EP0822928A1 - Derives benzophenone utiles comme photoinitiateurs - Google Patents

Derives benzophenone utiles comme photoinitiateurs

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Publication number
EP0822928A1
EP0822928A1 EP96910086A EP96910086A EP0822928A1 EP 0822928 A1 EP0822928 A1 EP 0822928A1 EP 96910086 A EP96910086 A EP 96910086A EP 96910086 A EP96910086 A EP 96910086A EP 0822928 A1 EP0822928 A1 EP 0822928A1
Authority
EP
European Patent Office
Prior art keywords
compound
group
general formula
polyol moiety
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96910086A
Other languages
German (de)
English (en)
Inventor
David George Anderson
Robert Stephen Davidson
Neil Richard Cullum
Elizabeth Sands
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lambson Ltd
Original Assignee
Lambson Fine Chemicals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lambson Fine Chemicals Ltd filed Critical Lambson Fine Chemicals Ltd
Publication of EP0822928A1 publication Critical patent/EP0822928A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring

Definitions

  • This invention relates to novel benzophenone derivatives, to their preparation, to their use as photoinitiators in polymerisation processes, and to polymeric products cured using such photoinitiators.
  • Photoinitiated curing processes may use photoinitiators which generate photo-excited species, which react with the curing agents, commonly called synergists, to produce radicals which are thought to be the species responsible for the polymerisation reaction.
  • the curing agents are aromatic tertiary amines.
  • Commercial amine curing agents are ethyl-4-(N,N- dimethylamino) benzoate (EDB) and 2-n-butoxyethyl 4- (dimethylamino) benzoate (BEDB) .
  • Photoinitiators which are available, and suitable for use with amine curing agents, are thioxanthone initiators, in particular isopropylthioxanthone (ITX) ; anthroquinone initiators; and benzophenone initiators, in particular 2- methylbenzoylbenzoate (2-MBB) .
  • the invention concerns improvements in benzophenone initiators. Whilst benzophenone/amine curing systems have been extremely important they are now less favoured. In part this is because the benzophenone components, for example 2-MBB, tend to migrate relatively easily from the cured polymers, and taint adjacent materials. When the polymer is, for example, a film, and the adjacent materials are, for example, foodstuffs, this is very undesirable.
  • Japanese published patent application 6263814 proposes photoinitiators obtained by reacting dihydric polyol compounds with ortho-benzoylbenzoic acid. These are said to be of use in curable coating compositions said to have reduced odour, and to be free from deterioration from curability.
  • di(benzoyl benzoate) compound of this type produced by reacting ortho- benzoylbenzoic acid with poly(ethylene glycol) ⁇ to migrate from a cured polymer at a relatively high rate.
  • each Z independently represents an alkylene polyol moiety or a polyalkylene polyol moiety, wherein hydroxyl groups of the polyol moiety are optionally alkylated
  • each Y independently represents an alkylene polyol moiety or a polyalkylene polyol moiety, wherein hydroxyl groups of the polyol moiety are optionally alkylated; or an alkoxy group
  • each E is independently selected from hydrogen or halogen atoms and alkyl, acyl, nitro, cyano, alkoxy, hydroxy, amino, alkylamino, sulphinyl, alkylsulphinyl, sulphonyl, alkylsulphonyl, sulphonate, amido, alkylamido, alkoxycarbonyl, halocarbonyl and haloalkyl groups
  • each F is independently selected from hydrogen or halogen atoms and alkyl, acyl, nitro, cyano, alkoxy,
  • b represents 1 or 2, preferably 1.
  • c represents 0 or 1, preferably 0.
  • each E represents a hydrogen atom.
  • p represents 0 or 1.
  • each F represents a hydrogen atom.
  • one or each group Z includes at least two ether functionalities.
  • the or each group Z independently represents an alkylene glycol or polyalkylene glycol moiety wherein hydroxyl groups of the moiety are optionally alkylated.
  • the or each group Z represents an ethylene glycol or polyethylene glycol moiety, wherein hydroxyl groups of the moiety are optionally alkylated.
  • one or preferably each, group Z represents a polyol moiety which is end-capped by an alkyl group.
  • an alkyl group which end caps the group Z is a C,_ 4 alkyl group. Preferably, it is a methyl group.
  • each group Z represents a polyol moiety wherein each hydroxyl group is alkylated.
  • each group Z is of the general formula -0-(CH 2 -CH 2 -0) e -alkyl where e has a mean value of from 2 to 20, preferably 4 to 15, most preferably 6 to 13 and the alkyl group is suitably a C M alkyl group, preferably methyl.
  • a said group COZ is located in the 2- or 4-position, most preferably in the 4-position.
  • one or each group Y includes at least two ether functionalities.
