T-ALKENYL PEROXY ESTERS AND THEIR USE AS INITIATORS AND CURING AGENTS

Abstract: This disclosure relates to novel peroxyesters carrying a t-alkenyl, e.g. 2-methyl-3-butene-2-yl , peroxy group. These peroxy esters have shorter half-life periods of decomposition and are more reactive polymerization initiators and unsaturated polyester resin curing agents than the correspon­ ding prior art peroxy esters carrying a t-alkyl, e.g. t-amyl, peroxy group.

Description: The invention relates to novel peroxy esters and to their use in the (co)­ polymerization of ethylenically unsaturated compounds and in the curing of unsaturated polyester resins. The use of t-alkyl peroxy esters as initiators and curing agents is general­ ly known. Examples thereof are described in, int.al., U.S. Patent Specifi­ cation Nos. 3 781 255, 4 057 567 and 4 219 675. On economical grounds, how­ ever, there is a continuous need for more efficient initiators and curing agents for the purpose of shortening the reaction times and increasing the production capacities. The invention has for its object to meet this need. The peroxy ester according to the invention corresponds to the general formula: wherein m = 1 or 2, and when m = 1, R₁ has the meaning of a cyclohexyl group, a cyclohexenyl group, a phenyl group which is substituted or not with one or more chlorine atoms or methyl groups, wherein R₇ and R₈ are the same or different and represent a hydrogen atom or an alkyl group containing 1-10 carbon atoms, and R₉ represents a hydrogen atom, an alkyl group containing 1-10 carbon atoms, an alkoxy group containing 1-6 carbon atoms, a phenyl group or a phenoxy group or wherein R₁₀ and R₁₁ are the same or different and represent a hydrogen atom or an alkyl group containing 1-4 carbon atoms; when m = 2, R₁ has the meaning of an alkylene group containing 1-11 carbon atoms, a cyclohexylene group, a phenylene group or a group of the formula -CH₂-O-CH₂-; R₂ and R₃ are the same or different and represent an alkyl group containing 1-4 carbon atoms or together represent a pentamethylene bridge; and R₄, R₅ and R₆ are the same or different and represent a hydrogen atom or an alkyl group containing 1-4 carbon atoms. The above-indicated upper limits with regard to the numbers of carbon atoms for R₁ up to and including R₁₁ are governed by practical considerations. The alkyl groups and the alkylene group indicated may be linear or branched. Essential to the peroxy esters according to the invention is the presence of the structural element where the carbon atom linked to the peroxide bond should have a tertiary structure and the double bond is separated from the peroxide bond by this carbon atom. It has been found that the t-alkenyl peroxy esters according to the inven­ tion have shorter half-life periods of decomposition and are more reactive initiators and curing agents than the prior art t-alkyl peroxy esters of otherwise the same structure. The peroxy esters according to the invention may be divided into monoperoxy esters (m=1) and diperoxy diesters (m=2). They may be prepared in the usual manner by reacting an acid chloride with a t-alkenyl hydroperoxide in the presence of a base. The acid chlorides suitable for this purpose are prepared by reacting a car­ boxylic acid with a chlorinating reagent, such as PCl₃, POCl₃, PCl₅, COCl₂ and SOCl₂. The carboxylic acid used has the general structural formula: wherein R₁ and m have the above-indicated meaning. As examples of suitable monocarboxylic acids may be mentioned cyclohexane-­ carboxylic acid, 2-cyclohexene-1-carboxylic acid, benzoic acid, o-, m- and p-methylbenzoic acid, o-chlorobenzoic acid, 2,4-dichlorobenzoic acid, acetic acid, n-heptanoic acid, lauric acid, 2-ethylhexanoic acid, 3,5,5-trimethyl­ hexanoic acid, phenylacetic acid, isobutyric acid, 2-methylbutyric acid, 2-­ ethylbutyric acid, 2-phenylbutyric acid, 2-methylpentanoic acid, 2,2-di­ methyloctanoic acid, pivalic acid, neohexanoic acid, neoheptanoic acid, neooctanoic acid, neononanoic acid, neodecanoic acid, neotridecanoic acid (the last five neo acids having such a structure that not more than one of the groups R₇, R₈ and R₉ is a methyl group, as described in US 3 624 123), methoxyacetic acid, ethoxyacetic acid, phenoxyacetic acid, acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid (of the last four acids methacrylic acid, crotonic acid and 2-methylcrotonic acid are prefer­ red). As examples of suitable dicarboxylic acids may be mentioned malonic acid, succinic acid, glutaric acid, 2,2-dimethyl-1,5-pentanedioic acid, adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and diglycolic acid. The t-alkenyl hydroperoxides suitable for the preparation of the present peroxy esters satisfy the general structural formula: wherein R₂ through R₆ have the above-indicated meaning. They are prepared in the usual manner by reacting a t-alkenyl alcohol with hydrogen peroxide in the presence of a strongly acid catalyst such as sulphuric acid. As examples of t-alkenyl hydroperoxides suitable to be used in the prepa­ ration of the present peroxyesters may be mentioned: 2-methyl-3-butene-2-yl hydroperoxide, 3-methyl-1-pentene-3-yl hydroperoxide, 3,4-dimethyl-1-pentene-3-yl hydroperoxide, 3-ethyl-1-pentene-3-yl hydroperoxide, 3-isopropyl-4-methyl-1-pentene-3-yl hydroperoxide, 3-methyl-1-hexene-3-yl hydroperoxide, 3-n-propyl-1-hexene-3-yl hydroperoxide, 1-vinylcyclohexyl-1-yl hydroperoxide, 2-methyl-3-pentene-2-yl hydroperoxide, and 2,3,4-trimethyl-3-pentene-2-yl hydroperoxide. As the starting alcohol is satisfactorily available, it is preferred that use should be made of 2-methyl-3-butene-2-yl hydroperoxide (where R₂ and R₃ represent methyl groups and R₄, R₅ and R₆ hydrogen atoms). All the peroxy esters according to the invention satisfy the above-described formula I. Preferred are those peroxy esters where in formula I when m = 1, R₁ has the meaning of a cyclohexyl group, a phenyl group, an o-chlorophenyl group, an o-methylphenyl group, wherein R₇ and R₈ are the same or different and represent a hydrogen atom or an alkyl group containing 1-10 carbon atoms and R₉ represents a hydrogen atom, an alkyl group containing 1-10 carbon atoms, a phenyl group or a phenoxy group or wherein R₁₀ and R₁₁ are the same or different and represent a hydrogen atom or a methyl group; when m = 2, R₁ has the meaning of an alkylene group containing 3-11 carbon atoms, more particularly 3-8 carbon atoms, a 1,4-cyclohexylene group, an o-, m- or p-phenylene group or a group of the formula -CH₂-O-CH₂-. Typical examples of suitable peroxyesters according to the invention are 2-methyl-3-butene-2-yl peroxycyclohexanecarboxylate, 2-methyl-3-butene-2-yl peroxy-2-cyclohexene-1-carboxylate, 2-methyl-3-butene-2-yl peroxybenzoate, 2-methyl-3-butene-2-yl peroxy-o-methylbenzoate, 2-methyl-3-butene-2-yl peroxy-o-chlorobenzoate, 2-methyl-3-butene-2-yl peroxyacetate, 2-methyl-3-butene-2-yl peroxyisobutyrate, 2-methyl-3-butene-2-yl peroxypivalate, 2-methyl-3-butene-2-yl peroxyneohexanoate, 2-methyl-3-butene-2-yl peroxyneoheptanoate, 2-methyl-3-butene-2-yl peroxyneooctanoate, 2-methyl-3-butene-2-yl peroxyneononanoate, 2-methyl-3-butene-2-yl peroxyneodecanoate, 2-methyl-3-butene-2-yl peroxyneotridecanoate, 2-methyl-3-butene-2-yl peroxy-2-methylbutyrate, 2-methyl-3-butene-2-yl peroxy-2-ethylbutyrate, 2-methyl-3-butene-2-yl peroxy-2-methylpentanoate, 2-methyl-3-butene-2-yl peroxy-2-ethylhexanoate, 2-methyl-3-butene-2-yl peroxy-3,5,5-trimethylhexanoate, 2-methyl-3-butene-2-yl peroxyphenylacetate, 2-methyl-3-butene-2-yl peroxy-2-phenylbutyrate, 2-methyl-3-butene-2-yl peroxylauroate, 2-methyl-3-butene-2-yl peroxyphenoxyacetate, 2-methyl-3-butene-2-yl