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    • 专利摘要:
    The present invention relates to a peroxide having the formula (1) consisting of a reaction of an alkyl vinyl ether having the formula (3a) or an acetal having the formula (3b) with a corresponding ketone peroxide having the formula (2) in the presence of a catalyst and a process for the preparation thereof: As; (Formula 1) In Formula 1, n is 1 or 2, and R 1 , R 2 , R 4 , R 5 and R 6 are hydrogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 Independently selected from the group comprising aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl, or R 1 and R 2 form a C 3 -C 12 cycloalkyl group, the groups being linear or Branched alkyl moieties, each of R 1 , R 2 , R 4 , R 5, and R 6 may be hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amido Optionally substituted with one or more groups selected from R 1 and R 2 may form a ring; R 3 is independently selected from the group comprising C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl, The groups may comprise linear or branched alkyl moieties, and R 3 is optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido Optionally a pair of optionally substituted R 3 , R 4 , R 5 and R 6 may form a ring) (Formula 2) (In Formula 2, n, R 1 and R 2 are the same as above) (Formula 3a) Formula 3b) (In the formulas 3a and 3b, R 3 , R 4 , R 5 and R 6 are the same as above); The invention also relates to the use of the peroxides in which the peroxides are used as polymerization initiators, curing agents and / or modifiers for unsaturated polyesters, and to combinations comprising the peroxides and carriers or diluents.
    公开号:KR20010072429A
    申请号:KR1020017001828
    申请日:1999-07-28
    公开日:2001-07-31
    发明作者:반데보벤캄프-보우만안나게르딘；마이저존；시에드에자츠아메트；호그트안드레아스헤르만；데브리에스베른하트
    申请人:샬크비즈크 피이터 코르넬리스; 페트귄터；아크조 노벨 엔.브이.；
    IPC主号:
    专利说明:

    Peroxide, its manufacturing method and use {PEROXIDES, THEIR PREPARATION PROCESS AND USE}
    [1] The present invention relates to certain peroxides, methods of preparation and uses thereof. In particular, the present invention relates to a process for the preparation of peroxides obtainable by reaction of the corresponding ketone peroxides with alkyl vinyl ethers or acetals. The invention also relates to the use of these peroxides used as polymerization initiators, curing agents for unsaturated polyesters and modifiers, and to formulations comprising these peroxides.
    [2] US-A-3,576,826 describes ether peroxy compounds and their preparation in alpha-substituted vinyl ethers. In the case of ether peroxides, adjacent peroxide groups may be separated by unclear aliphatic or cycloaliphatic groups.
    [3] It is an object of the present invention to provide novel peroxides useful as polymerization initiators, curing agents for unsaturated polyesters and modifiers.
    [4] It is also an object of the present invention to provide peroxides with higher reactivity to the compounds of US-A-3,576,826.
    [5] Another object of the present invention is to provide peroxides having better storage stability at room temperature for the compounds of US-A-3,576,826.
    [6] Accordingly, the present invention provides a process for preparing a peroxide having the formula (1) consisting of reacting an alkyl vinyl ether having the formula (3a) or an acetal having the formula (3b) with a corresponding ketone peroxide having the formula (2) in the presence of a catalyst Provides:
    [7]
    [8] In Formula 1, n is 1 or 2, and R 1 , R 2 , R 4 , R 5 and R 6 are hydrogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 Independently selected from the group comprising aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl, or R 1 and R 2 form a C 3 -C 12 cycloalkyl group, the groups being linear or Branched alkyl moieties; and R 1 , R 2 , R 4 , R 5 and R 6 are each hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amide Optionally substituted with one or more groups selected from the figures, and R 1 and R 2 may form a ring;
    [9] R 3 is independently selected from the group comprising C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl, The groups may comprise linear or branched alkyl moieties, and R 3 is optionally in one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido Optionally substituted, and any pair of optionally substituted R 3 , R 4 , R 5, and R 6 may form a ring)
    [10]
    [11] (In Formula 2, n, R 1 and R 2 are the same as above)
    [12]
    [13]
    [14] (In Chemical Formulas 3a and 3b, R 3 , R 4 , R 5 and R 6 are the same as above).
    [15] The ketone peroxide of Formula 2 may be so-called T 4 -ketone peroxide (n = 1) and / or so-called T 3 -ketone peroxide (n = 2).
