JPS6242963A - Organic peroxide having polymerization controlling capability - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 and R2 are H, 1-10C alkyl, etc.; R3 and R4 are 1-4C alkyl; when l is 1, R5 is 1-12C alkyl, and when lis 2, R5 is -CidenticalC- or -(CH2)m- (m is 2-4)]. EXAMPLE:t-Butylperoxyphenyl carbonate. USE:A radical polymerization initiator for unsaturated monomer having polymerization-controlling capability. PREPARATION:The objective compound of formula I can be produced by reacting the aryl chloroformate of formula II with the tertiary alkyl hydroperoxide of formula III in the presence of an alkali or a tertiary amine at -30-+40 deg.C. The compound of formula I has the following advantages. A polymer having lower molecular weight can be produced when the polymerization rate is adjusted to the same level as that of conventional polymerization initiator. There is no abrupt increase in the polymerization rate even if the viscosity of the polymerization system is increased and, accordingly, the gelling effect can be prevented. The compound is odorless and handleable easily.

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a functional peroxide of beluoquine aryl carbonate which can be used in radical polymerization or copolymerization of unsaturated monomers and has the ability to control polymerization. (Prior art) Radical polymerization of unsaturated t-heavy substance 7'=Jli? l
In polymerization, various factors related to polymerization tjM adjustment, such as polymerization rate, polymerization degree, and molecular fraction, are closely related to polymerization heat, polymer fluidity, additive properties, and mechanical properties. . For this reason, 61M regulation of polymerization has become the most important issue in the fields of polymers and chemistry, as well as in the fields of cattle and vegetables. Unsaturation generated at the beginning of radical polymerization! 1- The reciprocal number 41 of the number average degree of polymerization (P, , ) and the polymerization rate of a polymer of M form are determined from the Chemical Society of Japan Silk 1-New Experimental Chemistry Lecture β Old 9, Polymer Chemistry [T) J (Maruzen) No. 387 Pages to 388 pages (19
1975), the following (
It is expressed by equations 1) and (2). (where K, , M, , l and Ktr8i are the rate constants of chain transfer to the unsaturated dose, polymerization initiator, and polymerization modifier, respectively, and k and kp are the termination and propagation reactions, respectively) In addition, kd and " are the decomposition rate constant and initiator efficiency of the polymerization initiator, respectively. Furthermore, [I], [M] and [A]
are the concentrations of the polymerization initiator, the unsaturated 1j i1 form, and the polymerization initiator, respectively, R9 is the polymerization rate, and x is the ratio of the disproportionation termination reaction. ) In formula (1), the first, second, and third terms on the right side are terms due to chain transfer reactions of polymer radicals to unsaturated monomers, polymerization initiators, and polymerization modifiers, respectively,
The fourth term is a termination reaction term between polymer radicals. According to formula (1), the degree of polymerization of the polymer decreases as the polymerization rate increases, but it also decreases even if the concentration of the polymerization modifier increases. Therefore, the degree of polymerization of the resulting polymer is usually controlled by changing the polymerization rate or by adding a known polymerization modifier having a chain dynamic constant expressed by ktr^/. For example, the above-mentioned document states that formula (1) holds true in the polymerization of styrene using asoisobutynitrile and dibenzoylperkioxide 4. Two and two are shown,
Furthermore, Japanese Patent Publication No. 34-10046 discloses that by changing the concentration of dibenzoylperoquinde and adjusting the polymerization rate, polysaccharides having various degrees of polymerization can be obtained. For example, JP-A No. 48-52886 discloses that when alkyl mercaptan and carbon tetrabromide are used, the relative viscosity of the polymer solution is significantly reduced due to the reduction in the degree of polymerization of the polymer. Regarding peroxycarbonate, Belgian Patent No. 660383 has the following general formula (formerly R-o-
n-i': n-+i' (IT) (where, R represents a tertiary alkyl group and a tertiary alkyl group, and R' represents an alkyl group, an aralkyl group, an aryl group, and an alkoxyalkyl group.) It is disclosed that the compound represented by the formula can be used as a polymerization initiator for unsaturated monomers. (Problems to be Solved by the Invention) Conventional polymerization control techniques using polymerization initiators and polymerization regulators have limitations, and several drawbacks described below have been pointed out. As the polymerization rate increases, control of the polymerization reaction becomes extremely difficult due to an increase in polymerization heat and a rapid increase in the viscosity of the polymerization system. For example, in the production of methyl methacrylate resin plates, syrup is used to reduce the heat generated by polymerization and shrinkage of the polymer, but syrup is used to reduce the heat generated by polymerization and the shrinkage of the polymer. I am wanted. However, with commonly used polymerization initiators, it is difficult to control the polymerization reaction, and the viscosity of the syrup may increase significantly. Furthermore, in recent years in the V-structure of styrene resins, resins with excellent moldability are required due to higher speed and precision of injection molding machines. However, it is difficult to obtain polymers with excellent moldability due to the formation of very high molecular weight polymers due to the gel effect in the late stage of polymerization.