peroxyacrylate, di(2-methyl-3-butene-2-yl) diperoxyglutarate, di(2-methyl-3-butene-2-yl) diperoxyadipate, di(2-methyl-3-butene-2-yl) diperoxyazelate, di(2-methyl-3-butene-2-yl) diperoxysebacate, di(2-methyl-3-butene-2-yl) diperoxy-1,10-decanedicarboxylate, di(2-methyl-3-butene-2-yl) diperoxy-1,11-undecanedicarboxylate, di(2-methyl-3-butene-2-yl) diperoxy-1,4-cyclohexanedicarboxylate, di(2-methyl-3-butene-2-yl) diperoxyphthalate, di(2-methyl-3-butene-2-yl) diperoxyisophthalate, di(2-methyl-3-butene-2-yl) diperoxyterephthalate, di(2-methyl-3-butene-2-yl) diperoxydiglycolate. The peroxy ester according to the invention is very suitable to be used in the polymerization or copolymerization of ethylenically unsaturated com­ pounds. As examples of ethylenically unsaturated compounds may be mentioned olefins, such as ethylene, styrene, α-methylstyrene and chlorostyrene; diolefins, such as 1,3-butadiene and isoprene; vinyl esters, such as vinyl acetate and vinyl propionate; unsaturated nitriles, such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid and their esters and amides; vinyl halo and vinylidene halo compounds, such as vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride and vinylidene fluoride; perhalo olefins, such as tetrafluoroethylene; vinyl ethers, such as methyl vinyl ether and n-butyl vinyl ether; and mixtures thereof. It is preferred that the present peroxy ester should be used in the polymerization of vinyl chloride, styrene, ethylene or methyl methacrylate, more particularly in the suspension, emulsion or mass polymerization of vinyl chloride. The present peroxy esters may be used as such or in combination with other initiators. This last-mentioned embodiment is used to obtain a most constant reaction speed throughout the polymerization process. To this end use is made of a combination of a relatively rapid and a relatively slow initiator. As examples of combinations commonly used in actual practice may be men­ tioned acetylcyclohexane sulphonyl peroxide with dilauroyl peroxide and 2,4,4-trimethylpentane-2-yl peroxyphenoxy acetate with bis(4-t-butylcyclo­ hexyl)peroxydicarbonate. It has been found that upon replacement in these combinations of, respectively, acetylcyclohexane sulphonyl peroxide and 2,4,4-trimethylpentane-2-yl peroxyphenoxy acetate with the present peroxy esters, the resulting initiator combinations lead to satisfactory results in the polymerization of vinyl chloride. The present peroxy ester is to be used in an amount of 0,005 to 3% by weight, preferably 0,01 to 0,5% by weight, and in particular 0,02 to 0,2% by weight, calculated on the weight of the monomer. The temperature to be used is in the range of 20°C to 250°C, preferably 30°C to 200°C. The peroxy ester according to the invention is also suitable to be applied in the curing of unsaturated polyester resins. Such resins generally com­ prise an unsaturated polyester, a polymerizable monomer, and, optionally, fillers. An example of an unsaturated polyester resin is one of which the polyester component consists of the esterification product of 1,2-propylene glycol and maleic anhydride and phthalic anhydride and of which the poly­ merizable monomer is styrene. The amount of peroxy ester to be used is 0,05 to 5% by weight, preferably 0,5 to 2% by weight, calculated on the weight of the unsaturated polyester resin. The temperature to be used is in the range of about 20°C to 200°C. For the above-mentioned uses also combinations of the present peroxy esters may be employed. The peroxy esters according to the invention may be prepared, transported, stored and applied as such or formulated as solutions, aqueous suspensions or emulsions, pastes, etc. Which of these alternatives is to be preferred depends, int.al., on safety considerations (desensitizing) and considera­ tions regarding the nature of their use (the aqueousness or not of the poly­ merization system, feeding the peroxy esters into closed reaction systems, etc.). As suitable desensitizing agents may be mentioned the paraffinic hydro­ carbons commonly