JPH0352856A - Dialkyl peroxide, production thereof and use of same compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 is 4-8C tertiary alkyl or alpha-cumyl; R2 and R3 are 1-2C alkyl; R4 is 1-3C alkyl or H; R5 is 1-12C alkyl, 1-4C alkoxy, halogen or H; m is 1-3; n is 1-2; R1OOC(R2) (R3) is meta-position or para-position]. EXAMPLE:4-(1-t-butylperoxy-1-methyl ethyl)benzophenone. USE:Used as photo-decomposing radical generator. PREPARATION:Isoalkyl group-substituted benzophenone expressed by formula II is reacted with hydroperoxide expressed by the formula R1OOH in the presence of metallic salt of metal selected from IV- and V-group transition elements to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel dialkyl peroxide, a method for producing the same, and uses thereof.

(Prior art) Polymerization and curing methods for photopolymerizing and photocuring photopolymerizable (photocurable) monomers and photopolymerizable (photocurable) resin compositions are superior to thermal polymerization, thermosetting methods, and oxidative curing methods. It can be quickly polymerized and cured at low temperatures, and has many advantages such as improved productivity, energy saving, and no pollution.Also, selective curing is possible, so it can be used for printing inks, paints, adhesives, resin letterpress, and prints. Widely used for processing wiring boards, etc.

Various initiators have been developed for photopolymerization and photocuring methods. For example, photopolymerization initiators that generate radicals under the action of ultraviolet light are known, such as benzoin, benzoin ethers, benzyl, aryldiazunium salts, penzophenone derivatives, acetophenone derivatives, xanthates, thioxanthones, and halogenated hydrocarbons. Journal of Oil and Color Research Association (J.Oi1.Col.Asso.
c. ) Vol. 59, pp. 166-171 (1976)).

It is also known that organic peroxides such as benzoyl peroxide and di-t-butyl peroxide can be used as photopolymerization initiators. However, these organic peroxides
In general, only light of 320 nm or less is absorbed [chemical
Review (Chem.Rev). Volume 68, 125-1
51 pages (1965)]. Attempts have been made to use a sensitizer in combination, but the intermolecular light energy transfer efficiency from the sensitizer to the organic peroxide is low, resulting in a low photolysis efficiency of the organic peroxide. It has been reported that di-L-butyl peroxide, which is a dialkyl type organic peroxide, does not undergo photosensitized decomposition intermolecularly [Journal of the American Chemical Society (J.Am.
．． Chem. Soc. ), vol.87, 3413-34
17 pages (1965)].

In order to solve this problem, an ester type organic peroxide containing a benzophenone group as a light absorbing group in the molecule has been developed (US Pat. No. 4,416,826) (Japanese Patent Application Laid-open No. 197401/1983). However, these compounds had drawbacks such as poor dark storage stability and yellowing of the cured resin.

(Problems to be Solved by the Invention) The conventional photopolymerization initiators described above are each useful, but they still have some drawbacks that should be improved. For example, (1) Benzoin, benzoin ether [c. Poor storage stability in the dark.

(2) Benzophenone derivatives are used in combination with amines, etc.
Polymerized products and cured products turn yellow.

(3) Thioxanthones have low solubility in monomers and resins.

(4) Ester-type peroxides containing light-absorbing groups have poor thermal stability, and the cured resin also turns yellow.

The purpose of the present invention is to improve the shortcomings of conventional photopolymerization initiators, to have good thermal stability, little yellowing of polymerized products and cured products, and to have high efficiency in photopolymerization and photocuring. The object of the present invention is to provide a novel high peroxide, its production method and uses.

(Means for Solving the Invention) The objects of the present invention have been achieved by a novel light-absorbing group-containing dialkyl peroxide.

That is, the first feature of the present invention is the general formula (wherein R is a tertiary alkyl group having 4 to 8 carbon atoms or an α-cumyl group, R2+ Ra is an alkyl group having 1 to 2 carbon atoms, and R4 is a carbon R5 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, R5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, and m is 1. ~3, n represents 1 to 2. Also, R+
The 00C(Rz) (11+1) group is in the meta or para position. ) The second aspect of the present invention is a penzophenone group-containing dialkyl peroxide represented by the general formula (where R., R
．． is an alkyl group having 1 to 2 carbon atoms, R4 is selected from an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom, and R is an alkyl group having 1 to 3 carbon atoms.
~12 alkyl groups, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, and hydrogen atoms, m is 1 to 3, n
represents l~2. In addition, the CH(R!) (R.) group is
It is meta or para position. ) isoalkyl group-substituted penzophenone and the general formula R+00H (II) (
In the formula, R is a tertiary alkyl group having 4 to 8 carbon atoms, or α
-Represents a cumyl group. ) A benzophenone group-containing dialkyl represented by the general formula (1), which is characterized by reacting the hydroperoxide represented by the formula (1) in the presence of a metal salt of a metal selected from the fourth and fifth period transition elements. The third aspect of the present invention is a method for producing a peroxide, and the third aspect of the present invention is a method for producing a peroxide having a general formula (wherein R., R. is an alkyl group having 1 to 2 carbon atoms, R.
4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, and R is an alkyl group having 1 to 12 carbon atoms, and 1 to 4 carbon atoms.
is selected from alkoxy groups, halogen atoms, and hydrogen atoms, where ``an'' represents 1 to 3, and n represents 1 to 2.