  • each Y independently represents an alkylene glycol or polyalkylene glycol moiety, wherein hydroxyl groups of the moiety are optionally alkylated.
  • Y represents an ethylene glycol or polyethylene glycol moiety, wherein hydroxyl groups of the moiety are optionally alkylated.
  • group Y represents a polyol moiety which is end-capped by an alkyl group.
  • an alkyl group which end caps the group Y is a C M alkyl group.
  • it is a methyl group.
  • each group Y represents a polyol moiety wherein each hydroxyl group is alkylated.
  • each group Y is of the general formula -0-(CH 2 -CH 2 -0) e -alkyl where e has a mean value of from 2 to 20, preferably 4 to 15, most preferably 6 to 13.
  • a said group COY is located in the 2- or 4-position, most preferably in the 4-position.
  • a process for the preparation of a compound of the general formula I which comprises the esterification or transesterification of a precursor benzophenone compound to the compound of general formula I, with an appropriate optionally alkylated polyol compound having at least one hydroxyl group.
  • the preferred reaction is an esterification, using the appropriate benzoyl benzoic acid.
  • the preferred reaction is a transesterification, preferably from the appropriate di(methoxycarbonyl) benzophenone compound.
  • the favoured reaction is an esterification, using the appropriate precursor compound having one or more (as applicable) ester groups COY, where each Y represents an alkoxy group, and one group -COOH.
  • the esterification/transesterification may be carried out under standard conditions.
  • the esterification reaction may be carried out in an organic solvent, for example toluene, at an elevated temperature, preferably under reflux, with removal of water during the reaction process.
  • a catalyst is present. Suitable catalysts are tin (II) octanoate or an acid, suitably an organic acid, for example a sulphonic acid.
  • the transesterification reaction may be carried out in an organic solvent, for example toluene, in the substantial absence of water, at an elevated temperature, preferably under reflux.
  • a catalyst is present, preferably an alkyl titanate or an acid, suitably an organic acid, for example a sulphonic acid.
  • a polymer curing composition which may be in kit form, comprising a compound of general formula I as described above, together with a curing agent with which the compound of general formula I may react, when irradiated, to generate a polymerisation radical.
  • a polymerisable composition comprising a polymerisable material suitably present in an amount from 80 to 97 wt. %, a curing agent suitably present in an amount from 14 to 2 wt. %, and a compound of the general formula I, suitably present in an amount from 6 to 1 wt. %.
  • a suitable curing agent may, for example, be an aromatic amine compound, for example ethyl-4-(N,N- dimethylamino) benzoate (EDB) or 2-n-butoxyethyl 4- (dimethylamino) benzoate (BEDB) .
  • EDB ethyl-4-(N,N- dimethylamino) benzoate
  • BEDB 2-n-butoxyethyl 4- (dimethylamino) benzoate
  • it is a novel amine compound of the type defined in our co- filed patent application entitled "Novel Amine Curing Agents", the contents of which are incorporated herein by reference.
  • such a compound is of the general formula
  • each R l independently represents an alkyl group; each R 2 independently represents an alkyl group; each group X independently represents a polyalkylene polyol moiety wherein hydroxyl groups of the polyol moiety are optionally alkylated; n and m independently represent 1, 2 or 3; and each Q is independently selected from hydrogen or halogen atoms, and alkyl, acyl, nitro, cyano, alkoxy, hydroxy, amino, alkylamino, sulphinyl, alkylsulphinyl, sulphonyl, alkylsulphonyl, sulphonate, amido, alkylamido, alkoxycarbonyl, halocarbonyl and haloalkyl groups.
  • n and m independently represent 1 or 2, preferably 1.
  • each Q represents a hydrogen atom.
  • each R 1 represents the same alkyl group.
  • each R 1 represents a C M alkyl group, preferably methyl.
  • each R 2 represents the same alkyl group.
  • each R 2 represents a C M alkyl group, preferably methyl.
  • one or each group X includes at least two ether functionalities.
  • each X independently represents a polyalkylene glycol moiety, wherein hydroxyl groups of the moiety are optionally alkylated.
  • each X represents a polyethylene glycol moiety, wherein hydroxyl groups of the moiety are optionally alkylated.
  • group X represents a polyol moiety which is end-capped by an alkyl group.
  • the alkyl group which end caps the group X is a C alkyl group.
  • it is a methyl group.
  • each group X represents a polyol moiety wherein each hydroxyl group is alkylated.