    [16] A T 4 -ketone peroxide having the formula (2a) suitable for reaction with the alkyl vinyl ether of formula (3a) or the acetal of formula (3b) is formed from the following ketone:
    [17] Acetone, acetophenone, methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylisoamyl ketone, methylheptyl ketone, methylhexyl ketone, ethyl amyl ketone, diethyl ketone, dipropyl ketone, methyl ethyl ketone, Methylisobutyl ketone, methylisopropyl ketone, methylpropyl ketone, methyl-n-butyl ketone, methyl-t-butyl ketone, methyl cyclohexanone, isobutylheptyl ketone, diisobutyl ketone, methoxy acetone, cyclohexanone , 3,3,5-trimethyl cyclohexanone, N-butyllevulinate, ethyl acetoacetate, methylbenzyl ketone, phenylethyl ketone, methylchloromethyl ketone, methyl bromomethyl ketone; It is also possible to use other ketones having appropriate R 1 and R 2 and mixtures of two or more other ketones corresponding to the peroxide of formula (2).
    [18]
    [19] T 3 -ketone peroxides having the formula (2b) suitable for reaction with the alkyl vinyl ether of formula (3a) or acetal of formula (3b) are derived from the same group of ketones as mentioned in the T4-ketone peroxide.
    [20] Preferably, the ketone peroxide is formed or derived from methylethyl ketone, methylisopropyl ketone, methylisobutyl ketone, acetone, cyclohexanone and / or 3,3,5-trimethylcyclohexanone. Methyl isobutyl ketone and methyl ethyl ketone are most preferred.
    [21] Examples of alkyl vinyl ethers of Formula 3a (wherein R 4 is hydrogen) can be seen below:
    [22] Vinyl 2,2-bis (vinyloxymethyl) butyl ether, allyl 2,3-epoxypropyl ether, n-propyl vinyl ether, 1-ethoxy-4-methyl-1-nonene, tert-amyl vinyl ether, 2, 2-bis (4-vinyloxyphenyl) propane, hexadecyl vinyl ether, methyl vinyl ether, 4-methylhexyl vinyl ether, 2- (2-ethoxyethoxy) ethyl vinyl ether, 2-methoxyethylvinyl ether, 2-vinyloxy ethanol, 4-methyl-1-decenyl vinyl ether, benzyl 1-methyl vinyl ether, butanediol divinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, cyclohexanedimethanol divinyl ether, cyclohexyl Vinyl ether, ethylene glycol divinyl ether, 1-ethoxy-4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexene, allyl vinyl ether, isopropyl vinyl ether, ethyl vinyl ether, Tetraethyleneglycol divinyl ether, 1-methoxy-1-butene-3-yne, heptyl vinyl ether, 4- (1-ethoxyvinyl ) -3,3,5,5-tetramethylcyclohexanone, 2-butoxyethyl vinyl ether, allyl ethyl ether, divinyl ether, 1,3-divinyloxy-2,2-dimethylpropane, 4-vinyl Oxybutanol, diethylene glycol divinyl ether, 4- (vinyloxymethyl) cyclohexylmethanol, isopentyl vinyl ether, diethylene glycol monovinyl ether, n-butyl vinyl ether, 1,4-bis (2-vinyloxyethyl ) Benzene, hexanediol divinyl ether, 1-methoxy-1,3-butadiene, decyl vinyl ether, 4- (allyloxymethyl) -1,3-dioxolan-2-one, 1,1-diethylpropyl Vinyl ether, 2-methoxyvinyl benzene, octyl vinyl ether, bis (vinyloxy) methane, 1,4-dimethoxy-1,3-butadiene, triethyleneglycol divinyl ether, pentyl vinyl ether, octadecyl vinyl ether, Triethylene glycol methyl vinyl ether, 2,3-epoxypropyl vinyl ether, dodecyl vinyl ether, 1,1-bis (vinyloxy) butane, hexyl vinyl ether, 6-vinyloxyhexanol, (z) -1-methoxy-1-butene-3-yne, phenyl vinyl ether, 2-ethylhexyl vinyl ether, poly-THF-divinyl ether, fluriol-E-200 Divinyl ether, trimethylolpropane trivinyl ether, aminopropyl vinyl ether, 2-ethylaminoethyl vinyl ether, ethyl propenyl ether.
    [23] Examples of alkyl vinyl ethers of formula 3a wherein R 4 is alkyl are as follows:
    [24] 2-methoxy-2-butene, 1,1,3-trimethoxypropene, 2,3-dimethoxy-1,3-butadiene, 2-methoxypropene, 2-ethoxy propene, 2- Isobutoxypropene, 2-ethoxy-2-butene, 2-isobutoxy-2-propene.
    [25] Examples of trisubstituted and cyclic alkyl vinyl ethers are 1-methoxy-2-methyl cyclohexene and 2-methoxy-2-methyl-2-butene. Examples of cyclic alkyl vinyl ethers are 2-methyl-2,3-dihydrofuran, 2,3-dihydrofuran, 2-methyl-3,4-dihydropyran, 3,4-dihydropyran, 1- Methoxy cyclohexene. Preferred are ethyl vinyl ether, isobutyl vinyl ether, propyl vinyl ether and butyl vinyl ether. More preferably isobutyl vinyl ether.