Further, the C(OH) (R2) (L) group is in the meta or rose position. ) α-hydroxyisoalkyl group-substituted penzophenone represented by the general formula R. OOH (II)
(In the formula, R represents a tertiary alkyl group having 4 to 8 carbon atoms or an α-cumyl group.) A general method characterized by reacting a hydroperoxide represented by the following in the presence of an acid catalyst The fourth aspect of the present invention is a method for producing a benzophenone group-containing dialkyl peroxide represented by the formula (1), wherein R is an alkyl group having 1 to 2 carbon atoms, and R4 is an alkyl group having 1 to 2 carbon atoms. 3 selected from alkyl groups and hydrogen atoms, R,
is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, R,
represents a hydrogen atom or a methyl group, m represents 1-3, and n represents 1-2. Further, the RbHC=CCRz) group is at the meta or para position. ) isoalkenyl group-substituted penzophenone and the general formula R,OOH (If) (
In the formula, R is a tertiary alkyl group having 4 to 8 carbon atoms, or α
- Represents a Kudanru group. ) A method for producing a benzophenone group-containing dialkyl peroxide represented by the general formula (1), which is characterized by reacting the hydroperoxide represented by the formula (1) in the presence of an acid catalyst, and the fifth aspect of the present invention is Formula (wherein R!, R3 is an alkyl group having 1 to 2 carbon atoms, R
4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, and R is an alkyl group having 1 to 12 carbon atoms, and 1 to 4 carbon atoms.
selected from alkoxy groups, halogen atoms, and hydrogen atoms, X is a chlorine atom or a bromine atom, sea bream is 1 to 3, n is 1
~2. Further, the CX(Rg) (Ra) group is at the meta or para position. ) α~halogenated isoalkyl group-substituted penzophenone and the general formula R,OOH (II) (
In the formula, R is a tertiary alkyl group having 4 to 8 carbon atoms, or α
- Represents a group. The sixth aspect of the present invention is a method for producing a benzophenone group-containing dialkyl peroxide represented by the general formula (I), which is characterized by reacting the benzophenone group-containing dialkyl peroxide with a hydroperoxide represented by the general formula (I) in the presence of an alkali. In the formula, RZ, R. is an alkyl group having 1 to 2 carbon atoms, R
, is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, and R is an alkyl group having 1 to 12 carbon atoms, and 1 to 4 carbon atoms.
selected from alkoxy groups, halogen atoms, and hydrogen atoms, steel represents 1 to 3, and n represents 1 to 2.

Moreover, C(OOH) (Rg) (R3) group is meta,
Or in the para position. ) α-hydroperoxyisoalkyl group-substituted penzophenone represented by the general formula R,OH (■) (wherein, R is a tertiary alkyl group having 4 to 8 carbon atoms, or α-
Represents cumyl group. ) A method for producing a benzophenone group-containing dialkyl peroxide represented by the general formula (I), which is characterized by reacting the alcohol represented by the formula (I) in the presence of an acid catalyst,
The seventh aspect of the present invention is an α-hydroberoxyisoalkyl group-substituted penzophenone represented by the general formula (■), and a general formula RJllC=CIIR* (
IX) (wherein, R is an alkyl group having 1 to 5 carbon atoms or a phenyl group, R8 is an alkyl group having 1 to 2 carbon atoms, R
, represents a hydrogen atom or a methyl group. ) A method for producing a penzophenone group-containing dialkyl peroxide represented by the general formula (1), which is characterized by reacting an olefin represented by the formula (1) in the presence of an acid catalyst,
The eighth aspect of the present invention is an α-hydroberoxyisoalkyl group-substituted penzophenone represented by the general formula (■), and a general formula R,X (X) (wherein R is a tertiary Alkyl group, or α-
In the cumyl group, X represents a chlorine atom or a bromine atom. ) A method for producing a penzophenone group-containing dialkyl peroxide represented by the general formula (1), which is characterized by reacting an alkyl halide represented by the formula (1) with an alkyl halide represented by These are photolytic radical generators and thermally decomposable radical generators containing the novel dialkyl peroxide as an effective ingredient.

Here, the photodegradable radical generator refers to a photopolymerization initiator, a photocuring agent, a photocrosslinking agent, etc., and the pyrolytic radical generator refers to a polymerization initiator, a crosslinker, a crosslinker, etc. that generates radicals by heat.
Hardening agents, etc.

Specifically, the benzophenone group-containing dialkyl peroxides of the present invention are (1) 4-(1-t-butylperoxy-1-methylethyl)penzophenone (2) 4-(1-t-butylperoxy-1- methylethyl)penzophenone (3) 4-(1-t-hexylperoxy-1-methylethyl)penzophenone (4) 4-(1-t-octylberoxy-1-methylethyl)penzophenone (5) 4-( 1-cumylperoxy-1-methylethyl)penzophenone (6) 4-(1-t-butylperoxy-■-methylethyl)-2-methylbenzophenone (7) 4(1-t-butylperoxy-1 -methylethyl)-2-propylbenzophenone (8) 4-(1-t-butylberoxy=1-methylethyl)2,6-dipropylbenzophenone (9) 4-(1-t-butylberoxy=1-methylethyl) oxy-1-methylethyl) to 2,6-dibrobyl-4'-t-dodecylbenzophenone (10) 4-(1-t-butylperoxy-1-methylethyl)4'-chlorobenzophenone (11) 4-( 1-t-butylperoxy-1-methylethyl)-4'-bromobenzophenone (12) 4-(1-t-butylperoxy-1-methylethyl)-4'-butoxybenzophenone (13) 4 -(1-t-octylperoxy-1-methylprobyl)-2,6-dibrovir-2',3'
．． 4'-trimethoxybenzophenone (14) 4-(1-t-octylperoxy-1-methylprobyl)-2-,6-diprobyl-3',4'
-Diethoxybenzophenone (15) 3-(1-t-butylperoxy-1-methylethyl)benzophenone (16) 3-(1-t-octylperoxy-1-methylbropyl)-6-propyl-3',4' -Diethoxybenzophenone, etc. The compound represented by the general formula (1) of the present invention can be produced by the following four methods. In the first production method, the compound represented by the general formula (1) is obtained by reacting the isoalkyl group-substituted penzophenone derivative (1) with the hydroperoxide (II) in the presence of a metal salt.