  • one or each group X is of the general formula -0-(CH 2 -CH 2 -0) r -alkyl where z has a mean value of from 2 to 20, preferably 4 to 15, most preferably 6 to 13 and the alkyl group is suitably a C M alkyl group, preferably methyl.
  • at least one said group COX is located para to a said dialkyla ine group.
  • the corresponding primary amine compound can itself be prepared by similar hydrogenation, from the corresponding nitro compound.
  • the nitro compound may be easily prepared by reaction of the appropriate nitrobenzoic acid with the appropriate alkyl end-capped alkylene glycol compound, retaining a single hydroxyl group.
  • the appropriate nitrobenzoic acid chloride may be employed, suitably with a base, for example an amine base, suitably triethylamine.
  • the compounds of the general formula II may be prepared by esterification of the appropriate dialkylamine benzoyl chloride compound, with the appropriate optionally alkylated polyol compound, having at least one hydroxyl group.
  • This reaction suitably takes place in the presence of a base, for example an amine base, for example triethylamine.
  • This reaction suitably takes place at a temperature in the range -20°C to 40°c, preferably 0°C to ambient temperature.
  • the benzoyl chloride reactant may be prepared by the reaction of thionyl chloride with the corresponding benzoic acid, suitably at ambient temperature.
  • a suitable polymerisable material is any material whose polymerisation can be initiated by an amine radical.
  • the polymerisation is applied to acrylate systems where the polymerisable material (monomer) may, for example be 1,6-hexanediol diacrylate (HDDA) , 2- hydroxyethyl acrylate (HEA) , hydroxypropyl acrylate (HPA) and methyl methacrylate (MMA) .
  • HDDA 1,6-hexanediol diacrylate
  • HPA 2- hydroxyethyl acrylate
  • HPA hydroxypropyl acrylate
  • MMA methyl methacrylate
  • the polymerisable materials may be suitable for surface/coating/film applications. They may be formulated with other components, including inks, for printing applications.
  • the first step was to prepare 4,4 ' -dimethyl benzophenone. To do this, 25 ml of p-toluoyl chloride was added slowly to a stirred mixture of 30 g of anhydrous aluminium trichloride and 115 ml of dry toluene. The resulting solution was refluxed for 6 hours before the product was isolated by addition of the reaction solution to a solution of 200 ml water and 100 ml cone. HCl. The resulting red solid was distilled (short path) at 141°C at 4 mm Hg. The distillate solidified on cooling to a white solid.
  • the 4,4'-dimethyl benzophenone was then oxidised to the corresponding dicarboxylic acid.
  • a solution of glacial acetic acid and the 4,4 l -di ethyl benzophenone was added to a solution of aq. acetic acid 80 % v/v and chromium trioxide and stirred at ambient temperature for 24 hours.
  • the addition of water facilitated a pale green precipitate.
  • Isolation and H l NMR/elemental analysis showed partial oxidation. The reaction was driven to completion by refluxing, at 65°C, for 24 hours.
  • the dicarboxylic acid compound was esterified to form the dimethyl ester.
  • the esterification was achieved by refluxing in methanol and an acid for 24 hours.
  • the crude product was taken into THF and washed with water to remove free acid. Recrystallisation was from dry ethanol. Characterisation was by H 1 NMR which gave the AA'BB' aromatic splitting pattern (8.20-8.70 ppm) and a singlet assigned to the methyl protons (4.20 ppm). Integration was in the ratio 4 : 3.
  • This compound was prepared by transesterification of 2-methyl benzoylbenzoate with poly(ethylene glycol) 3j0 monomethylether, in accordance with the method described with reference to Compound 2.
  • the product structure was confirmed by 100 MHz proton NMR, the results being as follows: methyl ether 3.75 ppm singlet (3H) ethylene protons 3.65 ppm singlet (-30H) aromatic protons 7.20-7.80 ppm multiplet (9H)
  • This compound was the commercial product SPEEDCURE MBB obtainable from Lambson Fine Chemicals Limited, of Castleford, U.K.
  • N- methyldiethanolamine NMDA
  • 4-N,N-dimethylaminobenzoyl poly(ethylene glycol) 3S0 monomethylether This was prepared as follows.
  • PEG polyethylene glycol
  • hexanediol Diacrylate (monomer) 93 wt % amine curing agent : 5 wt % photoinitiator : 2 wt %.
  • Curing was by a medium pressure UV lamp.
  • the results presented below relate to the determination of whether the polymer cures and if so, how quickly, and to the propensity of the photoinitiators to migrate from a polymer film after curing.
  • the two methods employed to address these aspects were Real Time Infra Red (RT-IR) and High Pressure Liquid Chromography (HPLC) .
  • RT-IR allows the rate of cure of each of the samples to be analysed.
  • This method allows an infra ⁇ red spectrum to be taken, then a frequency is chosen, one at which the transmittance would change during polymerisation.