    [26] Examples of acetals of formula 3b include 2,2-dimethoxypropane, 2,2-diethoxypropane (R 4 is alkyl) or 1,1-dimethoxybutane, 2-propyl-1,3-dioxolane, 1, 1-dimethoxyethane, 1,1-diethoxyethane, 1,1-diethoxypropane and 1,1-dimethoxycyclohexane (R 4 is hydrogen). Preferably 1,1-dimethoxyethane.
    [27] The reaction between the ketone peroxide of formula (2) and the alkyl vinyl ether of formula (3a) or the acetal of formula (3b) is carried out under the conditions of a conventional addition reaction. The temperature is usually in the range of 0-50 ° C, preferably between 10-25 ° C. The reaction is carried out in the presence of an acid catalyst. The amount of the acid catalyst is usually 0.01-30 g / mol of ketone peroxide, preferably 0.1-15 g / mol.
    [28] Acid catalysts for the process are conventional acid catalysts such as C 1 -C 10 alkanes or aryl sulfonic acids, halogenated C 1 -C 10 alkanesulfonic acids or mixtures of one or more of these compounds. Preferred catalysts for use include, but are not limited to, p-toluenesulfonic acid and methane sulfonic acid. Although the reaction is carried out without solvent, it is preferred to carry out the reaction in a conventional homogeneous solvent system.
    [29] Suitable solvents are usually hydrocarbon solvents, esters, aromatic hydrocarbon solvents, aralkyl solvents, paraffin oils, white oils and silicone oils, as well as mixtures thereof. Useful solvents include, but are not limited to, oligomers of benzene, xylene, toluene, mesitylene, hexane, hydrogenated alkanes such as Isopar (trade name) products (manufactured by Exxon), shellsol (manufactured by Shell) products (manufactured by Shell). Pentane, heptane, decane, isododecane, decalin, dibutyl phthalate, dioctyl adipate, dioctyl terephthalate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, butylbenzoate, and the like. Include. Among the paraffin oils useful as solvents are paraffin diesel oils. Other oils, including white oil, epoxidized soybean oil, and silicone oils are useful in the present invention.
    [30] Preferably, R 4 is hydrogen because the peroxide shows better storage stability at room temperature and is less sensitive to hydrolysis. More preferably R 4 and R 5 and / or R 6 are hydrogen.
    [31] Usually, the process for preparing the peroxide is carried out such that the equivalent of alkyl vinyl ether of formula 3a or acetal of formula 3b is in the range of 1-5 equivalents. Preferably, the range is 1.5 to 3.0 equivalents, more preferably 2.0 to 2.5 equivalents. The equivalent is selected so that the chemical yield is appropriate.
    [32] In the preparation method, the ketone peroxide used may be pure (T 4 ) ketone peroxide of formula 2a or (T 3 ) ketone peroxide of formula 2b. For certain properties, it is recommended to use mixtures of T 4- and T 3- ketone peroxides. For example, T 3 -or T 4 -ketone peroxide consists of 5% -30%, for example 5% -25% and 10% -15% of other ketone peroxides.
    [33] The present invention also relates to a peroxide of formula (1) which can be obtained by the preparation process described above.
    [34] (Formula 1)
    [35]
    [36] (In Formula 1, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as above)
    [37] The peroxides according to the invention produced by the process according to the invention are initiators for the preparation of polymers, in particular poly (vinylchloride), acrylic (co) polymers, polystyrene, initiators for the production of polyethylene, initiators for curing unsaturated polyester resins. , And as initiators for polymer modification (such as monomer implantation).
    [38] In the present invention, the polymerization reaction is carried out by conventional methods except when a specific radical polymerization initiator (or composition) is used. The polymerization methods can be carried out by conventional methods such as, for example, bulk, suspension, emulsion or solution. In the case of the preparation of ethylene (co) polymers, this reaction is usually carried out at high pressure, such as from about 1000 to about 3500 bar.
    [39] The polymerization temperature, the capacity for removing the heat of polymerization, and the type of monomer used, if applicable, and the amount of initiator that can be changed depending on the application pressure should be in an appropriate amount to achieve polymerization. Usually, 0.001-25% by weight of peroxide based on the weight of the (co) polymer is used. Preferably, 0.001-20% by weight of peroxide is used, most preferably 0.001-15% by weight of peroxide.
    [40] For most of the reactions in the present invention, the polymerization temperature is usually 30 ° to 350 ° C, preferably 40 ° to 300 ° C. Generally, the polymerization time becomes too long when the temperature is 30 degrees C or less. However, if the temperature exceeds 350 ° C., the radical polymerization initiator is consumed in the initial stage of polymerization, making it difficult to achieve high conversion. However, in order to reduce the amount of unreacted monomer, it is possible to carry out the polymerization using a temperature profile, for example after the initial polymerization at below 100 ° C. and then at a temperature above 100 ° C. to complete the polymerization. It is carried out by raising. These modifications are all known to those skilled in the art, and the skilled person will have no difficulty in selecting the reaction conditions according to the specific polymerization reaction and the specific radical polymerization initiator to be used.