(In the formula, RI Rt+ R31 R41 Rs+ l+
The positions of n and RIOOC(Rz)(Ih) groups are as described above. ) The first compound (I[I) can be easily obtained by Friedel-Krach reaction of substituted benzene and substituted penzoyl chloride. In the reaction between compound (I[I) and hydroperoxide (ff) in the production method of the present invention, a metal salt of a metal selected from the fourth and fifth period transition elements can be used as a catalyst. Specific examples of metals in metal salts include copper, cobalt, manganese, iron, chromium, and zinc, and specific examples of ligands include halogens such as iodine, bromine, and chlorine, sulfuric acid, phosphoric acid, and nitric acid. , mineral acids such as carbonic acid, organic acids such as formic acid, acetic acid, naphthenic acid, octenoic acid, gluconic acid, cyanide, acetylacetonate, etc. The amount of metal salt used is o. oooi〜0
．． It is 1 mole. The reaction conditions vary depending on the metal salt used, but the reaction temperature is usually 30 to 100°C and the reaction time is 1.
~50 hours is preferred. Furthermore, benzene, toluene, etc. can be used as a solvent.

In the second production method, a compound represented by the general formula (1) is obtained by reacting an α-hydroxyisoalkyl group-substituted penzophenone derivative (IV) with a hydroperoxide (II) in the presence of an acid catalyst. It will be done.

(In the formula, R++ Rt+ R31 R41 RSI m
The positions of the I n and 11.00(Rz) (R2) groups are as described above. ) The first compound (IV) can be easily obtained by reducing the hydroperoxide produced by air oxidation of compound (I[[). In the reaction between compound (rV) and hydroperoxide (II) in the production method of the present invention, perchloric acid, hydrochloric acid,
Mineral acids such as sulfuric acid and phosphoric acid can be used. The amount of acid catalyst used is 0.00 per mole of compound (TV)
1-1 mol. Acetic acid or the like can be used as a solvent. Further, when a dehydrating agent such as magnesium sulfate is present in the reaction system, the yield can be improved. The reaction conditions are: the reaction temperature is usually 0 to 70°C, and the reaction time is 1
~10 hours is preferred. Furthermore, the reaction between the hydroperoxide (■) and the alcohol (■) is carried out in the same manner to obtain the compound represented by the general formula (1). In the third production method, the compound represented by the general formula (1) is obtained by reacting the isoalkenyl group-substituted benzophenone derivative (V) with the hydroperoxide (II) in the presence of an acid catalyst.

(V) (I) (wherein, R++ Rz+ R3+ R4+ R,,Rh
+ n and R, OOC (the position of the 1(pz) group is as described above). The first compound (V) is the compound (IV
) can be easily obtained by dehydrating.

Compound (V) and hydroperoxide (
In the reaction with II), mineral acids such as hydrochloric acid, sulfuric acid, and perchloric acid, and/or Lewis acids such as zinc chloride and aluminum chloride are used as acid catalysts. The amount of the acid catalyst used is 0.001 to 1 mol per 1 mol of compound (■). Regarding the reaction conditions, the reaction temperature is usually 0 to 70°C, and the reaction time is preferably 1 to 10 hours. Additionally, a solvent such as isopropyl alcohol can be used.

Also, hydroperoxide (■) and olefin (IX)
By performing the reaction with the compound in the same manner, a compound represented by the general formula (1) can be obtained.

The fourth production method is to react an α-halogenated isoalkyl group-substituted penzophenone derivative (VI) with a hydroperoxide (II) in the presence of an alkali to obtain a compound represented by the general formula (1). .

(Vl) (1) (wherein, RI+ RZ+ R31 R41 R51 XI m
The positions of the + n and RIOOC(R2) (Rz) groups are as described above. ) The first compound (Vl) can be easily obtained by halogenating compound (1111) with chlorine gas, N-bromosuccinimide, or the like.

In the reaction between compound (Vl) and hydroperoxide (II) in the production method of the present invention, sodium hydroxide, potassium hydroxide, pyridine, etc. can be used as the alkali. The amount of alkali used is preferably 0.8 to 3.0 mol per 1 mol of compound (■). Regarding the reaction conditions, the reaction temperature is usually 0 to 70°C, and the reaction time is preferably 1 to 10 hours. Moreover, hexane, benzene, toluene, ether, etc. can be used as a solvent.

Furthermore, the reaction between hydroperoxide (■) and alkyl halide (X) can be carried out in the same manner by -e formula (1
) is obtained.

