Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/72—Two oxygen atoms, e.g. hydantoin
• • 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

Definitions

• the new acrylic acid esters and methacrylic acid esters are odourless substances which can be polymerised in a known manner, whereby polymers with a reactive 1 NH- grouping in the hydantoin ring or dihydrouracil ring are obtained, which can advantageously be processsed together with other resins.
• ACRYLIC ACID ESTERS CONTAINING A N,N-HETEROCYCLIC RING The present invention relates to new acrylic acid esters and methacrylic acid esters of monohydroxyalkylated hydantoin compounds or dihydrouracil compounds, a process for their manufacture and the use of the new acrylic acid esters and methacrylic acid esters for the manufacture of polymers and copolymers.
• Acrylic acid esters and methacrylic acid esters of aliphatic alcohols are known and a number of these compounds have already found a broad use for the manufacture of polymers, for example Plexiglas or acrylic resin lacquers.
• the acrylic acid esters of aliphatic alcohols which industrially can be manufactured cheaply, are 'liquid and in most cases have a low vapour pressure and a pungent odour. Thus, appropriate safety precautions must be taken when working with these physiologically not entirely harmless acrylic acid esters.
• only linear polymers, which do not contain any reactive groups in the side chain, can be manufactured from these previously known monomers.
• the polymers obtained from the new acrylic acid esters possess lateral hydantoin rings or dihydrouracil rings with a free 1- NH grouping which is capable of further reaction, for example with phenolformaldehyde resins, melamine lacquers or epoxide resins.
• cycloaliphatic, araliphatic or aromatic hydrocarbon radical each represent a hydrogen atom or an alkyl radical
• R, and R independently of one another each represent a hydrogen atom or the methyl group.
• R represents a hydrogen atom, an alkyl group, an alkyl group interrupted by ether oxygen atoms. or the phenyl group. or R and R together denote the trimethylene or tetramethylene radical.
• the reactants can be present either in approximately stoichiometric amounts or in a stoichiometric excess relative to the acrylic acid and/or methacrylic acid.
• the esterification reaction is advantageously carried out using an inert azeotropic agent.
• the reaction is as a rule acidcatalysed and carried out in the temperature range of 35 200C, preferably 60 C.
• the reaction solutions are washed until free of acid, concentrated, provided with stabilisers and then dried to constant weight in vacuo.
• acrylic acid esters or methacrylic acid esters of lower aliphatic alcohols are perferably used, preferentially in a stoichiometric excess.
• the trans-esterification reactions are acid-catalysed and are also carried out in the abovementioned temperature range.
• the lower aliphatic alcohol produced in this reaction is continuously distilled from the hatch.
• the excess monoacrylic acid ester or monomethacrylic acid ester is also removed from the reaction mixture by distillation.
• the crude product is then dissolved in an organic inert solvent, for example benzene, and worked up analogously to the reaction solutions obtained by esterification.
• the monohydroxy compounds of the Formula ll are known compounds and can be manufactured according to the process described in US. Pat. No. 3,629,263. by adding onto 1 mol of a N-heterocyclic compound ofthe formula wherein Z has the same meaning as in the Formula I, 1 mol of a monoepoxide of the formula R CH (EH-R wherein R and R have the same meaning as in the Formula I, in the presence of a suitable catalyst.
• ethene oxide ethene oxide, propene oxide, n-butene oxide, 1,2-cyclopentene oxide or 1,2-cyclohexene oxide, styrene oxide and glycidyl alkyl ethers, such as butyl-, amyl-, octylor dodecenylglycid. 2'
• individual compounds there may be mentioned: 3-(2'-hydroxyethyl)-5,5-dimethyl- 6-isopropyl-5,6-dihydrouracil, 3-(2-hydroxy-npropyl)-5,5-dimethyl-6-isopr0pyl-5,6-dihydrouracil and 3-(2-hydroxy-2-phenyl)-5,5-dimethyl-6-isopropyl-5,5-dihydrouracil.
• the new acrylic acid esters of the Formula I are crystalline substances which melt in the range of 40l 20C.
• the new acrylic acid esters which are soluble in water and in numerous organic solvents, can easily be prepared in a pure form by recrystallisation, and this increases their storage stability and permits dispensing with the addition of customary inhibitors.
• the acrylic acid esters of the Formula l manufactured according to the invention are valuable compounds which can be polymerised by themselves or together with other polymerisable monomers, whilst being shaped or as sheet-like structures.
• Possible monomers which can be added to the new acrylic acid esters of the Formula I are both com pounds of the acrylic acid series, such as esters of acrylic acid or methacrylic acid and alcohols or phenols, for example methyl acrylate, butyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile and ethylene glycol dimethacrylate, and other reactive, olefinically unsaturated monomers, such as, for example, styrene, divinylbenzene and vinyl acetate.
