CA1340884C - Radiation-sensitive, ethylenically unsaturated, copolymerizable compounds and their preparation - Google Patents
Radiation-sensitive, ethylenically unsaturated, copolymerizable compounds and their preparationInfo
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- CA1340884C CA1340884C CA000602428A CA602428A CA1340884C CA 1340884 C CA1340884 C CA 1340884C CA 000602428 A CA000602428 A CA 000602428A CA 602428 A CA602428 A CA 602428A CA 1340884 C CA1340884 C CA 1340884C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/48—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polymerization Catalysts (AREA)
- Cephalosporin Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The ethylenically unsaturated organic compounds are of the general formula (see above formula) where R is alkyl, aryl or a radical R1, and R1 is a radical (see above formula) where R2 to R6 are each H, alkyl, OH, Oalkyl, SH, Salkyl, halogen, N(alkyl)2 or N(alkyl)(aryl), and not less than one but not more than three of the radicals R2 to R6 are each a radical (see above formula) where X is alkylene or oxaalkylene, each of 2 to 10 carbon atoms, and Y is H or CH3.
These compounds have particularly high photochemical reactivity in the medium-wavelength to relatively long-wavelength UV range.
These compounds have particularly high photochemical reactivity in the medium-wavelength to relatively long-wavelength UV range.
Description
.~3~~~g~
Radiation-sensitive, eth~rlenically unsaturated.
copolymerizable~ compounds and their preparation The present invention relates to novel radiation sensitive, - et:hylen:Lcally unsaturated acetophenone and benzophenone derivatives and a process for their preparation.
UV-sensitive acetophenones and benzophenones are frequently added to radiation-sensitive polymers as external initiatora~ (for example G. Li Bassi, J. Rad.
Cur. 14 (198'7), 18). In general, however, such pro-cedures are n.ot enitirely satisfactory since, after the initiators have been mixed with the polymers, problems arise with the compatibility, the uniformity of distribu-tion, the volatility, the odor and the toxicity and of exudation and migrai:ion of the additive, which frequently lead to an undesirable, premature and non-uniform reac-tion. During the actual process of irradiation, lower reactivity is then observed as a result of lower effect-ive initiator concentrations.
It is known that a number of the stated problems can be solved if i=he radiation-sensitive initiator is copolymerized with monomers by a conventional process, ie. incorporated in a polymer chain. The photosensitive photoinitiato:r is linked to the base polymer by an anchor group, ie. a spacer. The spacer also serves to reduce the influence of the base polymer chain on the photo-chemical behavior of the initiator.
In principle, therefore, copolymerizable initia-tors have the following structure:
Initiator ~ S acer Reactive P
double bond Scheme I
U.S. Patents 3,214,492 and 3,429,852 describe acryloxy- or methacryloxy-substituted acetophenone and 13~0~~3~-benzophenone derivatives, for example I. o ' o~
These can be copolymerized with ethylene or other vinyl monomers. This gives polymers which, for example after thermal deformation, are cured by irradiation. In the model according to Scheme I, the reactive double bond and the spacer are: represented by the acryloxy group in these radiation-sen;aitive monomers.
In the 4-(4'-vinylbenzyloxy)-benzophenones ' I
described in DE-A-28 18 763, this function is performed by the styrylbenzyloxy radical.
In Uvecryl' P36, a commercial product from UCB, a particularly long spacer consisting of four ethyleneoxy units separaites t.'he benzophenone from the acryloxy radical.
I ~ ( o~. ) 4~
I ~0 This compound, which is described in, for ex-ample, Technical Bulletin 2480/885 (1985) of UCB, can be used in photopolyme:rs for coating materials . The syn-thesis is expensive.
The a:bovementioned patent literature shows that the ether or ester group is an important part of the spacer ( cf . S<:heme I I ) .
13~(~~~<~
Radiation-sensitive, eth~rlenically unsaturated.
copolymerizable~ compounds and their preparation The present invention relates to novel radiation sensitive, - et:hylen:Lcally unsaturated acetophenone and benzophenone derivatives and a process for their preparation.
UV-sensitive acetophenones and benzophenones are frequently added to radiation-sensitive polymers as external initiatora~ (for example G. Li Bassi, J. Rad.
Cur. 14 (198'7), 18). In general, however, such pro-cedures are n.ot enitirely satisfactory since, after the initiators have been mixed with the polymers, problems arise with the compatibility, the uniformity of distribu-tion, the volatility, the odor and the toxicity and of exudation and migrai:ion of the additive, which frequently lead to an undesirable, premature and non-uniform reac-tion. During the actual process of irradiation, lower reactivity is then observed as a result of lower effect-ive initiator concentrations.
It is known that a number of the stated problems can be solved if i=he radiation-sensitive initiator is copolymerized with monomers by a conventional process, ie. incorporated in a polymer chain. The photosensitive photoinitiato:r is linked to the base polymer by an anchor group, ie. a spacer. The spacer also serves to reduce the influence of the base polymer chain on the photo-chemical behavior of the initiator.
In principle, therefore, copolymerizable initia-tors have the following structure:
Initiator ~ S acer Reactive P
double bond Scheme I
U.S. Patents 3,214,492 and 3,429,852 describe acryloxy- or methacryloxy-substituted acetophenone and 13~0~~3~-benzophenone derivatives, for example I. o ' o~
These can be copolymerized with ethylene or other vinyl monomers. This gives polymers which, for example after thermal deformation, are cured by irradiation. In the model according to Scheme I, the reactive double bond and the spacer are: represented by the acryloxy group in these radiation-sen;aitive monomers.
In the 4-(4'-vinylbenzyloxy)-benzophenones ' I
described in DE-A-28 18 763, this function is performed by the styrylbenzyloxy radical.
In Uvecryl' P36, a commercial product from UCB, a particularly long spacer consisting of four ethyleneoxy units separaites t.'he benzophenone from the acryloxy radical.
I ~ ( o~. ) 4~
I ~0 This compound, which is described in, for ex-ample, Technical Bulletin 2480/885 (1985) of UCB, can be used in photopolyme:rs for coating materials . The syn-thesis is expensive.
The a:bovementioned patent literature shows that the ether or ester group is an important part of the spacer ( cf . S<:heme I I ) .
13~(~~~<~
Initiator ~~-- ~o~ ; 'o ' Reactive i double bondl i Scheme II
The ether or ester groups serve predominantly as linking elements beaween the spacer and the initiator fragment.
A novel structural scheme is obtained by con-sidering the influence of the spacer as substituent on the photochemically excited acetophenone or benzophenone fragment. Foz: example, possible spacers are those which can have a stabilizing or destabilizing effect because of their structures.