The novel dialkyl peroxide produced as described above is obtained as a white solid or a transparent viscous liquid at room temperature. The structure of each compound obtained can be identified by infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum, mass spectrum, and elemental analysis.

The dialkyl peroxide of the present invention is used alone or in combination with other components as a photopolymerization initiator for photopolymerization or photocuring of radically polymerizable unsaturated compounds. At this time, 1
In the mixture of the species or two or more radically polymerizable unsaturated compounds and the photopolymerization initiator of the present invention, commonly used pigments, fillers, dyes, thermal polymerization inhibitors, plasticizers, solvents, and sensitizers can be added. In addition, additives such as other known photopolymerization initiators can be appropriately blended, and such photosensitive compositions can be used as paints, adhesives, printing inks, printing plates, printed wiring boards, and photosensitive compositions. Used for resists, etc.

Examples of radical unsaturated compounds that can be photopolymerized and photocured by blending the photopolymerization initiator and photocuring agent of the present invention include polymerizable monomers, polymerizable oligomers, and polymerizable unsaturated polymers. . Polymerizable monomers are compounds having one or more polymerizable double bonds, such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and , derivatives of these unsaturated carboxylic acids, such as monoesters such as methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, etc. -Hydroxyethyl (meth)acrylate, 2
-Hydroxy esters such as hydroxybutyr (meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neobentyl glycol di(meth)acrylate. Polyvalent esters such as acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate, (meth)acrylonitrile, (meth)acrylamide, and N-substituted (meth)acrylamide, vinyl acetate, vinyl Vinyl esters such as probionate, vinyl acetate, and vinyl succinate, vinyl ethers, styrene, alkylstyrene, halogenated styrene, divinylbenzene, vinylnaphthalene, N-vinylpyrrolidone, diallylphthalate, diallyl maleate, triallyl isocyanate , and vinyl compounds such as triallyl phosphate.

Examples of polymerizable oligomers and polymerizable unsaturated polymers include curable resins having maleate groups, fumarate groups, allyl groups, and (meth)acrylate groups, unsaturated polyesters,
Examples include unsaturated acrylic resins, isocyanate-modified acrylic oligomers, polyester acrylic oligomers, and polyether acrylic oligomers.

Polymers to be crosslinked that can be used in the photocrosslinking agent of the present invention include, for example, polyethylene, ethylene brobylene copolymer (EPM), ethylene propylene copolymer (EPDM), ethylene vinyl acetate polymer (EVA), and tetrafluorocarbon polymer. Ethylene vinylidene fluoride to hexafluoride propylene ternary cobolimer,
Chlorosulfonated polyethylene, chlorinated polyethylene,
Polybutene-1, polyisobutene, ethylene vinyl acetate copolymer polybutadiene, polyisoprene, polychloroprene, butadiene styrene copolymer, natural rubber, polyacrylate rubber, butadiene acrylonitrile copolymer, acrylonitrile butadiene styrene ternary copolymer, silicone rubber, polyurethane, and the like.

The amount of the photopolymerization initiator, photocuring agent, and photocrosslinking agent used in the present invention is basically 0.01 to 10% by weight, preferably 0.01 to 10% by weight based on the radically polymerizable unsaturated compound and the polymer to be crosslinked. .1 to 4% by weight, depending on the type of additive. For example, when mixing pigments with poor light transmittance,
It may be necessary to increase the dose. However, if the amount is too large, unreacted photopolymerization initiator may remain in the polymer, which may deteriorate the physical properties of the polymer. On the other hand, if the amount is too small, polymerization will not be completed and unreacted unsaturated compounds will remain.

Photopolymerization, photocuring, and photocrosslinking of the radically polymerizable unsaturated compound containing the photopolymerization initiator, photocuring agent, and photocrosslinking agent of the present invention are carried out by known methods at a wavelength of 250 to 500 nm, preferably 300 to 400 nlI1. This is done by irradiating light in a wavelength range. Usable light sources include sunlight, mercury lamps, mercury discharge tubes, xenon arc lamps, flash discharge tubes, tungsten lamps, halogen lamps, dye lasers, excimer lasers, and the like.

The present inventors further investigated the uses of the benzophenone group-containing dialkyl peroxide of the present invention and found that it also has effective performance in thermal polymerization and crosslinking.

Examples of vinyl monomers used in the thermal polymerization initiator of the present invention include styrene, α-methylstyrene, acrylonitrile, acrylic esters, methacrylic esters, maleic esters, fumaric esters, and maleimide. , butadiene, vinyl acetate, etc.

In addition to these monomers, various chain transfer agents, rubber or foaming agents such as bentane may be added.

The thermal polymerization initiator used in the invention may be used in combination with other initiators having different thermal decomposition temperatures.

The amount of initiator added varies depending on the type of monomers used for polymerization or their combination, but in general, the amount of monomers added is 100
The amount is 0.001 to 5 parts by weight, preferably 0.01 to 0.5 parts by weight, in terms of pure product. If the amount is less than 0.001 part by weight, the polymerization rate tends to be slow. Moreover, if it exceeds 5 parts by weight, it is uneconomical and undesirable.

The polymerization method used in the present invention is a conventional bulk polymerization, solution polymerization, or suspension polymerization method, and the polymerization temperature is generally 80°C.
-150'C, preferably in the temperature range of 80-130C. The polymerization temperature is a constant temperature or a relatively low temperature in the initial stage of polymerization, and a method is used in which the temperature is raised stepwise as the polymerization progresses.