    [41] Suitable monomers for polymerization using the peroxides according to the invention include, but are not substituted or unsubstituted, vinyl aromatics including olefins or ethylenically unsaturated monomers such as styrene, alpha-methylstyrene, P-methylstyrene, and halogenated styrenes. Monomers; Divinylbenzene; Ethylene; Such as (meth) acrylic acid, (meth) acrylic acid ester, butyl acrylate, hydroxyethyl (meth) acrylate, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and glycidyl methacrylate Ethylenically unsaturated carboxylic acids and derivatives thereof; Ethylenically unsaturated nitriles and amides such as acrylonitrile, methacrylonitrile and acrylamide; Substituted or unsubstituted ethylenically unsaturated monomers such as butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate and vinyl propionate; Mono- and diesters, anhydrides and imides such as maleic anhydride, citraconic anhydride, citraconic acid, itaconic acid, nad anhydride, maleic acid, fumaric acid, aryl, alkyl and aralkyl citraconimide and maleimide Ethylenically unsaturated dicarboxylic acids and derivatives thereof; Vinyl halides such as vinyl chloride and vinylidene chloride; Vinyl ethers such as methylvinyl ether and n-butylvinyl ether; Olefins such as isobutene and 4-methylpentene; (Di) allyl esters such as diallyl phthalate, allyl compounds such as (di) allyl carbonate and triallyl (iso) cyanurate.
    [42] During the (co) polymerization, the formulation may also include ordinary additives and fillers. Examples of such additives include stabilizers such as inhibitors of oxidation, heat or ultraviolet decomposition reactions, lubricants, diluent oils, pH adjusting substances such as calcium carbonates, release agents, colorants, fiber materials such as silica, cray, chalk, carbon black, and glass fibers. There are other types of reinforced or unreinforced fillers, plasticizers, diluents, chain transfer agents, accelerators and peroxides. The additives can be used in conventional amounts.
    [43] Finally, the polymerization process of the present invention can be used to introduce functional groups into the (co) polymer. This can be done by using peroxides with one or more functional groups attached. These functional groups remain completely in the free radicals formed by the peroxide and are introduced into the (co) polymers. Conventional polymerization conditions and apparatus can be used to achieve the objects of the present invention.
    [44] The peroxides according to the invention used as curing agents for unsaturated polyesters and unsaturated polyester resins according to the invention comprise unsaturated polyesters and one or more ethylenically unsaturated monomers. Suitable polymerizable monomers that can be copolymerized with unsaturated polyesters include styrene, alpha-methylstyrene, p-methylstyrene, chlorostyrene, bromostyrene, vinylbenzyl chloride, divinylbenzene, diallyl malate, dibutyl fumar Latex, triaryl phosphate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, methyl (meth) acrylate, n-butyl (meth) acrylate, methyl acrylate and mixtures thereof. Unsaturated polyesters include, for example, at least one ethylenically unsaturated di- or polycarboxylic acid, such as maleic acid, fumaric acid, glutamic acid, itaconic acid, mesaconic acid, citraconic acid, allylmalonic acid tetrahydrophthalic acid, Anhydride or acid halides with ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 2,2-dimethyl -1,3-propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-butene-1,4-diol, 2-butyne-1,4-diol, 2,4,4 It is a polyester obtained by esterification with saturated or unsaturated di- or polyols, such as -trimethyl-1,3-pentanediol, glycerol, pentaerythritol, and mannitol. Di- or polycarboxylic acids are saturated di- or polycarboxylic acids, such as adipic acid, succinic acid and other acids, and / or aromatic di- or poly, such as phthalic acid, trimellitic acid, pyromellitic acid, isophthalic acid and terephthalic acid. Partially substituted by carboxylic acid. The acid used may be substituted with a group such as halogen. Suitable halogenated acids include, for example, tetrachlorophthalic acid and tetrabromophthalic acid.
    [45] The peroxides of the present invention are suitably used in the modification of polymers such as degradation, crosslinking or grafting. More particularly, such peroxides can be used for grafting monomers onto polymers such as polyolefins and elastomers or for functionalizing polyolefins in the case of peroxides comprising the functional groups of the invention.
    [46] In general, peroxides are contacted with the (co) polymer in a variety of ways depending on the specific purpose of the modification. The polymeric material is, in the case of an elastomer, in the form of a solid, molten, in the form of a solution, in the form of a plastic or in a melt, in the melt, in the form of divided particles (flakes), pellets, films, sheets, in solution. The polymer may also be present in liquid form, such as liquid rubber.
    [47] In general, certain (co) polymers containing extractable hydrogen atoms in certain polyoliffins can be modified by this method.
