OR 6 、(CO)NR 5 R 6 、(SO 2 )‑R 6 、C 1 ‑C 28 Alkyl, if n is 2, then R 4 For example as C 1 ‑C 18 An alkylene group; r 5 For example hydrogen or C 1 ‑C 12 An alkyl group; r 6 For example as C 1 ‑C 12 An alkyl group; r 7 、R 8 And R 9 Independently of one another, e.g. C 1 ‑C 4 An alkyl group; r 10 For example as C 2 ‑C 18 An alkylene group; x 1 Is O or S; m is 1,2 or 3; q represents one or two charges m + Inorganic or organic cations of (a); these compounds can be obtained by the claimed process.)

1. A bisacylphosphine oxide or bisacylphosphine sulfide compound of formula (I):

wherein

R₁、R₂、R₃、R_1a、R_2aAnd R_3aIndependently of one another are C₁-C₄Alkyl radical, C₁-C₄Alkoxy or halogen;

R₄is Cl, F or Br, and X is a direct bond;

y is O or S;

n is 1.

2. Bisacylphosphine oxide or bisacylphosphine sulfide compounds of formula (I) according to claim 1, wherein

R₁、R₂、R₃、R_1a、R_2aAnd R_3aIndependently of one another are C₁-C₄An alkyl group;

R₄is Cl and X is a direct bond;

y is O or S;

n is 1.

3. A process for preparing bisacylphosphinic acid compounds and bisacylthiophosphinic acid compounds of formula (I):

wherein

Y is O or S;

x is a direct bond;

R₄is halogen; and

R₁、R₂、R₃、R1a、R₂a、R₃a and n are as defined in claim 1;

in which make

Wherein R is₄A compound of formula (I) wherein X and Y are O, or

Wherein R is₄A compound of formula (I) wherein X and Y are S, or

Wherein X₁And Y is O, or

Wherein X₁And a compound of formula (II) wherein Y is S,

with halogenating agents to give compounds

4. A photopolymerizable composition comprising

(a) At least one ethylenically unsaturated photopolymerizable compound, and

(b) at least one compound of formula (I) as defined in claim 1 as photoinitiator.

5. The photopolymerizable composition according to claim 4, additionally comprising at least one further photoinitiator (c) and/or further additives (d) in addition to said photoinitiator (b).

6. A photopolymerizable composition according to claim 5 comprising as further additive (d) a pigment or a mixture of pigments or a mixture of one or more pigments with one or more dyes.

7. A photopolymerizable composition according to claim 5 comprising as further additive (d) a dispersant or a mixture of dispersants.

8. A photopolymerizable composition according to anyone of claims 4-7 comprising from 0.05 to 25 wt.%, based on said composition, of photoinitiator (b) or photoinitiators (b) and (c).

9. A photopolymerizable composition according to anyone of claims 4-7 comprising as further additive (d) a photosensitizer.

10. A process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating a photopolymerizable composition according to any one of claims 4 to 8 with electromagnetic radiation in the range from 150-600nm or with electron beams or X-rays.

11. The process according to claim 10 for the production of pigmented and unpigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists for electronics, etch resists, both liquid and dry films, solder resists, resists for the manufacture of color filters for various display applications, encapsulating electrical and electronic components, the production of magnetic recording materials, micromechanical parts, waveguides, optical switches, electroplating masks, colour proofing systems, glass fibre cable coatings, screen printing stencils, three-dimensional objects by stereolithography, image recording materials, microelectronic circuits, decolorizing materials, formulations containing microcapsules and the formation of dielectric layers in successive build-up layers of printed circuit boards.

12. A coated substrate coated on at least one surface with a composition according to claim 4.

13. Use of a composition according to claim 4 for the production of pigmented and unpigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists for electronics, etch resists, both liquid and dry films, solder resists, resists for the manufacture of color filters for various display applications, encapsulation of electrical and electronic components, production of magnetic recording materials, micromechanical parts, waveguides, optical switches, electroplating masks, colour proofing systems, glass fibre cable coatings, screen printing stencils, three-dimensional objects by stereolithography, image recording materials, microelectronic circuits, decolorizing materials, formulations containing microcapsules and formation of dielectric layers in successive build-up layers of printed circuit boards.

14. Use of a compound of formula (I) as defined in claim 1 as photoinitiator for the photopolymerization of compounds containing ethylenically unsaturated double bonds.

Example 1Preparation of bis (2,4, 6-trimethylbenzoyl) -phosphinic acid

1a) System for makingPreparation of Na₃P

3.45g of sodium sand (150mmol, 3 eq., M. 22.99g/mol), 1.55g of purified red phosphorus (50.0mmol, 1 eq., M. 30.97g/mol) and 125mg of naphthalene (1.0mmol, M. 128.17g/mol) were suspended in 120ml of Dimethoxyethane (DME). The suspension was heated to 75 ℃ and kept at this temperature for 20 hours while stirring. A color change from green through reddish-brown to black occurs.