  • Commonly used is the acrylate stretch at 810 cm' 1 , the acrylate double bonds disappearing during curing.
  • Using the time drive facility it allows infra ⁇ red analysis while the sample is being irradiated with a medium pressure UV lamp, thus allowing the increase in transmittance to be monitored. This gives an indication of the rate of polymerisation.
  • a second spectrum was run. This showed the final position of the acrylate stretch.
  • HPLC method used for analysing the propensity of the initiators to migrate
  • the method for testing the propensity of the initiators to migrate was the same throughout.
  • the migratable initiator content of each film was analysed as follows. Initially a drop of the pre-polymer mixture was placed on a piece of satinised paper. This was then evenly spread over the surface using a "K" bar which gave a film thickness of between 50-60 ⁇ m.
  • the Colordry unit contains a medium pressure mercury lamp.
  • the samples are placed on a moving belt (in these trials this was set at 24 metres/minute) . It was important to ensure two main factors during this stage of the trial. Firstly, that all the samples taken, of satinised paper and film, were of the same size. It was for this reason that a metal template was made that gave samples of 21 x 28 mm. Secondly, that the curing of the film was as unaffected by oxygen inhibition as possible. This was ensured by placing the paper and uncured film in a cell with a quartz window. This cell was then evacuated with nitrogen and sealed. Only then was the sample passed through the Colordry unit.
  • the 21 x 28 mm samples of each pre-polymer mixture were then placed in individual 7 ml sample vials.
  • To each vial was added 5 ml of a de-gassed acetonitrile/water 50/50 mix, enough to immerse each sample.
  • the vials were then placed in a dark cupboard for 20 hours. After this time the vials were removed and the sample extracted from each vial. All that was left in each vial was the solvent containing the migratables that had leached out from the film in the 20 hour period.
  • each sample was injected on to the HPLC column. Each sample was run in acetonitrile/water 50/50 mixture. The data from each run was then used to analyse the migratable content of each film.
  • the curing agent was N- methyldiethanolamine (NMDA) .
  • novel PEG-substituted initiators and curing agents provide good rates of reaction and high degrees of polymerisation, in addition to the good or excellent self-migration properties, shown by the other tests.
  • novel photoinitiators of the type of compounds 1 to 3 can be expected to offer certain further advantages.
  • the use of PEG can be expected to have a plasticizing effect, useful to increase the flexibility, and hence the durability, of films.
  • the incorporation of PEG may be expected to increase the compatibility of the polymers, with paper surfaces. When polymer films cured using the novel photoinitiators are used in conjunction with paper, the extra adherence is desirable.
  • PEG compounds are likely to be highly soluble in water, such that the amine curing agents could be used in conjunction with aqueous curing formulations.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés benzophénone de la formule générale (I). Dans cette formule, chaque Z représente d'une manière indépendante un groupe alkylène polyol ou un groupe polyalkylène polyol, où les hydroxyles du polyol peuvent être alkylés; chaque Y représente d'une manière indépendante un groupe alkylène polyol ou un groupe polyalkylène polyol où les hydroxyles du polyol peuvent être alkylés, ou un groupe alcoxy; chaque E est choisi d'une manière indépendante parmi les atomes d'hydrogène ou d'halogènes et les groupes alkyle, acyle, nitro, cyano, alcoxy, hydroxy, amino, alkylamino, sulfinyle, alkylsulfinyle, sulfonyle, alkylsulfinyle, sulfonyle, alkylsulfonyle, sulfonate, amido, alkylamido, alcoxycarbonyle, halocarbonyle et haloalkyle; chaque F est choisi d'une manière indépendante parmi les atomes d'hydrogène ou d'halogènes et les groupes alkyle, acyle, nitro, cyano, alcoxy, hydroxy, amino, alkylamino, sulfinyle, alkylsulfinyle, sulfonyle, alkylsulfonyle, sulfonate, amido, alkylamido, alcoxycarbonyle, halocarbonyle et haloalkyle; b représente un nombre entre 1 et 5; c représente un nombre entre 0 et 4; et p représente un nombre entre 0 et 5. L'invention concerne également des procédés de préparation de ces composés. Les composés de la formule (I) sont utiles comme photoinitiateurs.
EP96910086A 1995-04-18 1996-04-17 Derives benzophenone utiles comme photoinitiateurs Withdrawn EP0822928A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9507811.9A GB9507811D0 (en) 1995-04-18 1995-04-18 Novel photoinitiators
GB9507811 1995-04-18
PCT/GB1996/000911 WO1996033156A1 (fr) 1995-04-18 1996-04-17 Derives benzophenone utiles comme photoinitiateurs