The polymers obtained in the present invention are GP type polystyrene, impact-resistant polystyrene, expanded polystyrene, polymethyl methacrylate, styrene/acrylonitrile copolymer, styrene/acrylonitrile/
Phenylmaleimide copolymer, butyl methacrylate/2
- Copolymers of various acrylic acids or methacrylic acid esters such as ethylhexyl methacrylate copolymers, etc. Polymers to be crosslinked used in the thermal crosslinking agent of the present invention include, for example, polyethylene, ethylene propylene copolymer, etc. (EPM), ethylene propylene diene copolymer (EPDM), ethylene vinyl acetate copolymer (BVA), tetrafluoroethylene vinylidene fluoride hexafluoropropylene ternary copolymer, chlorosulfonated polyethylene, chlorinated polyethylene, polybutene-1, polyisobutene , ethylene vinyl acetate copolymer, polyptadiene, polyisoprene, polychlorobrene, butadiene styrene copolymer,
Natural rubber, polyacrylate rubber, butadiene acrylonitrile copolymer, acrylonitrile butadiene styrene ternary copolymer, silicone rubber, polyurethane,
Examples include polysulfides.

The peroxide is generally 0% of the polymer to be crosslinked.
．． It is added in a range of 1 to 10 weight χ, preferably 1 to 3 weight χ.

The polymer to be crosslinked may also contain various additives commonly used in the crosslinking process, such as crosslinking coagents, antioxidants,
Pigments, UV stabilizers, fillers, plasticizers, etc. can be added.

In the present invention, the temperature at which the polymer and organic peroxide are mixed is generally 25 to 130°C. The temperature of the subsequent crosslinking is generally from 110 to 220°C, preferably from 150 to 19°C.
0°C is used.

(Effects of the Invention) The benzophenone group-containing dialkyl peroxide of the present invention has the following characteristics compared to conventional photopolymerization initiators.

(1) Since the penzophenone group-containing dialkyl peroxide of the present invention has a light-absorbing group and a radical generation source in the same molecule, it can efficiently generate radicals by irradiation with light. Therefore, the photopolymerization and photocuring rates are fast.

(2) Since the penzophenone group-containing dialkyl peroxide of the present invention is a dialkyl type peroxide, it has good thermal stability, and therefore, a photopolymerizable product containing it can be used for a long period of time without polymerizing or gelling. Can be saved.

(3) A polymer obtained by using the benzophenone group-containing dialkyl peroxide of the present invention as a photopolymerization initiator, photocuring agent, or photocrosslinking agent does not yellow.

<4> Since the penzophenone group-containing dialkyl peroxide of the present invention is a peroxide, if curing by photocuring is insufficient, after-curing by thermosetting is possible.

(5) The penzophenone group-containing dialkyl peroxide of the present invention is also effective as a thermal polymerization initiator and a crosslinking agent.

(6) The production method of the present invention can produce a penzophenone group-containing dialkyl peroxide with good yield.

As described above, the penzophenone group-containing dialkyl peroxide of the present invention is a novel compound with excellent characteristics as a photopolymerization, curing, crosslinking agent, and thermal polymerization and crosslinking agent, and has extremely high industrial value.

(Example) Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

EXAMPLE 11.2 g of 4-isopropylbenzophenone [which is obtained from cumene and penzoyl chloride] (0.4 g) was added to a 200-meter four-bottle flask equipped with a stirrer and a thermometer.
05 mol), t-butyl hydroperoxide 13.5 g
(0.15 mol), 0.05 g of cuprous chloride, and 50% of benzene were continuously stirred at 70°C for 25 hours under a nitrogen atmosphere, then 10% hydrochloric acid, 10% aqueous sodium hydroxide solution, and water. Wash sequentially with water, dry with magnesium sulfate,
After distilling off the solvent, 7.8 g of a white solid was obtained by crystallization in methanol or column chromatography. The results of infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum, mass spectrum, elemental analysis, and measurement of the melting point of this compound were as follows, and the results showed that this compound was 4-(1-t-butyl Peroxy
It was confirmed that it was penzophenone (1-methylethyl).

CH. CH. Infrared absorption spectrum 870 α-' (0-0 bond) 1660 as-' (C-0 bond) Nuclear magnetic resonance spectrum (δ) 1.27 ppm (9B) 1.62 ppm (6H) 7.4-8.2 ppm (911 ) Ultraviolet absorption spectrum (in dioxane) 342 nm
(ε 160) 256n customary (ε 18800) Mass spectrum 312 m/e (molecular ion beak) Elemental analysis C. 76.832 (calculated value 76.892)H. 7
．． 7X (calculated value 7.742) melting point 48-49°C 11 reached, respectively
A viscous liquid was obtained using -amyl hydroperoxide, t-hexylhydroperoxide, t-octyl hydroperoxide, and cumene hydroperoxide in a similar manner to that described in Example 1. Each of these compounds was analyzed in the same manner as in Example 1, and as a result, it was confirmed that these compounds were the desired peroxides. The obtained compounds and the results of each analysis are shown in Section I.
They are summarized in the table.