In particular, the carbamyl-substituted benzo-phenones of the type o NH R
Scheme III
constitute an interesting class of substances from this point of view. U.S. Patent 3,322,818 describes allyl substituted and methallyl-substituted carbamylbenzophen ones. However, they are only suitable as fungicides (cf.
Scheme IV).
Initiator Spacer Double bond Scheme IV
Carbamyl group However, an allyl or methallyl group is not suit-able for copolymerization. These benzoylphenyl allyl-carbamates are thei:efore of no practical importance in the polymer sector.
This appliea to an even greater extent to the polyurethane t(JV stabilizers described in DE-A-20 31 477.
Although these compounds contain a carbamyl group in the spacer, they :have no reactive double bond.
I ~ I ~ p~NH-Alkyl A photochemically interesting structure variant is described in EP-A-0 246 848. By reacting a reactive isocyanate with hydroxyethyloxybenzophenone, a radiation-sensitive monomer having a particularly long spacer is obtained.
0~ NH
This monomer is copolymerizable but has the decisive disadvantage that the radiation-sensitive moiety of the molecule is bonded to the spacer via a photochemi-cally only weakly activating ether group.
It is an object of the present invention to pro-vide a radiation-sensitive, ethylenically unsaturated acetophenone or beanzophenone derivative of a novel, previously unlknown type, in which the carbamyl group is bonded directly to the initiator moiety and which addi-tionally contains a reactive copolymerizable C-C double bond.
Initiator NH
Scheme V
The ether or ester groups serve predominantly as linking elements beaween the spacer and the initiator fragment.
A novel structural scheme is obtained by con-sidering the influence of the spacer as substituent on the photochemically excited acetophenone or benzophenone fragment. Foz: example, possible spacers are those which can have a stabilizing or destabilizing effect because of their structures.
In particular, the carbamyl-substituted benzo-phenones of the type o NH R
Scheme III
constitute an interesting class of substances from this point of view. U.S. Patent 3,322,818 describes allyl substituted and methallyl-substituted carbamylbenzophen ones. However, they are only suitable as fungicides (cf.
Scheme IV).
Initiator Spacer Double bond Scheme IV
Carbamyl group However, an allyl or methallyl group is not suit-able for copolymerization. These benzoylphenyl allyl-carbamates are thei:efore of no practical importance in the polymer sector.
This appliea to an even greater extent to the polyurethane t(JV stabilizers described in DE-A-20 31 477.
Although these compounds contain a carbamyl group in the spacer, they :have no reactive double bond.
I ~ I ~ p~NH-Alkyl A photochemically interesting structure variant is described in EP-A-0 246 848. By reacting a reactive isocyanate with hydroxyethyloxybenzophenone, a radiation-sensitive monomer having a particularly long spacer is obtained.
0~ NH
This monomer is copolymerizable but has the decisive disadvantage that the radiation-sensitive moiety of the molecule is bonded to the spacer via a photochemi-cally only weakly activating ether group.
It is an object of the present invention to pro-vide a radiation-sensitive, ethylenically unsaturated acetophenone or beanzophenone derivative of a novel, previously unlknown type, in which the carbamyl group is bonded directly to the initiator moiety and which addi-tionally contains a reactive copolymerizable C-C double bond.
Initiator NH
Scheme V
We have found that this object is achieved by ethylenically unsaturated copolymerizable, radiation-sensitive organic compounds of the general formula (I):
O
R-C-R (I) where R is a straigrht-chain alkyl radical of 1 to 4 carbon atoms, preferably methyl, ethyl or n-propyl, an l0 unsubstituted or substituted, branched alkyl radical of 3 or 4 carbon m=oms, such as isopropyl, sec-hydroxyiso-propyl or tert-butyl, aryl., such as phenyl, tolyl or naphthyl, or a radical R1, and R1 is a radical R6 ~ R4 where R2 to R6 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, (eg. methyl, ethyl, n-propyl, isopropyl), OH, OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, and not less than one but not more than three of the radicals R2 to R6 are each a radical -0-iI-NH-X-0-iI- i=CH z where X is a divalent alkylene radical -(CH2)m-, in which m is from 1 to l0, preferably ethylene, an oxaalkylene radical of the type -(CH2)n-O-(CH2)p-, in which n is from 1 to 5 and p is from 1 to 5, preferably n and p are each 2, ie. -C2H4-O-C:2H4-, which are bonded to one another via one or more -CH2-- groups, and Y is H or methyl.
Surprisingly, the novel compounds have a particularly Thigh plZOtochemical reactivity in the medium-wavelength to relatively long-wavelength W range.
It is a further object of the present invention to provide a process for the preparation of novel radiation-sensitive carbamylbenzophenones and carbamyl acetophenones having one or more terminal methacrylate or acrylate groups.
The synthesis of aryl carbamates without a copolymerizable terminal group is known. A good overview is given by C. Ferri, Reaktionen der organischen Synthese, G. 'Thieme Verlag, Stuttgart, 1978.
The most important preparation process is the reaction of an aromatic alcohol with an isocyanate (cf.
Houben-Weyl VIII, page 141; O.S. Petersen, Liebigs Ann.
Chem. 5f.~2 (1947), 205; J. Burkus, J. Org. Chem. 2~, (1961), 779; I.T. Ray and N. Punja, J. Chem. Soc., C
1968, 3011; a:nd L. Capuano and R. Zander, Chem. Ber. 104 (1971), 2212). The carbamates are formed in good to very good yields i:E the alcohol and the isocyanate are reacted with one another in a molar ratio of 1 : 1 in the absence of a solvent or in excess alcohol as a solvent. Where the alcohol or the phenol is in the form of a solid, aprotic solvesnts, eg. dichloromethane, dichloroethane, acetonitrile, toluene, etc., are used.
When this preparation process is used for isocyanatoalkyl (meah)acrylates of the general formula ( II ) , where ~: is an alkylene radical which may be per-fluorinated, .an oxaalkylene radical or a polyoxaalkylene radical, each of 2 to 12 carbon atoms, and Y is H- or CH3-, it has :been found, surprisingly, that the desired carbamylbenzo:phenones containing (meth)acrylate groups are formed in a high, virtually quantitative yield. This is surprising in i:hat acrylates or methacrylates can readily undergo many side reactions (crosslinking, polymerization) .
The ~ -isoc:yanatoalkyl (meth)acrylates required for the reaction of the hydroxyacetophenones or _ 7 _ hydroxybenzophenones can be prepared in good yield by the process described in. EP-A-083764 and DE-A-35 23 692.