• the acrylic acid series such as esters of acrylic acid or methacrylic acid and alcohols or phenols, for example methyl acrylate, butyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile and ethylene glycol dimethacrylate
• other reactive, olefinically unsaturated monomers such as, for example, styrene, divinylbenzene and vinyl acetate.
• the customary free radical-forming catalysts are used for the polymerisation or copolymerisation; there may be mentioned hydrazinederivatives, for example hydrazine hydrochloride, organo-metallic compounds, such as lead tetraethyl, and especially aliazo compounds, such as a, a-azoisobutyrodinitile, and organic peroxides or per-salts, such as, for example, peracetic acid, acetyl peroxide, chloroacetyl peroxide, trichloroacetyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, benzoylacetyl peroxide, propionyl peroxide, fluorochloropropionyl peroxide, lauroyl peroxide, cumene hydroperoxide, cyclohexanone hydroperoxide, tert.butyl hydroperoxide, di-tert.-butyl peroxide
• the amount added depends, in a known manner, on the desired course of the reaction or the desired properties of the polymer; advantageously, about 0.05 to 10 per cent by weight of the catalyst, relative to the total weight of the polyacrylate mixture or polyacrylate-monomer mixture are employed, the total amount of the catalyst being added either at the beginning or in portions over the course of the polymerisation.
• cationic or anionic catalysts can also be used.
• the acrylic acid esters manufactured according to the invention can be used in surface protection. in compression moulding compositions. as casting resins and the like.
• the present application also relates to curable mixtures which are suitable for the manufacture of shaped articles, including sheet-like structures; and which contain the acrylic acid esters according to the invention, optionally together with other polymerisable monomers, and the polymerisation catalysts customary for the polymerisation curing.
• the polymerisable mixtures suitable for the manufacture of coatings and compression moulding compositions can additionally also contain plasticisers, fillers and preferably pigments, for example titanium dioxide.
• the homopolymers or copolymers obtained from the new monomeric acrylic acid esters of the Formula 1 ac cording to known polymerisation processes are hard, high-melting substances which are preferably used in surface protection agents or in compression moulding compositions.
• the present invention also relates to new homopolymers or copolymers having the recurring structural unit of the formula wherein Z, R,, R and R have the same meaning as in the Formula 1 and n is a number greater than 4.
• Z denotes the diva lent radical of the formula wherein X and X each denote a hydrogen atom or an alkyl radical with l 4 carbon atoms or together denote the tetramethylene or pentamethylene radical, R, and R independently of one another each represent a hydrogen atom or the methyl group and R denotes a hydrogen atom or the methyl or phenyl group, or
• R and R together denote the trimethylene or tetramethylene radical, and n denotes a number having a value of 5 250.
• the homopolymers and copolymers having the structural characteristic of the Formula Vll contain lateral N-heterocyclic rings with a free-l-NH- grouping, which is capable of further reaction, for example with phenol-formaldehyde resins, melamine resins or epoxide resins.
• the reactive linear polymers according to the Formula Vll are therefore suitable. by themselves or preferably in combination with compounds which possess several functional groups capable of reaction with the reactive l-NH- grouping. for the manufacture of lacquers or coatings. films, compression moulding compositions and the like.
• EXAMPLE 1 A mixture of 1,033.2 g of 3-(2'-hydroxyethyl)-5.5- dimethylhydantoin (6 mols), 775 g of methacrylic acid (9 mols; corresponding to 50% excess of methacrylic acid), 3 litres of toluene, 20 ml of 50% strength sulphuric acid, 0.45 g of phenothiazine and 3 g of triphenylphosphite is brought to 103C internal temperature whilst stirring, at 160C bath temperature, in a stirred flask of 6 litres capacity provided with a thermometer, stirrer, dropping funnel, water separator with reflux condenser and receiver.
• reaction mixture obtained is twice extracted by shaking with 500 ml of an aqueous solution which contains 10% of ammonia and 5% of ammonium sulphate.
• the following stabiliser mixture is added to the organic phase: 0.5 g of hydroquinone, 0.14 g of pyrocatechol, 0.04 g of copper naphthenate (87: strength) and 0.05 g of NaNO in 0.15 g of H 0.
• the new methacrylate can be purified, for example, by recrystallisation from a tetrahydrofuran/hexane (1:1) solvent mixture or from cyclohexane.
• a 200 g sample recrystallised from cyclohexane yields 138 g of colourless crystals (without working up the mother liquor) melting at 809C (Mettler FP 51; speed of heating: 1C/minute).
• the purity can be estimated to be approx. 96% from the H-NMR spectrum, from the ratio of the integral of 2. 195 g of a clear, light yellow, viscous liquid, which crystallises throughout after a few hours, are obtained.
• the content of acrylate groups is 97.6% of theory, according to titration; micro-hydrogenation indicates a value of of theory and the H-NMR spectrum shows a purity of about 97% of theory.