The production method described in Example 1 was followed except that 4-isoprobylhenzophenone with various substituents was used instead of 4-isoprobylbenzophenone. The obtained compounds were analyzed in the same manner as in Example 1, and as a result, it was confirmed that these compounds were the desired peroxides. The obtained compounds and the results of each analysis are summarized in Table 2. 2旌明dan 2danProcessed in a manner similar to the production method described in Example 1, except that 3-isopropylbenzophenone having various substituents was used instead of 4-isopropylbenzophenone. The obtained compounds were analyzed in the same manner as in Example 1, and as a result, it was confirmed that these compounds were the desired peroxides. The obtained compounds and the results of each analysis are summarized in Table 3. Example II: In a 100 d four-necked flask equipped with a stirrer and a thermometer, 12.0 g (0.05 mol) of 4-(α-hydroxyisopropyl)penzophenone and 5.0 g (0.0 mol) of L-butyl hydroperoxide were added. .055 mol), magnesium sulfate2. L in 0g suspension! Acetic acid solution of perchloric acid 5
．． 0 g (0.0005 mol) was added dropwise while keeping the temperature below 25°C, and after raising the temperature to 40°C, stirring was continued for 2 hours. After cooling, the mixture was washed with a 5x aqueous sodium hydroxide solution and then with water, dried over anhydrous magnesium sulfate, the solvent was distilled off, and 11.8 g of a white solid was obtained by crystallization in methanol or column chromatography. As a result of infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum, mass spectrum, elemental analysis, and measurement of melting point, this compound was found to be 4-(1-t-butylperoxy-1-methylethyl ) was confirmed to be penzophenone.

In a 100 d four-neck flask equipped with a stirrer and a thermometer was added 11.1 g of 4-isopropenylbenzophenone (0
．． 1.0 g (0.01 mol) of concentrated hydrochloric acid and then 5.0 g (0.055 mol) of t-butyl hydroperoxide were added to a solution of 0.05 mol) of isopropyl alcohol at 25°C.
The solution was added dropwise while maintaining the temperature below, and after raising the temperature to 40°C, stirring was continued for 2 hours. After cooling, it was washed with a 5z aqueous sodium hydroxide solution and then with water, dried over magnesium sulfate, and the solvent was distilled off.
10.7 g of white solid was obtained by crystallization in methanol or column chromatography. This compound was subjected to infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum, mass spectrum, elemental analysis, and measurement of melting point.
-butylperoxyl-methylethyl)penzophenone.

40 in a 200 ml four-loaf flask equipped with a stirrer and a thermometer. Sodium hydroxide aqueous solution 12.5g (0.
125 moles), 25 g of benzene, and 75 g of dioxane were added, stirred, cooled with water, and heated to t-
11.3 g (0.125 mol) of butylhydroberoxide and 25.9 g (0.10 mol) of 4-(α-chloroisopropyl)penzophenone were added. then 5
The reaction was continued for 4-5 hours at °C. The organic layer was removed from the reaction mixture and treated with 1(IX) sodium hydroxide twice;
Next, after washing with saturated brine 2 to 3 times, drying with anhydrous magnesium sulfate, distilling off the solvent, crystallizing in methanol,
Or white solid 22. by column chromatography.
1g was obtained. Regarding this compound, infrared absorption spectrum, nuclear magnetic resonance spectrum, ultraviolet absorption spectrum,
As a result of mass spectrometry, elemental analysis, and melting point measurements, it was confirmed that this compound was 4-(1-t-butylperoxy-1-methylethyl)penzophenone.

Instead of 4-(α-hydroxyisobutyl)penzophenone and t-butyl hydroperoxide, t-
Example 1 except that butyl alcohol and 4-(α-hydroperoxyisopropyl)penzophenone are used.
The obtained compounds were analyzed in the same manner as in Example 15, and the results showed that these compounds were 4-(1-t-butylperoxy-l- It was confirmed that it was (methylethyl)penzophenone. As described in Example 16, but instead of 4-isopropylbenzophenone and t-butyl hydroperoxide, 2-methyl=1-pentene and 4-(α-hydroperoxyisopropyl)penzophenone were used. The obtained compounds were analyzed in the same manner as in Example 16, and the results showed that these compounds were 4-(1-t-hexylberoxy-■
-Methylethyl)penzophenone.

tert-butyl chloride and 4-(α-hydroperoxyisopropyl) instead of 4-(α-chloroisopropyl)penzophenone and t-butylhydroperoxide
The manufacturing method described in Example 17 was followed except that penzophenone was used, and the obtained compounds were analyzed in the same manner as in Example 17. As a result, these compounds were found to be 4-(1 -thexylperoxy-1-
It was confirmed that it was penzophenone (methyl ethyl).

0.01 t each of methyl methacrylate containing no polymerization inhibitor and the photopolymerization initiator of the present invention were placed in a photopolymerization tube made of Fujikoku quartz.
ool/I! After adding nitrogen and replacing with nitrogen by freeze-thaw method, 2
Using a merry-go-round type light irradiation device (manufactured by Taishina Kogyo Co., Ltd., trade name MGR-P type) in a constant temperature bath at 0°C, 400-1 high-pressure mercury lamp (UVT 36A 7 I/I/Yuichi used) Te3
After irradiating with 65 nm ultraviolet light from a distance of 8 cm for 30 minutes, the polymerization conversion rate and polymerization rate (Rp) were measured gravimetrically using methanol precipitation. The results obtained are shown in Table 4.