    [48] The amount of peroxide used in the modification process of the present invention should be an amount effective to obtain significant modification of the (co) polymer when treating the (co) polymer. More particularly, 0.001-15.0% by weight of peroxide is used based on the weight of the (co) polymer. More preferably 0.005-10.0% by weight is used. Most preferably an amount of 0.01-5.0% by weight is used.
    [49] The peroxides can be prepared, transported, stored and used in the form of powders, particles, pellets, pastels, flakes, slabs, pastes, solid masterbatches and liquids. Such formulations may take the form of dispersions, such as suspensions or emulsions. This can be viscous depending on the specific peroxide or its concentration in the formulation, if necessary. This form depends in part on the way in which it is to be mixed and the use to be used. In addition, in terms of stability, the viscosity agent may serve to be combined with certain compositions to ensure safe handling.
    [50] Formulations of the present invention are transportable, storage stable, and may comprise 1.0% -90% of one or more peroxides according to the present invention. Portability means that the formulation of the present invention passes the pressure vessel test (PVT). By storage stability is meant that the formulations of the invention are chemically and physically stable over long periods of storage under standard conditions.
    [51] The formulations according to the invention preferably comprise 10-90% by weight of one or more peroxides, more preferably 30-90wt% of peroxides, more preferably 40-80wt% of peroxides. It is to include.
    [52] Formulations of the present invention may be liquid, solid or paste depending on the melting point of the peroxide and diluent used. Liquid formulations can be prepared using liquid viscosities for ketone peroxides, liquid plasticizers, organic peroxides and mixtures thereof as diluents. The liquid component is generally present in a liquid formulation consisting of a liquid diluent in an amount of 1-99% by weight of the composition, preferably 10-90% by weight, more preferably 30-90% by weight, most preferably 40- Present at 80% by weight.
    [53] Certain viscosifiers are not suitable for use with all peroxides of the present invention. More particularly, to obtain a safe composition, the viscosity agent has a minimum freezing point and boiling point for the decomposition temperature of the peroxide and the viscosity agent does not boil in the thick, unstable ketone peroxide. As such, the low boiling point viscosifiers mentioned below can only be used in certain substituted peroxides of the present invention having low decomposition temperatures.
    [54] In liquid formulations liquid carriers or diluents are used. Preferably such carrier or diluent is a solvent. Examples of solvents are those disclosed above for the preparation of various peroxides.
    [55] Solid carrier materials are used in the solid and / or paste formulations of the present invention. Examples of such solid carriers include dicyclohexyl phthalate, dimethyl fumarate, dimethyl isophthalate, triphenyl phosphate, glyceryl tribenzoate, trimethyl oleethane tribenzoate, dicyclohexyl terephthalate, paraffin wax, dicyclohexyl isophthalate Low melting point solids such as, polymers and inorganic supports. Inorganic supports include materials such as stolen silica, precipitated silica, hydrophobic silica, chalk, whistle, surface treated craies such as silane treated cray, calcined cray and talc.
    [56] Polymers used in the formulations of the present invention include polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / propylene / diene monomer terpolymers, chlorosulfonate polyethylene, chlorinated polyethylene, polybutylene, polyisobutylene, ethylene / vinyl acetate Copolymers, polyisoprene, polybutadiene, butadiene / styrene copolymer, natural rubber, polyacrylate rubber, butadiene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene terpolymer, silicone rubber, polyurethane, polysulfide, Solid paraffins, polycaprolactones, and the like.
    [57] Storage stability formulations must be physically and chemically stable. Physically stable formulation means a formulation in which no phase separation occurs upon storage. The physical stability of the present formulations can be enhanced by adding one or more thixotropic agents selected from cellulose esters, hydrogenated castor oils and stolen silicas. Examples of such cellulose esters are the reaction products of cellulose with acid compounds selected from acetic acid, propionic acid, butyric acid, phthalic acid, trimellitic acid and mixtures thereof.
    [58] Chemically stable formulations mean those formulations which do not lose a significant amount of active oxygen content upon storage. The chemical stability of the formulations may include one or more well known additives, including sequestrants such as dipicolinic acid and / or antioxidants such as 2,6-di (t-butyl) -4-methyl phenol and para-nonyl phenol. It can be improved by adding.
    [59] Formulations of the present invention may also include other optional additives as long as they do not have a significant adverse effect on the carrying capacity and / or storage stability of the formulation. Examples of such additives include anti-caking agents, free flow agents, anti-ozonants, antioxidants, antidegradants, UV stabilizers, coagulants, bactericides, antistatic agents, pigments, dyes, binders, dispersants, browning agents, lubricants, processed oils and Mold-release agents and the like. Such additives are used in moderate amounts.