Publications (1)

Publication Number Publication Date
EP0822928A1 true EP0822928A1 (fr) 1998-02-11

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EP96910086A Withdrawn EP0822928A1 (fr) 1995-04-18 1996-04-17 Derives benzophenone utiles comme photoinitiateurs

Country Status (4)

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EP (1) EP0822928A1 (fr)
CA (1) CA2221599A1 (fr)
GB (1) GB9507811D0 (fr)
WO (1) WO1996033156A1 (fr)

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WO2011117591A2 (fr) 2010-03-25 2011-09-29 Sun Chemical B.V. Agents synergistes

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DE19631244A1 (de) * 1996-08-02 1998-02-12 Clariant Gmbh Neue Lichtstabilisatoren auf Basis von sterisch gehinderten Aminen
US6479706B1 (en) 1997-02-04 2002-11-12 Albemarle Corporation Aminobenzophenones and photopolymerizable compositions including the same
US6254802B1 (en) 1997-05-16 2001-07-03 Cryovac, Inc. Low migratory photoinitiators for oxygen-scavenging compositions
US6139770A (en) 1997-05-16 2000-10-31 Chevron Chemical Company Llc Photoinitiators and oxygen scavenging compositions
WO2004060406A2 (fr) 2002-12-31 2004-07-22 Nektar Therapeutics Al, Corporation Reactifs polymeres comprenant une cetone ou un groupe fonctionnel apparente
BR112012020628B1 (pt) 2010-02-23 2019-12-10 Coloplast As fotoiniciador de éter polialquílico, uso de um fotoiniciador de éter polialquílico, e, método para curar uma composição de matriz
TWI403501B (zh) * 2010-05-13 2013-08-01 Double Bond Chemical Ind Co Ltd 光敏感劑
US8841354B2 (en) 2010-06-22 2014-09-23 Coloplast A/S Hydrophilic gels from polyalkylether-based photoinitiators
WO2012062334A1 (fr) 2010-11-12 2012-05-18 Coloplast A/S Nouvelles voies d'obtention de polyacrylates
DK2638077T3 (en) 2010-11-12 2015-04-20 Coloplast As HOWEVER UNKNOWN POLYMER PHOTO INITIATORS
IN2014DN09563A (fr) 2012-05-16 2015-07-17 Coloplast As
WO2013170858A1 (fr) 2012-05-16 2013-11-21 Coloplast A/S Nouveaux photoinitiateurs polymères et monomères de photoinitiateurs
US10040893B2 (en) 2012-05-16 2018-08-07 Coloplast A/S Polymeric photoinitiators and photoinitiator monomers
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US9562133B2 (en) 2012-12-20 2017-02-07 Sabic Global Technologies B.V. Cross-linked polycarbonate resin with improved chemical and flame resistance
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WO2011117591A2 (fr) 2010-03-25 2011-09-29 Sun Chemical B.V. Agents synergistes

Also Published As

Publication number Publication date
WO1996033156A1 (fr) 1996-10-24
CA2221599A1 (fr) 1996-10-24
GB9507811D0 (en) 1995-05-31

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