• a sample is recrystallised from a solvent mixture consisting of tetrahydrofurune/hexane (1:1) in the ratio of 1:1.
• a colourless crystal powder is obtained, which melts at 91.2C (Mettler FP 51", using a speed of heating of 1C/minute) and of which the acrylate group content is determined by titration to be 4.08 equivalents/kg (corresponding to 98.3% of theory).
• the new acrylate corresponds to the following formula:
• the reaction product obtained is worked up accord ing to the procedure described in Example 1 and 253.6 g of a crude product which is coloured pale red-brown and is solid at room temperature (83. 91 oftheory) are obtained, wherein the content of acrylic ester groups corresponds to 69.5% of theory.
• the new acrylate accordingly corresponds to the following structure:
• the mixture is heated to 106C whilst stirring and the separation of water then commences 175C bath temperature).
• the acrylic acid ester of 3(2-hydroxycyclohexyl)- 5,5-dimethylhydantoin is manufactured by reacting the following reaction mixture in accordance with the conditions described in Example 5: g of 3-(2- hydroxycyclohexyl)-5,5-dimethylhydantoin (0.155 mol), 16.74 g ofacrylic acid (0.232 mol), 95 m1 oftolucne. 0.5 m1 of H 50, strength), 0.012 g of phenothiazine and 0.08 g of triphenylphosphite.
• Remnants ofunreacted starting material are removed by dissolving in toluene. After concentration and drying, a light yellow substance which crystallises at room temperature is obtained, the purity of which is found to be 94-9557: by titrimetric determination of the acrylate double bonds.
• the new acrylate corresponds to the following structure:
• EXAMPLE 7 The methacrylic acid ester of 3-(2-hydroxy-npropyl)-5,5-tetramethylenehydantoin is manufactured by reacting the following reaction mixture under the reaction conditions described in Example 62.2 g of 3-(2'-hydroxy-n-propyl)-5,S-tetramethylenehydantoin (0.31 mol), 48.9 g of methacrylic acid (0.46 moi), 2.5 g of H 80 (50% strength), 0.028 g of phenothiazine and 0.18 g of triphenylphosphite.
• the substance can be purified by recrystallisation from toluene. Colourless, fine crystals are obtained, the melting point of which is l15.lC (Mettler FP 51", speed of heating: 2C/per minute).
• phenylethyl)-5 ,5-pentamethylenehydantoin is man ufactured analogously to Example 7 by reaction of the following reaction mixture: 153 g of 3-(2'-hydroxy-2' phenylethyl)-5,S-pentamethylenehydantoin (0.53
• the molecular weight determined by vapour pressure osmometry shows a numerical average molecular weight of 16,650 (i 10%
• the polymer has essentially the following structure:
• Use example 7.0 g of the acrylate manufactured according to Example 9 are mixed with 70 mg of benzoyl peroxide and the mixture is heated to 120C for 1 hour.
• the viscous substance changes to a product which is glassy at room temperature and has a glass transition temperature of 80C (Kofler bench).
• This polymer is treated with 4 g of a 75% strength solution of a melamine-formaldehyde-n-butylether resin in nbutyl alcohol and 8.5 g of ethylglycol acetate.
• 0.5 ml ofa strength solution of p-toluenesulphonic acid in ethanol is added to the homogeneous solution.
• This clear lacquer is applied to degreased aluminium sheets and cured for 40 minutes at 180C. This yields scratch-resistant, hard films which are also resistant to toluene. alcohol and acetone.
• the melamine-formaldehyde-n-butyl-ether resin used is a condensation product of l mol melamine, 5.5 mols of formaldehyde and 3.5 mols of n-butyl alcohol. It is commercially available as a 75% strength solution in butyl alcohol.
• Acrylic acid esters of the formula c--c--o 2 l an N-CH-CH-O-CC CH approx 69 wherein X and X each represent a hydrogen atom or an alkyl radical with l-4 carbon atoms or together represent the tetramethylene or pentamethylene radical, R and R independently of one another each represent a hydrogen atom or the methyl group and R represents a hydrogen atom or the methyl or phenyl group, or wherein R and R together represents the trimethylene or tetramethylene radical.
• a compound as claimed in claim I. which is 3- (methacryloyloxyethyl)-5.S-dimethylhydantoin.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (1)

• 1972
  • 1972-07-12 CH CH1042472A patent/CH570379A5/xx not_active IP Right Cessation
• 1973
  • 1973-06-29 GB GB3116073A patent/GB1405540A/en not_active Expired
  • 1973-07-09 DE DE19732334826 patent/DE2334826A1/de not_active Withdrawn
  • 1973-07-09 US US377698A patent/US3864357A/en not_active Expired - Lifetime
  • 1973-07-11 JP JP48078854A patent/JPS50100061A/ja active Pending
  • 1973-07-12 FR FR7325541A patent/FR2192104B1/fr not_active Expired

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