    [60] The peroxides according to the invention can also be used as dispersions, preferably as polar media. The medium in which the initiator is dispersed in accordance with the invention should be inert to the initiator and the initiator is polar and hardly soluble. The initiator is preferably dispersed in water or alcohol. Most preferred is that the initiator is dispersed in water. The use of such a medium makes it relatively easy to remove any residue after deformation of the (co) polymer if desired. In addition, the use of water or alcohol has fewer water solubility and other disadvantages than using organic diluents such as toluene and xylene, which are well known to date.
    [61] As is well known to those of ordinary skill in the art, the use of other auxiliaries in the initiator dispersion is desirable or necessary to ensure the chemical and / or physical stability of the dispersion for a sufficient period of time. For example, if the storage temperature of the initiator dispersion is lower than the freezing point of the medium in which the initiator is dispersed, an appropriate freezing point depressant may be attached to prevent freezing. In addition, a wide range of materials can be used to alter the flow of formulation. For this purpose it is generally possible to use one or more surfactants and one or more thickening agents. If desired, other additives may be included in the formulation. Such additives include pH buffers, biocides, chemical stabilizers that prevent premature degradation of initiators, and anti-aging agents that prevent the growth of particle size in dispersions.
    [62] The following examples illustrate the preparation of peroxides according to the invention and their use.
    [63] Example 1
    [64] Preparation of a mixture of 2,2-bis (1- (1-methylpropoxy) ethylperoxy) butane and bis [1-methyl-1 (1- (2-methylpropoxy) ethylperoxy) propyl] peroxide
    [65] 25 g methylethyl comprising 14.4 wt% bis (1-hydroperoxy-1-methylpropyl) peroxide T3 and 27.82 wt% 2,2-bis (hydroperoxy) butane T4 ketone peroxide in dimethylphthalate 0.86 g of p-toluene sulfonic acid monohydrate is added to the stirred solution of ketone peroxide. 18.3 g of isobutyl vinyl ether is added within 16 minutes and the reaction temperature is maintained at 20 ° C. by cooling with an ice water bath. The mixture is stirred at 20 ° C. for 2 minutes, washed with bicarbonate solution and dried over magnesium sulfate to give 41.6 g of product having an active oxygen content of 6.33% (chemical yield: 90%).
    [66] Table 1 below describes the results of the preparation of other peroxides according to the invention (R 1 = methyl; R 4 , R 5 and R 6 = H).
    [67] ExampleR3R2n = 1: n = 2 mol / molmenstruumYield (%)Free radicals (%) 1aethylethyl56:44Dimethyl phthalate877.04 1bethylethyl77:23Dimethyl phthalate907.52 1cIsobutylethyl56:44Dimethyl phthalate916.24 1dIsobutylethyl77:23Dimethyl phthalate916.33 1eethylIsobutyl16:84Pentadecane975.89 1fn-propylIsobutyl43:57Isododeccan936.53 1 gn-propylIsobutyl43:57Isododeccan886.20 1hIsobutylIsobutyl43:57Isododeccan906.41 1iIsobutylIsobutyl96: 4Ethyl acetate775.46 1jIsobutylIsobutyl0: 100Isododeccan706.26
    [68] Example 2
    [69] 2,2-bis (1-methoxy-1-methylethylperoxy) -4-methyl pentane and bis (1- (1-methoxy-1-methylethylperoxy) -1,3-dimethylbutyl) perox Preparation of a Mixture of Seeds
    [70] 50 g methylisobutyl ketone peroxide comprising 36.84 wt% bis (1-hydroperoxy-1,3-dimethylbutyl) peroxide and 7.89 wt% dihydroperoxy-1,3-dimethylbutane in pentadecane To a stirred solution of is added 0.60 g of acetic acid. 13.73 g of 2-methoxypropene is added within 10 minutes and the reaction temperature is maintained at 20 ° C. by cooling with an ice water bath. The mixture is stirred for 30 minutes and 1.20 g of acetic acid is added. The mixture is left overnight to yield 65 g of product having an active oxygen content of 6.15%. Chemical yield: 97%.