employed for this purpose, such as isododecane and white spirit, plasticizers, such as esters of phthalic acid, solid carrier materials, such as silica, water, etc. For the formulation of aqueous sus­ pensions (in the case of solid peroxy esters) or emulsions (in the case of liquid peroxy esters) use may be made of the emulsifiers and/or thickening agents commonly employed to this end. Examples of such emulsifiers and thickening agents are described in U.S. Patent Specification No. 3 988 261. If for safety reasons said suspensions and emulsions are to be transported and stored at low temperature, then there may optionally be added to them anti-freeze agents, such as methanol, ethanol, propanol, isopropanol and butanol. The following examples serve to illustrate the invention. Example I Preparation of 2-methyl-3-butene-2-yl hydroperoxide To a stirred mixture cooled at 5°C of 9,7 g of 70%-hydrogen peroxide (0,20 moles) and 0,9 g of 85%-sulphuric acid (0,008 moles) there were added dropwise over a period of 5 minutes 8,6 g of 2-methyl-3-butene-2-ol (0,10 moles), care being taken that the temperature of the reaction mixture re­ mained between 5° and 10°C. Subsequently, the mixture was stirred for 20 minutes at 10°C, and then for 60 minutes at 20°C. Next, 6 g of solid sodium sulphate were added to the reaction mixture. After the organic layer had been isolated, it was washed three times with a saturated aqueous solution of sodium sulphate. Finally, the organic layer was dried with MgSO₄. After filtration 9,2 g of product were obtained as colourless liquid. Its active oxygen content was 13,56%, which corresponds to a yield of 78%. The identity of the product was confirmed by NMR and IR spectroscopy. Example 2 Preparation of 2-methyl-3-butene-2-yl peroxypivalate To a stirred mixture cooled at 10°C of 10 g of demineralized water, 17,3 g of a 45% by weight-potassium hydroxide solution in water (0,139 moles) and 12,9 g of 2-methyl-3-butene-2-yl hydroperoxide (0,120 moles) there were added over a period of 25 minutes 14,5 g of pivaloyl chloride (0,120 moles); the temperature of the reaction mixture was kept at 10°-12°C. Stirring was continued for 1 hour, after which the organic layer was isolated. It was washed successively with an aqueous solution of 10% by weight-KOH (15 min, 10°C), an aqueous bisulphite/acetate buffer (20 min., 10°C) and a dilute solution of sodium bicarbonate in water (2x). Finally, the organic layer was dried with MgSO₄ and the product was isolated by filtration. There were ob­ tained 17,3 g of colourless oil containing 97,7% of peroxy ester, which corresponds to a yield of 75,6%. The identity of the product was confirmed by IR and NMR spectroscopy (¹H and ¹³C). Example 3 Preparation of other 2-methyl-3-butene-2-yl peroxy esters Use being made of the same procedure as described in Example 2, except that the pivaloyl chloride was replaced with the appropriate acid chlorides in the appropriate amounts, the following peroxy esters were prepared. All products obtained were colourless oils. 2-methyl-3-butene-2-yl peroxyneodecanoate assay: 95% yield: 72,9% 2-methyl-3-butene-2-yl peroxyneohexanoate assay: 93,8% yield: 79,6% 2-methyl-3-butene-2-yl peroxy-2-ethylhexanoate assay: 98,3% yield: 88,8% 2-methyl-3-butene-2-yl peroxybenzoate assay: 98,8% yield: 85,2% 2-methyl-3-butene-2-yl peroxyphenylacetate assay: 95,1% yield: 72,7% 2-methyl-3-butene-2-yl peroxy-2-methylpropanoate assay: 96,8% yield: 80% di(2-methyl-3-butene-2-yl) diperoxyazelate assay: 95,4% yield: 57,3% di(2-methyl-3-butene-2-yl) diperoxydiglycolate assay: 94,2% yield: 70,1% Of all products the identity was confirmed by IR and NMR spectroscopy. Example 4 Decomposition tests were conducted in chlorobenzene as solvent (concen­ tration: 1 mole/litre). Of the peroxy esters prepared in Example 2 and 3 the temperatures are given in Table 1 at which the half life periods of decom­ position