The hydroxyacetophenones and hydroxybenzophenones required as further :starting materials can be prepared by known processes. For example, 4-hydroxybenzophenone is obtained in about 90% yield by subjecting phenol to a Friedel-Crafts acyla.tion with benzoyl chloride in nitro benzene in the presence of A1C13 or TiCla (Houben-Weyl 7/2a, page 186) or is obtained free of isomers by oxida Lion of 4-hydi:oxydiphenylmethane with 5, 6-dichloro-2, 3-dicyano-p-benzoquinone (Houben-Weyl 7/2a, page 681).
The present invention furthermore relates to a process for th,e preparation of compounds of the general formula (I), wherein a compound of the general formula (II) OCN-X-4-i~-i=CHy ( II ) where X and Y have ithe abovementioned meanings, prefer-ably, for example, isocyanatoethyl methacrylate or 5-isocyanato-3-oxapent.yl methacrylate, is reacted with a compound of the c3ene~ral formula (III) R~_C) I ~ R9 ( III ) R11 ~ R10 where R' is a straight-chain alkyl radical of 1 to 4 carbon atoms, preferably methyl, ethyl or n-propyl, an unsubstituted or substituted, branched alkyl radical of 3 or 4 carbon atoms,, such as isopropyl, sec-hydroxyiso-propyl or tert~-butyl, or aryl, eg. phenyl, tolyl or naph-thyl, preferably ph~anyl, and R8 to Rl2 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, (eg. methyl, ethyl, n-propyl or isopropyl), OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, with the proviso that one or more of the radicals R8 to R12 are hydroxyl, in an equimolar ratio or in two or three times this ratio, if necessary with not more than a 20~ excess 13G08g~.
g of the isocyanate, in the absence of moisture, in the presence or absence of an inert solvent or solvent mix-ture and of a basic catalyst, at from 0 to 100°C, prefer-ably from 2-0 t:o 50°C.
Regarding the preparation process, the following may be stated specii:ically.
The i.socyanates used in the reaction react readily with nucleophiles, including water. In the reaction, it is therefore essential to ensure strict absence of moisture by using dried nonnucleophilic sol-vents, eg. acetonitrile, dichloromethane, dichloroethane, tetrahydrofura~n, to:Luene, chlorobenzene, ethyl acetate, chloroform, etc . and, to maintain an inert gas atmosphere, for example nitrogen, argon or carbon dioxide.
As a =wle, a solution of the hydroxy compound in an inert solvent, which may be omitted if the compound of the general formula (III) is liquid, is initially taken at from 0 to 100°C, preferably from 20 to 50°C. The liquid isocyanate is then added dropwise, while stirring.
To initiate the reaction, a basic, nonnucleophilic amine, preferably triLethyl~~nine, 4-dimethylaminopyridine, 1, 4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicycl.o[5.4.0]undec-7-ene, polyvinylpyrid-ine, etc., advantageously dissolved in an inert organic solvent, can then be: added dropwise to this mixture at a rate such that the internal temperature can be kept below 100°C, preferably at from 20 to 50°C.
This procedosre is very suitable for laboratory experiments.
For work on a larger scale, the synthesis is pre-ferably carried out in the slightly modified manner below.
A compound of the general formula (III) and the amine in a inert :solvent are initially taken in the absence of moisture at from 20 to 60°C, and the isocyan-ate, preferably without being diluted with a solvent, is added dropwis;e at a rate such that the internal ~~~o~s~
_ g -temperature can be kept in the stated range.
After stirring has been carried out for a further 1-20 hours at from 10 to 30°C, the solvent is distilled off under -reduced pressure until the weight of the residue remains constant. Crystalline products can additionally :be readily recrystallized from an alcohol, eg. isopropanol.
The structure of all compounds stated in the Examples below was; confirmed by 1H-NMR, IR and mass spectra.
p-N-(Methacry.loylethyl)-carbamyloxyacetophenone In a four-necked flask equipped with a stirrer, a reflux condenser, an internal thermometer and a drop ping funnel, 20 ml of toluene were initially taken at room temperature and 3.5 g (25 millimoles) of 4-hydroxy acetophenone and 4.25 g (27.5 millimoles) of isocyanato ethyl methacrylate were dissolved therein. 0.2 g (2 millimoles) of t:riethylamine in 10 ml of tetrahydro furan was then added dropwise at an internal temperature of 20-26°C, and stirring was continued for 2 hours at room temperature. After the addition of a fairly small amount of phenothiaz;ine, the solvent was distilled off under reduced pressure from a water pump and the residue was recrystallize~d from isopropanol.
Yields 6.1 g (84%) of virtually colorless crystals Mp. 87-88°C
p-N-(Methacryl-4-o:~capentamethylene)-carbamyloxyaceto-phenone The synthesis was carried out similarly to the method stated in E~:ample 1. The following amounts were used:
3.4 g (25 millimoles) of 4-hydroxyacetophenone, 20 ml of toluene, 5.5 g (27.5 millimoles) of 5-isocyanato-3-oxapentyl methacrylate and ~3~~~8~
- to -0.2 g (2 millimoles) of triethylamine.
Yields 8.2 g (98$) of yellowish oil p-N-(Methacryloyl-4~-oxapentaanethylene)-carbamyloxybenzo-phenone Method 1 109.5 g (0..55 mole) of 5-isocyanato-3-oxapenta-methylene methacrylate and 99 g (0.5 mole) of 4-hydroxy-benzophenone in 90 ml of toluene were initially taken at room temperature, and a solution of 2.1 g of triethyl-amine in 75 ml of tetrahydrofuran was slowly added drop-wise at 20-25~°C (sl.ight cooling required). During this procedure, the internal temperature increased to about 40°C. The reaction mixture was left to stand for 12 hours, after which it had cooled to room temperature, 100 mg of phe~nothiazine were then added and the mixture was evaporated down to constant weight in a rotary evaporator under reduced pressure from an oil pump, at a bath temperature of: not more than 35°C .
Yield: 197 g (quantitative) of a honey-colored, viscous oil Method 2 90 kc3 (0.5 kilomoles) of 4-hydroxybenzophenone were dissolved in a~ mixture of 90 1 of anhydrous toluene and 125 1 oi: dry tetrahydrofuran at from 20 to 30°C.
Thereafter, :3.5 kg~ of triethylamine were added, while stirring. 109.5 kg (0.55 kilomole) of 5-isocyanato-3-oxapentyl methacrylate were metered in at an internal temperature of 20 t:o 25°C at a rate such that the inter-nal temperature did not exceed 30°C. Stirring was con-tinued for la hours at 20 to 25°C, after which 100 g of phenothiazines were added and the solvent mixture was dis-tilled of f to a maximum bath temperature of 35°C under about 10-15 mbar.