    [71] Example 3
    [72] Preparation of 1,1-bis (1-isobutoxyethylperoxy) cyclohexane
    [73] 0.4 g of p-toluene sulfonic acid is added to a stirred solution of 30 g of 1,1-dihydroperoxycyclohexane in ethyl acetate. Then, 19.6 g of isobutyl vinyl ether is added within 10 minutes, and the reaction temperature is maintained at 20 ° C. while cooling with an ice water bath. The mixture is stirred for 60 minutes. The mixture is washed with sodium bicarbonate solution and dried over MgSO 4 . 35 g of product having an active oxygen content of 6.75% are obtained. Chemical yield: 67%
    [74] Example 4
    [75] Preparation of 2,2-bis (1-ethoxypropylperoxy) -4-methyl pentane
    [76] 0.05 g of p-toluene sulfonic acid was added to a stirred solution of 5 g of methyl isobutyl ketone peroxide containing 35.7 wt% of bis (1-hydroperoxy-1,3-dimethylbutyl) peroxide in isododecane. Add. Then, 1.8 g of ethyl propenyl ether is added within 10 minutes, and the reaction temperature is maintained at 20 ° C. while cooling with an ice water bath. The mixture is stirred at 15 ° C. for 20 minutes. The mixture is washed with bicarbonate solution and dried over magnesium sulfate to yield 5.8 g of product having an active oxygen content of 5.12%. Chemical yield: 91%
    [77] Example 5
    [78] Preparation of a mixture of 2,2-di (1-methoxybutylperoxy) butane and di (1- (1-methoxybutylperoxy) 1-methylpropyl) peroxide
    [79] Stirring of 25 g methylethyl ketone peroxide comprising 14.4 wt% bis (1-hydroperoxy-1-methylpropyl) peroxide in dimethyl phthalate and 27.82 wt% 2,2-bis (hydroperoxy) butane 0.86 g of p-toluene sulfonic acid monohydrate is added to the prepared solution. 21.8 g of 1,1-dimethoxybutane is added within 16 minutes, and the reaction temperature is maintained at 20 ° C. while cooling with an ice water bath. The mixture was stirred at 20 ° C. for 20 minutes, washed with bicarbonate and dried over magnesium sulfate to give 35.2 g of product having an active oxygen content of 6.68%. (Chemical yield: 90%)
    [80] Example 6
    [81] Curing of Unsaturated Polyester
    [82] The curing performance of peroxide as a curing agent for unsaturated polyesters is measured and compared with tertiary butyl peroxy 2-ethyl hexanoate. The time-temperature curve is measured at 100 ° C. on a compound comprising 100 parts of polyester resin, 150 parts of sand with filler and 1 part of peroxide. This is done according to the method suggested by the Society of Plastic Institute. Pour 25 g of compound into the test tube and place the thermocouple through the stopper at the center of the test tube. The glass tube is then placed in an oil bath maintained at the specified test temperature and the time-temperature curve is measured. From the curve the following variables are calculated.
    [83] Gelation time (GT) = time (minutes) when bath temperature elapsed between 16.7 ° C and above 5.6 ° C
    [84] Time to exothermic peak (TTP) = time elapsed between the start of the experiment and the moment the peak temperature is reached
    [85] Exothermic peak (PE) = maximum temperature reached. The results are set forth in Table 2 below.
    [86] PeroxideTest temperature (℃)GT (min)TTP (minutes)PE (℃) t-butyl peroxy-2-ethyl hexanoate1000.873.4197 Example 1c1002.175.57184 Example 1 g1000.783.38197 Example 1h1000.673.22195
    [87] Example 7
    [88] Highly Cohesive Acrylic Resin Synthesis
    [89] The adequacy of the peroxide according to the invention in the preparation of the high coagulation acrylic resin is measured and compared with tert-butyl peroxide-2-ethyl hexanoate.
    [90] The polymerization is carried out in a jacketed glass reactor with a turbine stirrer, thermoelectric pair, reflux condenser and inlet inlet under nitrogen. The peroxide initiator is added as a monomer. The mixture is added to the solvent in the stirred vessel through a laboratory pump at a temperature set to approximately 4 hours. The reaction continues for an additional hour and the remaining monomer / initiator is reduced. From the obtained resin, the molecular weight, color and solid ratio are measured. The temperature is 165 ° C. The results are shown in Table 3 below.
    [91] InitiatorInitiator meq / 100g MSolid content (%)Mw (g / mol)Mn (g / mol)Disp. Example 13071.0540027002.0 t-butyl peroxy-2-ethyl hexanoate3074.3540029001.9
    [92] Furtherance:
    [93] Monomer (parts by weight)
    [94] n-butyl acrylate (BA): 40
    [95] Styrene (STY): 20
    [96] 2-hydroxyethyl methacrylate (HEMA): 28
    [97] Methyl methacrylate (MMA): 10
    [98] Methacrylic acid (MA): 2
    [99] Solvesso 100 (S-100): 40 (solvent)
    [100] Initiator concentration: 30 meq / 100g monomer
    [101] Temperature: 165 ℃
    [102] Molecular weights are determined by gel permeation chromatography using polystyrene standards according to the AR / 94.14-1 / HPLC method available from Akzo Nobel. Solids content is measured as the proportion of nonvolatiles (0.5 hours at 150 ° C.).
    权利要求:
    Claims (14)
    [1" claim-type="Currently amended] A process for preparing a peroxide having the formula (1) characterized by the reaction of an alkyl vinyl ether having the formula (3a) or an acetal having the formula (3b) and a corresponding ketone peroxide having the formula (2) in the presence of a catalyst.