Furthermore, methyl methacrylate was polymerized according to Example 2I, except that the conventional photopolymerization initiator shown in Table 4 was used instead of the photopolymerization initiator of the present invention, and the polymerization conversion rate and The polymerization rate was measured. The results are shown in Table 4.

The results in Table 4 show that the compounds of the present invention have effective photopolymerization performance.

The 4-(1-t-butylperoxy-1-methylethyl)penzophenone of the present invention was added to methyl methacrylate.
．． 01io1/l was added, polymerization was carried out using the same apparatus as in Example 21, and the same operation was performed while changing the light irradiation time, and the polymerization conversion rate was measured. The relationship between the irradiation time and the polymerization conversion rate obtained is shown in FIG.

Methyl methacrylate was polymerized according to Example 26, except that the conventional photopolymerization initiator shown in Table 4 was used instead of the photopolymerization initiator of the present invention, and the resulting irradiation The relationship between time and polymerization conversion rate is shown in FIG.

From FIG. 1, it can be seen that when the photopolymerization initiator of the present invention is used, the polymerization activity is large.

4-(1-t-butylberoxy-1-methylethyl)penzophenone of the present invention was placed on a glass plate.
Ester acrylate resin added by weight part [Gumi or "Aronix M-8060J (Toa Gokaisha product name)
“Aronixst 5700J (Toa Gotosha product name =
4/6] was applied to a film thickness of 100 μm, and the resin was cured using a conveyor-type ultraviolet curing device (concentrating type). There was no visible yellowing of this resin.

Comparison dish main 4-(1-t-Butylperoxy-1-methylethyl) instead of penzophenone, 1,2-diphenyl-
The ester acrylate resin was cured according to Example 27 except that 2.3-dimethoxyethane-1-one was used. This resin was yellowed.

Ester acrylate resins (same as the resin used in Example 27) to which 2 parts by weight of the photopolymerization initiator of the present invention were added were placed in a glass bottle, and the bottles were placed in an incubator for 60 minutes. Dark storage stability was investigated at 'C. The results were expressed as the number of days in which gelation occurred visually. The obtained dark storage stability is shown in Table 5.

Comparative brain soil 2i Dark storage stability was measured according to Example 28, except that the conventional photopolymerization initiators shown in Table 5 were used instead of the photopolymerization initiators of the present invention. The results obtained are shown in Table 5.

Table 1) "Irgacure 65i J": Ciba Geigy's product name "Darocure 1173.";Merck's product name: Practical group H inhibition i120d glass ampoule tube containing the 4-
10 g of styrene to which 0.005 mol/l of (t-butylperoxy-■-methylethyl)penzophenone had been added was added, and after vacuum degassing, the tube was sealed. This ampoule tube was polymerized for a predetermined time in a constant temperature oil bath at 120''C. Each polymerized product was poured into methanol and reprecipitated, and the polymerization conversion rate was calculated from the weight of the obtained white powder.

In addition, gel permeation stomatography (GP)
C), the polymerization average molecular weight (Mw) was measured. The results are shown in Table 6.

Comparison: 10 g of styrene to which 0.005 mol/l of t-butylcumyl peroxide was added instead of 4-(t-butylperoxy-1°-methylethyl)penzophenone
Polymerization was carried out according to the method described in Example 33, except that the following was used, and the results are shown in Table 6.

It can be seen from Table 6 that the compounds of the present invention have effective performance as thermal polymerization initiators.

Is the specific gravity 0.45 and particle size AST seen in a Henschel mixer (stirring blade: standard type) with a capacity of 7i? I30 mesh 99
, 5χ bath, M130.5, 20 kg of powdered polyethylene with a density of 0.956 and 4-(t-butylberoxy-1
-Methylethyl)penzophenone (0.2 kg) was added at the same time and mixed at about 75 rpm for 2 minutes and at 1500 rpm for 8 minutes.

Using the resulting mixture, a casting mold was used to obtain a product using the two-axis rotation method. The appearance and mechanical properties of the obtained product were as shown in Table 7.

The method described in Example 34 was followed except that dicumyl peroxide was used instead of 4-(t-butylberoxy-1-methylethyl)penzophenone, and the results are shown in Table 7. .

Table 7, Figure 1 is a diagram showing the relationship between the irradiation time of the photopolymerization initiator and the polymerization conversion rate in Example 26 and Comparative Example 2 of the present invention. Figure 1 O f0 20 At the time of the 20th day of the 1990s, the written amendments to the procedures for the Mc war, August 25, 1997