Yields 198 l~:g (quantitative) Further fur.~ctionalized isocyanates can be reacted _ I3A~~g~.
with hydroxybenzophenones by the method described in Example 3. The following reactions are Examples:
Example Isocyanate~ Benzophenone Yield Mp.
(1.2 mole (1 mole) j%1 4 ~C,~NGO 4-hydroxy- 81 101-102°C
o benzophenone 5 ~C~~NCO 2-hydroxy- 98 yellow Io benzophenone oil 5 ~o~.~NCO 2,4-dihydroxy- 85* yellowish IoI benzophenone oil 2_hy~oxy- 98 yellow Io benzophenone oil g ~p~~o~NCO 2, 4-dihydroxy- 90* yellow IoI benzophenone oil * Only the 4-:hydroxyl group reacts In the acetophenone or benzophenone moiety of the carbamates too, the: substituents can be varied.
Naphthyl 2-ac:etyl-9r-ethyl-7-methoxy-1-N-(methacryloyleth-ylene)-carbam~ate 12.2 g (50 millimoles) of 2-acetyl-4-ethyl-7-methoxy-1-nap~hthol and 8 . 6 g ( 55 millimoles ) of isocyana-toethyl methE~cryla~.e in 50 ml of dry toluene were ini-tially taken and 0.5 g of triethylamine in 15 ml of tetrahydrofuran was added dropwise in the course of 5 minutes. Stirring was carried out for 52 hours at room temperature, after which the precipitated crystals were filtered off under suction, washed with toluene and dried under reducedl pressure.
Yield: 11 g (53%) of colorless crystals Mp.: 124-126.°C (decomposition) ~3~0~8~:
The 4-carbamic ester of methyl 3-benzoyl-4-hydroxy-6-methoxy-1-.naphthylacetate could be prepared in 64% yield by reaction with isocyanatoethyl methacrylate, similarly to t:he synthesis of the compound described in Example 9.
Mp. 147-148°C (decomposition) 4,4'-Bis-((N-methaczyloxyethyl)-carbamyloxy)-benzophenone 34.2 c~ (0.22 mole) of isocyanatoethyl meth-acrylate and 22 g (0.1 mole) of 4,4'-bishydroxybenzophen-one were dissolved in 300 ml of toluene in the absence of moisture, and a solution of 0.7 g of triethylamine in 50 ml of tetrahydx~ofuran was added dropwise at room temperature. The exothermic reaction was kept at 28-30°C
by cooling in an ice bath, and stirring was continued for 10 hours at room temperature. The precipitated crystals were washed with toluene, dried, and recrystallized from isopropanol.
Yield: 43 g (82%) of virtually colorless crystals of melting point 135-1:36°C
The less reactive 4,4'-bis-(p-hydroxyphenylene oxy)-benzophenone can also be converted into the carbamic ester as described in Example 11. No exothermic reaction is observed anal the reaction mixture is left to stand for 72 hours at room temperature before being worked up. The toluene filtrate is evaporated down under reduced pres sure from an oil pump and the residue is recrystallized from isopropanol.
Yield: 64%
Mp.: decomposition above 140°C (complete decomposition at 270°C) Analysis (Example la):
CssH3sNa~11 Calculated C 66.1 H 5.09 r1 3.95 Found 66.2 5.2 3.9 1~AU~~~
N-(Benzoyl-p-phenyleane)-N'-(methacryloxyethylene)-carbo-diimide 8.5 g (55 millimoles) of isocyanatoethyl meth-s acrylate and 9~ . 8 g ( 50 millimoles ) of 4-aminobenzophenone in 50 ml of toluene were initially taken in the absence of moisture. 0.7 g of triethylamine in 15 ml of tetra-hydrofuran waf; added, after which the mixture was stirred for 15 hours at 55"C, cooled, and then evaporated down under reducedl pressure from a water pump. The oily residue was triturated with acetone/petroleum ether and the resulting crystals were crystallized from isopropanol with the addiltion of a small amount of phenothiazine.
Yields 12 g (68%) oaf colorless crystals of melting point 134-137°C
4'-Dimethylam.ino-4--(N-(methacryloylethyl)-carbamyloxy)-benzophenone 0.35 g of i~riethylamine, dissolved in 13 ml of tetrahydrofuran, wars added dropwise at from 15 to 20°C to a solution oi: 11.6 g (50 millimoles) of 4-hydroxy-4' dimethylaminohenzophenone and 8.6 g (55 millimoles) of isocyanatoethyl met,hacrylate in 50 ml of toluene. The temperature wits found to increase slightly to about 30°C.
After stirring had :been carried out for 10 hours at room temperature, the precipitated crystals were filtered off under suction, washed with toluene and recrystallized from isopropanol.
Yield: 16.5 g (83%) of colorless crystals of melting point 127-130"C
4-Dimethylamino-4'-(N-(methacryloyl-4-oxapentamethylene)-carbamyloxy)-benzophenone The compound was prepared similarly to Example 12 and a corresponding amount of 11 g (55 millimoles) of 5 isocyanato-3-oxapentyl methacrylate was used.
Yield: 22 g (quantitative) of a pale yellow oil
O
R-C-R (I) where R is a straigrht-chain alkyl radical of 1 to 4 carbon atoms, preferably methyl, ethyl or n-propyl, an l0 unsubstituted or substituted, branched alkyl radical of 3 or 4 carbon m=oms, such as isopropyl, sec-hydroxyiso-propyl or tert-butyl, aryl., such as phenyl, tolyl or naphthyl, or a radical R1, and R1 is a radical R6 ~ R4 where R2 to R6 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, (eg. methyl, ethyl, n-propyl, isopropyl), OH, OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, and not less than one but not more than three of the radicals R2 to R6 are each a radical -0-iI-NH-X-0-iI- i=CH z where X is a divalent alkylene radical -(CH2)m-, in which m is from 1 to l0, preferably ethylene, an oxaalkylene radical of the type -(CH2)n-O-(CH2)p-, in which n is from 1 to 5 and p is from 1 to 5, preferably n and p are each 2, ie. -C2H4-O-C:2H4-, which are bonded to one another via one or more -CH2-- groups, and Y is H or methyl.
Surprisingly, the novel compounds have a particularly Thigh plZOtochemical reactivity in the medium-wavelength to relatively long-wavelength W range.