are 10 hours (t½₁₀), 1 hour (t½₁) and 0,1 hour (t½₀ , ₁). For com­ parison the Table also gives the temperatures for t½₁₀, t½₁, and t½₀ , ₁ of esters which are derived from the same carboxylic acids but carry the prior art t-amyl (=2-methylbutane-2-yl) peroxy group. The results show that the 2-methyl-3-butene-2-yl peroxy esters according to the invention display a higher rate of decomposition than the corresponding t-amyl peroxy esters which are of nearly identical structure but are outside the scope of the invention. Example 5 In this Example the results obtained with peroxy esters according to the invention used as initiators in the polymerization of vinyl chloride are compared with those obtained with the corresponding t-amyl peroxy esters which are of nearly identical structure but are outside the scope of the invention. The following general procedure was used. To a solution in 340 g of water of 0,2 g of polyvinyl alcohol (Gohsenol KP-08, a commercial product of Nippon Gohsei) and 0,84 g of sodium bicar­ bonate contained in an autoclave (1-litre) there were added, under an atmosphere of nitrogen, 200 g of vinyl chloride and the initiator. The stirring speed was 750 r.p.m. The reaction mixture was heated and after a certain reaction time (including the heating time) the reaction mixture was cooled and unreacted vinyl chloride removed, after which polyvinyl chloride was isolated by filtration. The product was washed and finally dried for 16 hours at 50°C. From the weight of the resulting polymer the conversion was calculated. The process data as regards type of peroxy ester, amount of peroxy ester (calculated as pure peroxy ester), reaction temperature and reaction time are summerized in Table 2. Also summarized in Table 2 are the conversions of vinyl chloride obtained. Judged by their higher conversion rates the peroxy esters according to the invention are clearly more active initiators than the corresponding t-amyl peroxy esters. Example 6 In this Example the results obtained with peroxy esters according to the invention used as initiators in the polymerization of methyl methacrylate are compared with those obtained with the corresponding t-amyl peroxy esters which are of nearly identical structure but are outside the scope of the invention. The following general procedure was used. Into each of three 4-ml ampules which all contained a mixture of 0,97 g of methyl methacrylate and 0,53 g of toluene the initiator was introduced under a nitrogen atmosphere. After respectively 2, 4 and 6 hours' reaction time at elevated temperature the reaction was stopped by mixing the contents of an ampule with 20 g of dichloromethane containing 0,048 g of 2,6-di-t-butyl-4-­ methylphenol. Subsequently, the degree of conversion was determined by gaschromatographic analysis, use being made of benzene as internal standard. The process data as regards type of peroxy ester, amount of peroxyester (calculated as pure peroxy ester) and reaction temperature are summarized in Table 3. Also summarized in the Table are the conversions of methyl meth­ acrylate obtained. As clearly shown by their higher conversion rates the peroxy esters of the invention are more active initiators than the cor­ responding t-amyl peroxy esters. Example 7 Into each of two 4-ml ampules styrene was mass polymerized at 110°C using an initiator according to the invention, viz. 2-methyl-3-butene-2-yl peroxy­ benzoate, in an amount of 0,375 mmoles (calculated as pure peroxy ester) per 100 g of styrene in the one experiment and di(2-methyl-3-butene-2-yl) di­ peroxyazelate in an amount of 0,40 mmoles (calculated as pure diperoxy di­ ester) per 100 g of styrene in the other. In both experiments a conversion of more than 99%, as determined by gaschromatographic analysis, was ob­ tained after 8 hours' reaction time. Example 8 In this Example the results obtained with peroxy esters according to the