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 is a tertiary alkyl group having 4 to 8 carbon atoms or α-cumyl group, R_2 and R_3 are An alkyl group having 1 to 2 carbon atoms, R_4 is selected from an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom, and R_5 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. , selected from hydrogen atoms, where m represents 1 to 3 and n represents 1 to 2.Also, R_1OOC(R_2)(R_3) group is in the meta or para position.) Containing a benzophenone group represented by Dialkyl peroxide. 2. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (In the formula, R_2 and R_3 are alkyl groups with 1 to 2 carbon atoms,
R_4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, m represents 1-3, and n represents 1-2. Also, CH
The (R_2) (R_3) groups are in the meta or para position. ) and a hydroperoxide represented by the general formula R_1OOH(II) (wherein R_1 represents a tertiary alkyl group having 4 to 8 carbon atoms or an α-cumyl group), General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1, R_2, R_3, R_4, R_5 are the same as above, and m and n are also the same as above. Also, R_1OOC(R_2) (R_3) group is at meta or para position. Method for producing group-containing dialkyl peroxide. 3. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (IV) (In the formula, R_2 and R_3 are alkyl groups with 1 to 2 carbon atoms,
R_4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, m represents 1-3, and n represents 1-2. Also, C(
The OH)(R_2)(R_3) group is in the meta or para position. ) and a hydrocarbon represented by the general formula R_1OOH(II) (wherein R_1 represents a tertiary alkyl group having 4 to 8 carbon atoms or an α-cumyl group). General formulas ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1, R_2, R_3, R_4, R_5 are the same as above. and m and n are the same as above. Also, the R_1OOC(R_2)(R_3) group is at the meta or para position.) A method for producing a benzophenone group-containing dialkyl peroxide. 4. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) (In the formula, R_3 is an alkyl group with 1 to 2 carbon atoms, R_4 is an alkyl group with 1 carbon number ~3 selected from alkyl groups and hydrogen atoms,
R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, R_6 is a hydrogen atom or a methyl group, m is 1 to 3, and n is 1 to 2. represents. Further, the R_6HC=C(R_3) group is at the meta or para position. ) and a hydroperoxide represented by the general formula R_1OOH(II) (wherein R_1 represents a tertiary alkyl group having 4 to 8 carbon atoms or an α-cumyl group), General formulas ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formulas, R_1, R_2, R_3, R_4, R_5 are the same as above, m and n are also the same as above.Also, the R_1OOC(R_2)(R_3) group is at the meta or para position.) A method for producing a benzophenone group-containing dialkyl peroxide. 5. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (VI) (In the formula, R_2 and R_3 are alkyl groups with 1 to 2 carbon atoms,
R_4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, x is a chlorine atom or a bromine atom, m is 1 to 3,
n represents 1-2. Further, the CX(R_2)(R_3) group is at the meta or para position. ) and a benzophenone substituted with an α-halogenated isoalkyl group; General formulas ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1, R_2, R_3, R_4, R_5 are the same as above. and m and n are the same as above. Also, the R_1OOC(R_2)(R_3) group is at the meta or para position.) A method for producing a benzophenone group-containing dialkyl peroxide. 6. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (VII) (In the formula, R_2 and R_3 are alkyl groups with 1 to 2 carbon atoms,
R_4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, m represents 1-3, and n represents 1-2. Also, C(
The OOH)(R_2)(R_3) group is in the meta or para position. ) and an α-hydroperoxyisoalkyl group-substituted benzophenone represented by the general formula R_1OH(VIII) (wherein R_1 represents a tertiary alkyl group having 4 to 8 carbon atoms or an α-cumyl group). General formulas ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1, R_2, R_3, R_4, R_5 are the same as above.) Characterized by reacting alcohol in the presence of an acid catalyst. and m and n are the same as above. Also, the R_1OOC(R_2)(R_3) group is at the meta or para position.) A method for producing a benzophenone group-containing dialkyl peroxide. 7. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (VII) (In the formula, R_2 and R_3 are alkyl groups with 1 to 2 carbon atoms,
R_4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, m represents 1-3, and n represents 1-2. Also, C(
The OOH)(R_2)(R_3) group is in the meta or para position. ) and an α-hydroperoxyisoalkyl group-substituted benzophenone represented by the general formula R_7R_8C=CHR_9(IX) (wherein R_7 is an alkyl group or phenyl group having 1 to 5 carbon atoms, and R_8 is an alkyl group having 1 to 2 carbon atoms. group, R_9 represents a hydrogen atom or a methyl group) is reacted in the presence of an acid catalyst.There are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼(I) (Formula (R_1, R_2, R_3, R_4, R_5 are the same as above, and m and n are also the same as above. Also, R_1OOC(R_2) (R_3) group is in the meta or para position.) A method for producing a benzophenone group-containing dialkyl peroxide represented by 8. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (VII) (In the formula, R_2 and R_3 are alkyl groups with 1 to 2 carbon atoms,
R_4 is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, m represents 1-3, and n represents 1-2. Also, C(
The OOH)(R_2)(R_3) group is in the meta or para position. ) with the general formula R_1X(X) (wherein R_1 is a tertiary alkyl group having 4 to 8 carbon atoms or an α-cumyl group, and X is a chlorine atom or bromine There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ ( I ) (where R_1, R_2, R_3 , R_4, R_5 are the same as above, and m and n are also the same as above. Also, R_1OOC(R_2)(R_3) group is in meta or para position.) A benzophenone group-containing dialkyl represented by Method for producing peroxide. 9. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 is a tertiary alkyl group with 4 to 8 carbon atoms or α-cumyl group, R_2 and R_3 are tertiary alkyl groups with 1 to 2 carbon atoms, The alkyl group, R_4, is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, and R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom. (R_1OOC(R_2)(R_3) group is in the meta or para position.) A photodegradable radical generator. 10. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 is a tertiary alkyl group having 4 to 8 carbon atoms or α-cumyl group, R_2 and R_3 are tertiary alkyl groups having 4 to 8 carbon atoms, and R_2 and R_3 are The alkyl group, R_4, is selected from an alkyl group having 1 to 3 carbon atoms and a hydrogen atom, and R_5 is selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom. (R_1OOC(R_2)(R_3) group is in the meta or para position.) A thermal decomposition type radical generator.