It is a further object of the present invention to provide a process for the preparation of novel radiation-sensitive carbamylbenzophenones and carbamyl acetophenones having one or more terminal methacrylate or acrylate groups.
The synthesis of aryl carbamates without a copolymerizable terminal group is known. A good overview is given by C. Ferri, Reaktionen der organischen Synthese, G. 'Thieme Verlag, Stuttgart, 1978.
The most important preparation process is the reaction of an aromatic alcohol with an isocyanate (cf.
Houben-Weyl VIII, page 141; O.S. Petersen, Liebigs Ann.
Chem. 5f.~2 (1947), 205; J. Burkus, J. Org. Chem. 2~, (1961), 779; I.T. Ray and N. Punja, J. Chem. Soc., C
1968, 3011; a:nd L. Capuano and R. Zander, Chem. Ber. 104 (1971), 2212). The carbamates are formed in good to very good yields i:E the alcohol and the isocyanate are reacted with one another in a molar ratio of 1 : 1 in the absence of a solvent or in excess alcohol as a solvent. Where the alcohol or the phenol is in the form of a solid, aprotic solvesnts, eg. dichloromethane, dichloroethane, acetonitrile, toluene, etc., are used.
When this preparation process is used for isocyanatoalkyl (meah)acrylates of the general formula ( II ) , where ~: is an alkylene radical which may be per-fluorinated, .an oxaalkylene radical or a polyoxaalkylene radical, each of 2 to 12 carbon atoms, and Y is H- or CH3-, it has :been found, surprisingly, that the desired carbamylbenzo:phenones containing (meth)acrylate groups are formed in a high, virtually quantitative yield. This is surprising in i:hat acrylates or methacrylates can readily undergo many side reactions (crosslinking, polymerization) .
The ~ -isoc:yanatoalkyl (meth)acrylates required for the reaction of the hydroxyacetophenones or _ 7 _ hydroxybenzophenones can be prepared in good yield by the process described in. EP-A-083764 and DE-A-35 23 692.
The hydroxyacetophenones and hydroxybenzophenones required as further :starting materials can be prepared by known processes. For example, 4-hydroxybenzophenone is obtained in about 90% yield by subjecting phenol to a Friedel-Crafts acyla.tion with benzoyl chloride in nitro benzene in the presence of A1C13 or TiCla (Houben-Weyl 7/2a, page 186) or is obtained free of isomers by oxida Lion of 4-hydi:oxydiphenylmethane with 5, 6-dichloro-2, 3-dicyano-p-benzoquinone (Houben-Weyl 7/2a, page 681).
The present invention furthermore relates to a process for th,e preparation of compounds of the general formula (I), wherein a compound of the general formula (II) OCN-X-4-i~-i=CHy ( II ) where X and Y have ithe abovementioned meanings, prefer-ably, for example, isocyanatoethyl methacrylate or 5-isocyanato-3-oxapent.yl methacrylate, is reacted with a compound of the c3ene~ral formula (III) R~_C) I ~ R9 ( III ) R11 ~ R10 where R' is a straight-chain alkyl radical of 1 to 4 carbon atoms, preferably methyl, ethyl or n-propyl, an unsubstituted or substituted, branched alkyl radical of 3 or 4 carbon atoms,, such as isopropyl, sec-hydroxyiso-propyl or tert~-butyl, or aryl, eg. phenyl, tolyl or naph-thyl, preferably ph~anyl, and R8 to Rl2 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, (eg. methyl, ethyl, n-propyl or isopropyl), OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, with the proviso that one or more of the radicals R8 to R12 are hydroxyl, in an equimolar ratio or in two or three times this ratio, if necessary with not more than a 20~ excess 13G08g~.
g of the isocyanate, in the absence of moisture, in the presence or absence of an inert solvent or solvent mix-ture and of a basic catalyst, at from 0 to 100°C, prefer-ably from 2-0 t:o 50°C.
Regarding the preparation process, the following may be stated specii:ically.
The i.socyanates used in the reaction react readily with nucleophiles, including water. In the reaction, it is therefore essential to ensure strict absence of moisture by using dried nonnucleophilic sol-vents, eg. acetonitrile, dichloromethane, dichloroethane, tetrahydrofura~n, to:Luene, chlorobenzene, ethyl acetate, chloroform, etc . and, to maintain an inert gas atmosphere, for example nitrogen, argon or carbon dioxide.
As a =wle, a solution of the hydroxy compound in an inert solvent, which may be omitted if the compound of the general formula (III) is liquid, is initially taken at from 0 to 100°C, preferably from 20 to 50°C. The liquid isocyanate is then added dropwise, while stirring.
To initiate the reaction, a basic, nonnucleophilic amine, preferably triLethyl~~nine, 4-dimethylaminopyridine, 1, 4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicycl.o[5.4.0]undec-7-ene, polyvinylpyrid-ine, etc., advantageously dissolved in an inert organic solvent, can then be: added dropwise to this mixture at a rate such that the internal temperature can be kept below 100°C, preferably at from 20 to 50°C.
This procedosre is very suitable for laboratory experiments.
For work on a larger scale, the synthesis is pre-ferably carried out in the slightly modified manner below.
A compound of the general formula (III) and the amine in a inert :solvent are initially taken in the absence of moisture at from 20 to 60°C, and the isocyan-ate, preferably without being diluted with a solvent, is added dropwis;e at a rate such that the internal ~~~o~s~
_ g -temperature can be kept in the stated range.
After stirring has been carried out for a further 1-20 hours at from 10 to 30°C, the solvent is distilled off under -reduced pressure until the weight of the residue remains constant. Crystalline products can additionally :be readily recrystallized from an alcohol, eg. isopropanol.
The structure of all compounds stated in the Examples below was; confirmed by 1H-NMR, IR and mass spectra.
p-N-(Methacry.loylethyl)-carbamyloxyacetophenone In a four-necked flask equipped with a stirrer, a reflux condenser, an internal thermometer and a drop ping funnel, 20 ml of toluene were initially taken at room temperature and 3.5 g (25 millimoles) of 4-hydroxy acetophenone and 4.25 g (27.5 millimoles) of isocyanato ethyl methacrylate were dissolved therein. 0.2 g (2 millimoles) of t:riethylamine in 10 ml of tetrahydro furan was then added dropwise at an internal temperature of 20-26°C, and stirring was continued for 2 hours at room temperature. After the addition of a fairly small amount of phenothiaz;ine, the solvent was distilled off under reduced pressure from a water pump and the residue was recrystallize~d from isopropanol.