1b) Preparation of NaPH₂

Cooling the reaction mixture of step 1a) to-10 ℃ to-15 ℃.10 ml of tert-butanol (0.1mol, 2 eq., M. 74.12g/mol) in 10ml of DME were added over 20 minutes while stirring. An almost clear brown solution was obtained, which contained a small amount of unreacted sodium. Stirring was continued for another 20 minutes.

1c) Preparation of

Acyl) sodium phosphide × DME, { Na [ P (COMes))₂]×DME}

16.8ml of 2,4, 6-trimethylbenzoyl chloride (TMBCl) (0.1mol, 2 equivalents, M. 182.65g/mol) were added quickly to the reaction mixture of step 1b), resulting in a yellow color. The reaction mixture was stirred under ice-cooling for another 20 minutes, and then stirred at room temperature for 1 hour.³¹The P NMR spectrum showed bis (at 82 ppm)Acyl) sodium phosphide × DME { Na [ P (COMes))₂]Signal of x DME: (>95％)。

1c-1) isolation of { Na [ P (COMes))₂]×DME}

The reaction mixture of step 1c) is concentrated under high vacuum. The resulting orange-yellow foam was dissolved in 100ml of toluene and then filtered. The filter cake was washed with toluene to give a clear orange-yellow filtrate. The filtrate was concentrated under vacuum to a volume of about 70ml, then carefully covered with hexane (30 ml). Yellow verticalThe square crystals are separated from the solution and are made of³¹P-、¹H-and¹³the C-NMR spectrum method is identified as di (

Acyl) sodium phosphide × DME { Na [ P (COMes))₂]×DME}(C₂₄H₃₂NaO₄P, M-438.47 g/mol). In addition, single crystal X-ray structural analysis showed that the crystal was represented by the formula [ Na ]₃[P(COMes)₂]₄][Na(DME)₃]Is formed by the ion-pair complex of (a).

M.p.＝208℃；³¹P{H}-NMR(C₆D₆，25℃)：δ＝84.1(br.)。

1c-2) if the toluene filtrate from step 1c-1) is first completely concentrated under vacuum, a DME-free product is obtained. The residue was suspended in n-hexane (80ml) and the resulting yellow solid was filtered off and then dried under high vacuum. The product was determined by NMR spectroscopy to be free of DME { Na [ P (COMes)₂}(C₂₀H₂₂NaO₂P, M-348.35 g/mol).

Or, two (

Acyl) sodium phosphide DME can be prepared via acylation with 2,4, 6-trimethylbenzoyl chloride of a different type of phosphine metal complex prepared by one of the following methods described in WO 2006056541:

1. from red phosphorus, lithium powder and naphthalene as solvent, but without proton source (examples 2a-c),

2. from red phosphorus, lithium powder, naphthalene and 3-methyl-3-pentanol (examples 5a-c),

3. from red phosphorus, lithium particles, naphthalene and 3-methyl-3-pentanol (examples 7a-c),

4. from phosphorus trichloride, sodium and 3-methyl-3-pentanol (examples 4a-c) and e) from sodium phosphide and sodium tert-butoxide (examples 12 and 13) ].

1d) Bis (2,4, 6-trimethylbenzoyl) phosphinic acid

In a 150ml Schlenk flask, 5.33g (15.3mmol) of bis (R) (N-dimethylformamide) are placed under an inert atmosphere

Acyl) sodium phosphide (prepared according to 1c-1) was dissolved in 20ml dimethoxyethane. While stirring the solution, acetic acid (0.875ml, 15.3mmol) was added at room temperature. After 3 hours the solvent was removed in vacuo and 30ml of toluene was added to the remaining solid to give a yellow suspension. Removal of sodium acetate by filtration over Celite to give HP (COMes)₂A clear yellow solution of (a). 4ml of 30% aqueous hydrogen peroxide (35.2mmol) were then added over 15 minutes at 0 ℃ under exclusion of light. The mixture was stirred at room temperature overnight, then the solution was concentrated and the precipitate was isolated by filtration. The white precipitate was washed with hexane (3X 10ml), dissolved in 50ml of THF and dried over sodium sulfate. After filtration the solvent was removed in vacuo and the residual solid was dissolved in 75ml of toluene at 60 ℃. After slow cooling to-15 ℃ 4.353g (12.15mmol, 80%) of bis (2,4, 6-trimethylbenzoyl) phosphinic acid were obtained as an off-white solid with a melting point of 133 ℃.

¹H-NMR(CDCl₃)：δ＝7.9(s，14H，P-OH)，6.65(s，4H，Mes CH)，2.38(s，12H，Mes o-CH₃)，2.13(s，6H，Mes p-CH₃)。

³¹P-NMR(121.5MHz，CDCl₃)：δ＝-1.86ppm。