invention used as curing agents for unsaturated polyester resins are com­ pared with those obtained with t-amyl peroxy esters which are of nearly identical structure but are outside the scope of the invention, use being made of the procedures outlined in SPI Handbook of Reinforced Plastics, published by the Reinhold Publishing Corp., New York, pp. 36-37 (1964). The unsaturated polyester resin used was a mixture of an unsaturated poly­ ester and styrene monomer. The unsaturated polyester was an alkyd resin prepared by esterifying (to an Acid No. of about 50) the following compo­ nents: maleic anhydride (1 mole), phthalic anhydride (1 mole), ethylene glycol (1,1 mole) and propylene glycol (1,1 mole). To the resulting resin were added 100 ppm of hydroquinone inhibitor, after which 65 parts of this resin were diluted with 35 parts of styrene. To 25 g of the above-described unsaturated polyester resin were added 250 mg of peroxy ester (calculated as pure peroxy ester); subsequently, the time-­ temperature characteristics were determined in accordance with SPI, use being made of various bath temperatures. The results are summarized in Table 4. They show that in the curing of un­ saturated polyester resin the peroxy esters according to the invention are more active than the corresponding t-amyl peroxy esters. In Table 4 the following abbreviations are used: gt = gel time mct = minimum cure time ttp = time to peak pe = peak exotherm

Claims: 1. A peroxy ester of the general formula: wherein m = 1 or 2, and when m = 1, R₁ has the meaning of a cyclohexyl group, a cyclohexenyl group, a phenyl group which is substituted or not with one or more chlorine atoms or methyl groups, wherein R₇ and R₈ are the same or different and represent a hydrogen atom or an alkyl group containing 1-10 carbon atoms, and R₉ represents a hydrogen atom, an alkyl group containing 1-10 carbon atoms, an alkoxy group containing 1-6 carbon atoms, a phenyl group or a phenoxy group or wherein R₁₀ and R₁₁ are the same or different and represent a hydrogen atom or an alkyl group containing 1-4 carbon atoms; when m = 2, R₁ has the meaning of an alkylene group containing 1-11 carbon atoms, a cyclohexylene group, a phenylene group or a group of the formula -CH₂-O-CH₂-; R₂ and R₃ are the same or different and represent an alkyl group con­ taining 1-4 carbon atoms or together represent a pentamethylene bridge; and R₄, R₅ and R₆ are the same or different and represent a hydrogen atom or an alkyl group containing 1-4 carbon atoms. 2. A peroxy ester according to claim 1, characterized in that R₂ and R₃ represent methyl groups and R₄, R₅ and R₆ hydrogen atoms. 3. A peroxy ester according to claim 2, characterized in that when m=1, R₁ has the meaning of a cyclohexyl group, a phenyl group, an o-chlorophenyl group, an o-methylphenyl group, wherein R₇ and R₈ are the same or different and represent a hydrogen atom or an alkyl group containing 1-10 carbon atoms and R₉ represents a hydrogen atom, an alkyl group containing 1-10 carbon atoms, a phenyl group or a phenoxy group or wherein R₁₀ and R₁₁ are the same or different and represent a hydrogen atom or a methyl group; when m=2, R₁ has the meaning of an alkylene group containing 3-11 carbon atoms, a 1,4-cyclohexylene group, an o-, m- or p-phenylene group or a group of the formula -CH₂-O-CH₂-. 4. A peroxy ester according to claim 1, characterized in that the peroxy ester is selected from the group consisting of 2-methyl-3-butene-2-yl peroxypivalate, 2-methyl-3-butene-2-yl peroxy-2-ethylhexanoate, 2-methyl-3-butene-2-yl peroxyneodecanoate, 2-methyl-3-butene-2-yl peroxyneohexanoate, 2-methyl-3-butene-2-yl peroxybenzoate, 2-methyl-3-butene-2-yl peroxy-2-methylpropanoate, 2-methyl-3-butene-2-yl peroxyphenylacetate, 2-methyl-3-butene-2-yl peroxy-3,5,5-trimethylhexanoate, di(2-methyl-3-butene-2-yl) diperoxy-1,4-cyclohexanedicarboxylate, di(2-methyl-3-butene-2-yl) diperoxyazelate and di(2-methyl-3-butene-2-yl) diperoxydiglycolate. 