Yields 6.1 g (84%) of virtually colorless crystals Mp. 87-88°C
p-N-(Methacryl-4-o:~capentamethylene)-carbamyloxyaceto-phenone The synthesis was carried out similarly to the method stated in E~:ample 1. The following amounts were used:
3.4 g (25 millimoles) of 4-hydroxyacetophenone, 20 ml of toluene, 5.5 g (27.5 millimoles) of 5-isocyanato-3-oxapentyl methacrylate and ~3~~~8~
- to -0.2 g (2 millimoles) of triethylamine.
Yields 8.2 g (98$) of yellowish oil p-N-(Methacryloyl-4~-oxapentaanethylene)-carbamyloxybenzo-phenone Method 1 109.5 g (0..55 mole) of 5-isocyanato-3-oxapenta-methylene methacrylate and 99 g (0.5 mole) of 4-hydroxy-benzophenone in 90 ml of toluene were initially taken at room temperature, and a solution of 2.1 g of triethyl-amine in 75 ml of tetrahydrofuran was slowly added drop-wise at 20-25~°C (sl.ight cooling required). During this procedure, the internal temperature increased to about 40°C. The reaction mixture was left to stand for 12 hours, after which it had cooled to room temperature, 100 mg of phe~nothiazine were then added and the mixture was evaporated down to constant weight in a rotary evaporator under reduced pressure from an oil pump, at a bath temperature of: not more than 35°C .
Yield: 197 g (quantitative) of a honey-colored, viscous oil Method 2 90 kc3 (0.5 kilomoles) of 4-hydroxybenzophenone were dissolved in a~ mixture of 90 1 of anhydrous toluene and 125 1 oi: dry tetrahydrofuran at from 20 to 30°C.
Thereafter, :3.5 kg~ of triethylamine were added, while stirring. 109.5 kg (0.55 kilomole) of 5-isocyanato-3-oxapentyl methacrylate were metered in at an internal temperature of 20 t:o 25°C at a rate such that the inter-nal temperature did not exceed 30°C. Stirring was con-tinued for la hours at 20 to 25°C, after which 100 g of phenothiazines were added and the solvent mixture was dis-tilled of f to a maximum bath temperature of 35°C under about 10-15 mbar.
Yields 198 l~:g (quantitative) Further fur.~ctionalized isocyanates can be reacted _ I3A~~g~.
with hydroxybenzophenones by the method described in Example 3. The following reactions are Examples:
Example Isocyanate~ Benzophenone Yield Mp.
(1.2 mole (1 mole) j%1 4 ~C,~NGO 4-hydroxy- 81 101-102°C
o benzophenone 5 ~C~~NCO 2-hydroxy- 98 yellow Io benzophenone oil 5 ~o~.~NCO 2,4-dihydroxy- 85* yellowish IoI benzophenone oil 2_hy~oxy- 98 yellow Io benzophenone oil g ~p~~o~NCO 2, 4-dihydroxy- 90* yellow IoI benzophenone oil * Only the 4-:hydroxyl group reacts In the acetophenone or benzophenone moiety of the carbamates too, the: substituents can be varied.
Naphthyl 2-ac:etyl-9r-ethyl-7-methoxy-1-N-(methacryloyleth-ylene)-carbam~ate 12.2 g (50 millimoles) of 2-acetyl-4-ethyl-7-methoxy-1-nap~hthol and 8 . 6 g ( 55 millimoles ) of isocyana-toethyl methE~cryla~.e in 50 ml of dry toluene were ini-tially taken and 0.5 g of triethylamine in 15 ml of tetrahydrofuran was added dropwise in the course of 5 minutes. Stirring was carried out for 52 hours at room temperature, after which the precipitated crystals were filtered off under suction, washed with toluene and dried under reducedl pressure.
Yield: 11 g (53%) of colorless crystals Mp.: 124-126.°C (decomposition) ~3~0~8~:
The 4-carbamic ester of methyl 3-benzoyl-4-hydroxy-6-methoxy-1-.naphthylacetate could be prepared in 64% yield by reaction with isocyanatoethyl methacrylate, similarly to t:he synthesis of the compound described in Example 9.
Mp. 147-148°C (decomposition) 4,4'-Bis-((N-methaczyloxyethyl)-carbamyloxy)-benzophenone 34.2 c~ (0.22 mole) of isocyanatoethyl meth-acrylate and 22 g (0.1 mole) of 4,4'-bishydroxybenzophen-one were dissolved in 300 ml of toluene in the absence of moisture, and a solution of 0.7 g of triethylamine in 50 ml of tetrahydx~ofuran was added dropwise at room temperature. The exothermic reaction was kept at 28-30°C
by cooling in an ice bath, and stirring was continued for 10 hours at room temperature. The precipitated crystals were washed with toluene, dried, and recrystallized from isopropanol.
Yield: 43 g (82%) of virtually colorless crystals of melting point 135-1:36°C
The less reactive 4,4'-bis-(p-hydroxyphenylene oxy)-benzophenone can also be converted into the carbamic ester as described in Example 11. No exothermic reaction is observed anal the reaction mixture is left to stand for 72 hours at room temperature before being worked up. The toluene filtrate is evaporated down under reduced pres sure from an oil pump and the residue is recrystallized from isopropanol.
Yield: 64%
Mp.: decomposition above 140°C (complete decomposition at 270°C) Analysis (Example la):
CssH3sNa~11 Calculated C 66.1 H 5.09 r1 3.95 Found 66.2 5.2 3.9 1~AU~~~
N-(Benzoyl-p-phenyleane)-N'-(methacryloxyethylene)-carbo-diimide 8.5 g (55 millimoles) of isocyanatoethyl meth-s acrylate and 9~ . 8 g ( 50 millimoles ) of 4-aminobenzophenone in 50 ml of toluene were initially taken in the absence of moisture. 0.7 g of triethylamine in 15 ml of tetra-hydrofuran waf; added, after which the mixture was stirred for 15 hours at 55"C, cooled, and then evaporated down under reducedl pressure from a water pump. The oily residue was triturated with acetone/petroleum ether and the resulting crystals were crystallized from isopropanol with the addiltion of a small amount of phenothiazine.
Yields 12 g (68%) oaf colorless crystals of melting point 134-137°C
4'-Dimethylam.ino-4--(N-(methacryloylethyl)-carbamyloxy)-benzophenone 0.35 g of i~riethylamine, dissolved in 13 ml of tetrahydrofuran, wars added dropwise at from 15 to 20°C to a solution oi: 11.6 g (50 millimoles) of 4-hydroxy-4' dimethylaminohenzophenone and 8.6 g (55 millimoles) of isocyanatoethyl met,hacrylate in 50 ml of toluene. The temperature wits found to increase slightly to about 30°C.