    (Formula 1)

    In Formula 1, n is 1 or 2, and R 1 , R 2 , R 4 , R 5 and R 6 are hydrogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 Independently selected from the group comprising aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl, or R 1 and R 2 form a C 3 -C 12 cycloalkyl group, the groups being linear or Branched alkyl moieties, each of R 1 , R 2 , R 4 , R 5, and R 6 may be hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amido Optionally substituted with one or more groups selected from R 1 and R 2 may form a ring;
    R 3 is independently selected from the group comprising C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl, The groups may comprise linear or branched alkyl moieties, and R 3 is optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido Optionally a pair of optionally substituted R 3 , R 4 , R 5 and R 6 may form a ring)
    (Formula 2)

    (In Formula 2, n, R 1 and R 2 are the same as above)
    (Formula 3a)

    Formula 3b)

    (In Chemical Formulas 3a and 3b, R 3 , R 4 , R 5 and R 6 are the same as above).
    [2" claim-type="Currently amended] The method of claim 1,
    R 4 is a method for producing a peroxide, characterized in that hydrogen.
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    R 5 and / or R 6 is a method for producing a peroxide, characterized in that hydrogen.
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
    The equivalent of the alkyl vinyl ether of Formula 3a or the acetal of Formula 3b is in the range of 1-5 equivalents, preferably in the range of 1.5-3.0 equivalents, more preferably in the range of 2.0-2.5 equivalents. Manufacturing method.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4,
    The ketone peroxide of Formula 2 is a mixture of ketone peroxide having the formula (2a) and ketone peroxide having the formula (2b).
    (Formula 2a)

    (Formula 2b)

    [6" claim-type="Currently amended] The method according to any one of claims 1 to 5,
    The ketone peroxide is derived from methylethyl ketone, methylisopropyl ketone, methylisobutyl ketone, acetone, cyclohexanone and / or 3,3,5-trimethyl cyclohexanone, preferably methylisobutyl ketone or methyl A process for producing a peroxide, characterized in that it is derived from ethyl ketone.
    [7" claim-type="Currently amended] The method according to any one of claims 1 to 6,
    The alkyl vinyl ether of formula 3a is selected from ethyl vinyl ether, isobutyl vinyl ether, propyl vinyl ether and butyl vinyl ether, preferably isobutyl vinyl ether, and acetal of formula 3b is 2,2-dimethoxypropane, 2 , 2-diethoxypropane, 1,1-dimethoxybutane, 2-propyl-1,3-dioxolane, 1,1-dimethoxyethane, 1,1-diethoxyethane, 1,1-diethoxypropane and 1,1-dimethoxycyclohexane, preferably 1,1-dimethoxyethane.
    [8" claim-type="Currently amended] A peroxide having the following formula (1), which is obtained by the process according to any one of claims 1 to 7.
    (Formula 1)

    (In Formula 1, n, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as above)
    [9" claim-type="Currently amended] Use of a peroxide according to claim 8 or a peroxide prepared according to any one of claims 1 to 7 as a polymerization initiator, curing agent for unsaturated polyesters and / or modifiers. .
    [10" claim-type="Currently amended] 10. A combination comprising a peroxide according to claim 9 and a carrier or diluent.
    [11" claim-type="Currently amended] The method of claim 10,
    Wherein said peroxide is 1.0-99 wt%, preferably 10-90 wt%, more preferably 30-90 wt%, most preferably 40-80 wt%.
    [12" claim-type="Currently amended] The method of claim 10 or 11,
    Said carrier or diluent is a solid, liquid or paste.
    [13" claim-type="Currently amended] The method according to any one of claims 10 to 12,
    Wherein said liquid is a polar solvent.
    [14" claim-type="Currently amended] The method according to any one of claims 10 to 13,
    Said combination in the form of a dispersion, such as a suspension or emulsion.
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    同族专利:
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    DE69904337D1|2003-01-16|
    BR9912922A|2001-10-16|
    HU0102988A2|2001-11-28|
    JP2002522524A|2002-07-23|
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    AT229002T|2002-12-15|
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    HU0102988A3|2003-04-28|
    ID28467A|2001-05-24|
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    ZA200101155B|2002-05-09|
    WO2000009478A1|2000-02-24|
    AU5290099A|2000-03-06|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-08-12|Priority to EP98202708
    1998-08-12|Priority to EP98202708.8
    1999-07-28|Application filed by 샬크비즈크 피이터 코르넬리스; 페트귄터, 아크조 노벨 엔.브이.
    1999-07-28|Priority to PCT/EP1999/005478
    2001-07-31|Publication of KR20010072429A
    优先权:
    申请号 | 申请日 | 专利标题
    EP98202708|1998-08-12|
    EP98202708.8|1998-08-12|
    PCT/EP1999/005478|WO2000009478A1|1998-08-12|1999-07-28|Peroxides, their preparation process and use|
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