5. A process for the (co)polymerization of an ethylenically unsaturated compound in the presence of a peroxy ester, characterized in that the peroxy ester is a peroxy ester according to claim 1. 6. A process according to claim 5, characterized in that the ethylenically unsaturated compound used is vinyl chloride, ethylene, styrene or methyl methacrylate. 7. A process for curing an unsaturated polyester resin in the presence of a peroxy ester, characterized in that the peroxy ester is a peroxy ester according to claim 1. Claims for the contracting State :AT 1. A process for the preparation of a peroxy ester of the general formula: wherein m = 1 or 2, and when m = 1, R₁ has the meaning of a cyclohexyl group, a cyclohexenyl group, a phenyl group which is substituted or not with one or more chlorine atoms or methyl groups, wherein R₇ and R₈ are the same or different and represent a hydrogen atom or an alkyl group containing 1-10 carbon atoms, and R₉ represents a hydrogen atom, an alkyl group containing 1-10 carbon atoms, an alkoxy group containing 1-6 carbon atoms, a phenyl group or a phenoxy group or wherein R₁₀ and R₁₁ are the same or different and represent a hydrogen atom or an alkyl group containing 1-4 carbon atoms; when m = 2, R₁ has the meaning of an alkylene group containing 1-11 carbon atoms, a cyclohexylene group, a phenylene group or a group of the formula -CH₂-O-CH₂-; R₂ and R₃ are the same or different and represent an alkyl group containing 1-4 carbon atoms or together represent a pentamethylene bridge; and R₄, R₅ and R₆ are the same or different and represent a hydrogen atom or an alkyl group containing 1-4 carbon atoms. 2. A process according to claim 1, characterized in that R₂ and R₃ represent methyl groups and R₄, R₅ and R₆ hydrogen atoms. 3. A process according to claim 2, characterized in that when m=1, R₁ has the meaning of a cyclohexyl group, a phenyl group, an o-chlorophenyl group, an o-methylphenyl group, wherein R₇ and R₈ are the same or different and represent a hydrogen atom or an alkyl group containing 1-10 carbon atoms and R₉ represents a hydrogen atom, an alkyl group containing 1-10 carbon atoms, a phenyl group or a phenoxy group or wherein R₁₀ and R₁₁ are the same or different and represent a hydrogen atom or a methyl group; when m=2, R₁ has the meaning of an alkylene group containing 3-11 carbon atoms, a 1,4-cyclohexylene group, an o-, m- or p-phenylene group or a group of the formula -CH₂-O-CH₂-. 4. A process according to claim 1, characterized in that the peroxy ester is selected from the group consisting of 2-methyl-3-butene-2-yl peroxypivalate, 2-methyl-3-butene-2-yl peroxy-2-ethylhexanoate, 2-methyl-3-butene-2-yl peroxyneodecanoate, 2-methyl-3-butene-2-yl peroxyneohexanoate, 2-methyl-3-butene-2-yl peroxybenzoate, 2-methyl-3-butene-2-yl peroxy-2-methylpropanoate, 2-methyl-3-butene-2-yl peroxyphenylacetate, 2-methyl-3-butene-2-yl peroxy-3,5,5-trimethylhexanoate, di(2-methyl-3-butene-2-yl) diperoxy-1,4-cyclohexanedicarboxylate, di(2-methyl-3-butene-2-yl) diperoxyazelate and di(2-methyl-3-butene-2-yl) diperoxydiglycolate. 5. A process for the (co)polymerization of an ethylenically unsaturated compound in the presence of a peroxy ester, characterized in that the peroxy ester is a peroxy ester prepared according to the process of claim 1. 6. A process according to claim 5, characterized in that the ethylenically unsaturated compound used is vinyl chloride, ethylene, styrene or methyl methacrylate. 7. A process for curing an unsaturated polyester resin in the presence of a peroxy ester, characterized in that the peroxy ester is a peroxy ester prepared according to the process of claim 1.

Inventors: BOELEMA, ELTJO, MEIJER, JOHN, WESTMIJZE,, HANS
Applicants: AKZO N.V.
Application year: 1986
Main classification: C07C409
IPC codes: C07C409, C08F4, C07C407, C07C67