After stirring had :been carried out for 10 hours at room temperature, the precipitated crystals were filtered off under suction, washed with toluene and recrystallized from isopropanol.
Yield: 16.5 g (83%) of colorless crystals of melting point 127-130"C
4-Dimethylamino-4'-(N-(methacryloyl-4-oxapentamethylene)-carbamyloxy)-benzophenone The compound was prepared similarly to Example 12 and a corresponding amount of 11 g (55 millimoles) of 5 isocyanato-3-oxapentyl methacrylate was used.
Yield: 22 g (quantitative) of a pale yellow oil
Claims (11)
1. An ethylenically unsaturated copolymerizable, radiation-sensitive organic compound of the formula (I):
where R is a straight-chain alkyl radical of 1 to 4 carbon atoms, an unsubstituted or hydroxy substituted, branched alkyl radical of 3 or 4 carbon atoms, aryl or a radical R1, and R1 is a radical where R2 to R6 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, and not less than one but not more than three of the radicals R2 to R6 are each a radical where X is a divalent alkylene radical -(CH2)m- in which m is from 1 to 10, an oxaalkylene radical of the type -(CH2)n-O-(CH2)p- in which n is from 1 to 5 and p is from 1 to 5, or a polyoxaalkylene radical having 2 to 12 carbon atoms and 2 to 5 oxygen atoms, which are bonded to one another by one or more -CH2- groups, and Y is H or methyl.
where R is a straight-chain alkyl radical of 1 to 4 carbon atoms, an unsubstituted or hydroxy substituted, branched alkyl radical of 3 or 4 carbon atoms, aryl or a radical R1, and R1 is a radical where R2 to R6 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, and not less than one but not more than three of the radicals R2 to R6 are each a radical where X is a divalent alkylene radical -(CH2)m- in which m is from 1 to 10, an oxaalkylene radical of the type -(CH2)n-O-(CH2)p- in which n is from 1 to 5 and p is from 1 to 5, or a polyoxaalkylene radical having 2 to 12 carbon atoms and 2 to 5 oxygen atoms, which are bonded to one another by one or more -CH2- groups, and Y is H or methyl.
2. A process for the preparation of a compound of the formula (I) as defined in claim 1, wherein a compound of the formula (II):
where X and Y have the meanings stated in claim 1, is reacted with a compound of the formula (III):
where R7 is a straight-chain alkyl radical of 1 to 4 carbon atoms, an unsubstituted or hydroxy substituted, branched alkyl radical of 3 or 4 carbon atoms or aryl and R8 to R12 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, OCH3, OC2H5, N(CH3)2, N(CH2H5)2 or N(CH)C6H5, with the proviso that one or more of the radicals R8 to R12 are hydroxyl, in an equimolar ratio or in two or three times this ratio, in the presence or absence of an inert solvent or solvent mixture and of a basic catalyst, at from 0 to 100°C under anhydrous conditions.
where X and Y have the meanings stated in claim 1, is reacted with a compound of the formula (III):
where R7 is a straight-chain alkyl radical of 1 to 4 carbon atoms, an unsubstituted or hydroxy substituted, branched alkyl radical of 3 or 4 carbon atoms or aryl and R8 to R12 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, OCH3, OC2H5, N(CH3)2, N(CH2H5)2 or N(CH)C6H5, with the proviso that one or more of the radicals R8 to R12 are hydroxyl, in an equimolar ratio or in two or three times this ratio, in the presence or absence of an inert solvent or solvent mixture and of a basic catalyst, at from 0 to 100°C under anhydrous conditions.
3. A process as claimed in claim 2, wherein the compound of the formula (II) is an .omega.-isocyanatoalkyl (meth) acrylate.
4. A process as claimed in claim 2 or 3, wherein from 1 to 1.2 moles of the isocyanate of the formula (II) are reacted per mole of the compound of the formula (III).
5. A process as claimed in claim 2 or 3, wherein not less than a catalytic amount of a strong, nonnucleophilic base is present.
6. A process as claimed in claim 5, wherein the strong nonnucleophilic base is an amine.
7. A process as claimed in claim 4, wherein not less than a catalytic amount of a strong nonnucleophilic base is present.
8. A process as claimed in claim 7, wherein the strong nonnucleophilic base is an amine.
9. A process as claimed in claim 2, wherein the reaction temperature is from 20 to 50°C.
10. A process as claimed in claim 2, wherein the procedure is carried out in an inert and anhydrous solvent in the absence of moisture.
11. An ethylenically unsaturated copolymerizable, radiation-sensitive organic compound of the formula (I):
where R is a straight-chain alkyl radical of 1 to 4 carbon atoms, an unsubstituted or hydroxy substituted, branched alkyl radical of 3 or 4 carbon atoms, an aryl of 6 to 10 carbon atoms or a radical R1, and R1 is a radical where R2 to R6 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, and not less than one but not more than three of the radicals R2 to R6 are each a radical where X is a divalent alkylene radical -(CH2)m- in which m is from 1 to 10, an oxaalkylene radical of the type -(CH2)n-O-(CH2)p- in which n is from 1 to 5 and p is from 1 to 5, or a polyoxaalkylene radical having 2 to 12 carbon atoms and 2 to 5 oxygen atoms, which are bonded to one another by one -CH2- groups, and Y is H or methyl.
where R is a straight-chain alkyl radical of 1 to 4 carbon atoms, an unsubstituted or hydroxy substituted, branched alkyl radical of 3 or 4 carbon atoms, an aryl of 6 to 10 carbon atoms or a radical R1, and R1 is a radical where R2 to R6 are identical or different and are each H, alkyl of 1 to 3 carbon atoms, OCH3, OC2H5, N(CH3)2, N(C2H5)2 or N(CH3)C6H5, and not less than one but not more than three of the radicals R2 to R6 are each a radical where X is a divalent alkylene radical -(CH2)m- in which m is from 1 to 10, an oxaalkylene radical of the type -(CH2)n-O-(CH2)p- in which n is from 1 to 5 and p is from 1 to 5, or a polyoxaalkylene radical having 2 to 12 carbon atoms and 2 to 5 oxygen atoms, which are bonded to one another by one -CH2- groups, and Y is H or methyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3820463.0 | 1988-06-16 | ||
| DE3820463A DE3820463A1 (en) | 1988-06-16 | 1988-06-16 | RADIATION-SENSITIVE, ETHYLENICALLY UNSATURATED, COPOLYMERIZABLE CONNECTIONS AND METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1340884C true CA1340884C (en) | 2000-01-25 |
Family
ID=6356646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000602428A Expired - Fee Related CA1340884C (en) | 1988-06-16 | 1989-06-12 | Radiation-sensitive, ethylenically unsaturated, copolymerizable compounds and their preparation |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0346788B1 (en) |
| JP (1) | JP2716527B2 (en) |
| AT (1) | ATE74590T1 (en) |
| CA (1) | CA1340884C (en) |
| DE (2) | DE3820463A1 (en) |
| ES (1) | ES2030241T3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10407701B2 (en) | 2016-02-26 | 2019-09-10 | Lg Chem, Ltd. | Method for preparing (meth)acrylate group-containing benzophenone for optical adhesive use and optical adhesive composition |
| US11505520B2 (en) | 2018-05-23 | 2022-11-22 | Evonik Operations Gmbh | Method for preparing keto-functionalized aromatic (meth)acrylates |
| US11512043B2 (en) | 2018-07-26 | 2022-11-29 | Evonik Operations Gmbh | Process for preparing N-methyl(meth)acrylamide |
| US11912648B2 (en) | 2018-07-17 | 2024-02-27 | Evonik Operations Gmbh | Method for preparing C-H acidic (meth)acrylates |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3930097A1 (en) * | 1989-09-09 | 1991-03-14 | Basf Ag | UV CROSSLINKABLE COPOLYMERISATE |
| DE4016549A1 (en) * | 1990-05-23 | 1991-11-28 | Basf Ag | SYNTHETIC RESINS |
| DE4037079A1 (en) * | 1990-11-22 | 1992-05-27 | Basf Ag | UNSATURATED PHENONE DERIVATIVES AND THEIR USE AS ADHESIVE ADHESIVES |
| ATE203744T1 (en) * | 1995-12-13 | 2001-08-15 | Lilly Co Eli | NAPHTHYL-ACETAMIDE AS SPLA2 INHIBITORS |
| EP0978507A1 (en) * | 1998-07-06 | 2000-02-09 | Dsm N.V. | Radiation curable acrylic acid esters containing amide groups |
| DE19903725A1 (en) | 1999-01-30 | 2000-08-10 | Basf Coatings Ag | Binder mixtures and their use in coating materials curable with actinic radiation and / or thermally |
| DE10150486A1 (en) | 2001-10-16 | 2003-04-24 | Basf Ag | Radically-copolymerizable photoinitiators for UV-curable materials, e.g. hot melt adhesives, are prepared by reacting polyisocyanate with isocyanate-reactive acrylic compound and aceto- or benzo-phenone derivative |
| DE10206987A1 (en) | 2002-02-19 | 2003-08-21 | Basf Ag | A new copolymerizate useful as a UV curable binder or adhesive, e.g. a contact adhesive, contains aceto- or benzophenone derivatives in polymerized form |
| DE102004041196A1 (en) * | 2004-08-26 | 2006-03-02 | Degussa Ag | Products from polymer-analogous reactions |
| CN101679555B (en) * | 2007-05-23 | 2012-05-23 | 昭和电工株式会社 | Reactive urethane compound having ether bond, curable composition and cured product |
| DE102008054611A1 (en) | 2008-12-15 | 2010-06-17 | Evonik Röhm Gmbh | Process for the preparation of methacrylated benzophenones |
| DE102013220127A1 (en) | 2013-10-04 | 2015-04-09 | Evonik Röhm Gmbh | Process for the preparation of methacrylated benzophenones |
| JP7260847B2 (en) * | 2019-02-26 | 2023-04-19 | 株式会社リコー | Active energy ray-polymerizable initiator, active energy ray-polymerizable composition, active energy ray-polymerizable ink, ink container, image forming method, and image forming apparatus |
| CN114341259B (en) * | 2019-09-18 | 2023-11-10 | 太阳控股株式会社 | Curable composition, dry film, cured product, and electronic component |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3322818A (en) * | 1963-03-04 | 1967-05-30 | Upjohn Co | New benzoylphenyl carbamates |
| US3429852A (en) * | 1967-03-30 | 1969-02-25 | Nat Starch Chem Corp | Ethylenically unsaturated derivatives of benzophenone and crosslinkable polymers thereof |
| JPS4843656B1 (en) * | 1969-06-27 | 1973-12-20 | ||
| DE3345104A1 (en) * | 1983-12-13 | 1985-06-13 | Bayer Ag, 5090 Leverkusen | ARYLAMINE DERIVATIVES POLYMERIZABLE IN UNSATURATED RESINS, THEIR PRODUCTION AND THEIR USE AS A CURING ACCELERATOR |
| US4737559A (en) * | 1986-05-19 | 1988-04-12 | Minnesota Mining And Manufacturing Co. | Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers |
-
1988
- 1988-06-16 DE DE3820463A patent/DE3820463A1/en not_active Withdrawn
-
1989
- 1989-06-10 EP EP89110564A patent/EP0346788B1/en not_active Expired - Lifetime
- 1989-06-10 AT AT89110564T patent/ATE74590T1/en active
- 1989-06-10 DE DE8989110564T patent/DE58901114D1/en not_active Expired - Lifetime
- 1989-06-10 ES ES198989110564T patent/ES2030241T3/en not_active Expired - Lifetime
- 1989-06-12 CA CA000602428A patent/CA1340884C/en not_active Expired - Fee Related
- 1989-06-16 JP JP1152469A patent/JP2716527B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10407701B2 (en) | 2016-02-26 | 2019-09-10 | Lg Chem, Ltd. | Method for preparing (meth)acrylate group-containing benzophenone for optical adhesive use and optical adhesive composition |
| US11505520B2 (en) | 2018-05-23 | 2022-11-22 | Evonik Operations Gmbh | Method for preparing keto-functionalized aromatic (meth)acrylates |
| US11912648B2 (en) | 2018-07-17 | 2024-02-27 | Evonik Operations Gmbh | Method for preparing C-H acidic (meth)acrylates |
| US11512043B2 (en) | 2018-07-26 | 2022-11-29 | Evonik Operations Gmbh | Process for preparing N-methyl(meth)acrylamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0240351A (en) | 1990-02-09 |
| DE3820463A1 (en) | 1989-12-21 |
| ES2030241T3 (en) | 1992-10-16 |
| ATE74590T1 (en) | 1992-04-15 |
| JP2716527B2 (en) | 1998-02-18 |
| EP0346788A1 (en) | 1989-12-20 |
| EP0346788B1 (en) | 1992-04-08 |
| DE58901114D1 (en) | 1992-05-14 |
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