If the amount of polymerization initiator is avoided in order to lower the molecule m, the mechanical properties will deteriorate due to the formation of a low molecular weight polymer. As described above, the problem of uniformity of polymer molecular weight is an important issue. Furthermore, in the method using carbon tetrabromide, the thermal stability of the polymer deteriorates, resulting in severe color decomposition at processing temperatures, which reduces the practical value of the molded product. Furthermore, in the case of alkyl mercaptans, it is known that not only do they have an unpleasant odor that hinders their use, but also unreacted mercaptans remaining in the polymer have an adverse effect. Furthermore, in the case of beluoquine carbonate represented by the general formula (formerly), isopropylene is

[-] Pyl group, benzyl group, cyclohexyl group, etc. are used,
These have very little effect on polymerization control ability. (Means for Solving the Problems) In order to solve the above-mentioned drawbacks, the present invention provides the following formula (where Ro and R2 are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a chlorine atom, R3 and R1 represent a lower alkyl group having 1 to 4 carbon atoms; R8 represents an alkyl group having 1 to 12 carbon atoms when p is 1; When is 2, -CmiC- group or m is an integer of 2 to 4, 4CH
Indicates a 2h group. ), i.e., peroxyl carbonate. This organic peroxide can be produced by conventional methods and has unsaturated 'J
When using as a polymerization initiator when polymerizing the ilt form,
It has been found that when a conventional polymerization initiator is used and the polymerization rate is the same, a polymer with a significantly lower degree of polymerization is obtained, and this fact has an effective effect on controlling polymerization. Specifically, the organic peroxides of the present invention include 'PH class butyl human VJ peroxide, tertiary amylhydroberoquinde, tertiary hekynruhydroberoxide and 1.1
．． ．． 31-butramethylbutyl hydroperoxide,
Pheninobe 2-methylphenyl, 3-methylphenyl,
2.4-dimethylphenyl, 216-dimethylphenyl, 2-isopropylphenyl, 2-4 secondary butylphenyl, 4-111th butylphenyl, 4- (1,1,
Carbonates such as 3゜3-tetramethylbutyl) pheninobe2]ruphenyl, 3-chlorophenyl, 4〈Y]ruphenyl, 214-dichlorophenyl, 2-chloro4-methylphenyl, and 2,5-dimethyl-
2,5-di(phenoquinecarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(4-methylphenoxycarbonylperoxy)hexane, 2,5-dimethyl-2°5-di(4-di) 2,5-dimethyl-2,5-di(
Examples include phenoxycarbonyl persoxy)hexyne. These peroxy"γ-lyl carbonates 1- are
It is usually a colorless liquid or white crystal and is odorless, and specific details are shown in the examples. The organic peroxides of the present invention can be prepared in a conventional manner, i.e. in the presence of an alkali or tertiary amine, with the general formula (IIT
) (In the formula, R1 and 1ma2 are the same as in the case of general formula (1) above.) Aryl chloroformate and general formula (rV) represented by
■ The tertiary alkyl hydrober oxide represented by
It is obtained by reacting at 0°C to 40°C. Belgian [(-1 Patent No. [i 8038]
In Publication No. 3, the π-th contained in the r general formula (11)
Class aralkyl per-quinyl γ-aryl carbonates (in the formula, R represents a tertiary aralkyl group and [R' represents an aryl group) cannot be produced by the above method because they exhibit specific reactivity. The chemical properties of the peroxides of the present invention can be determined by infrared absorption spectra and nuclear magnetic resonance spectra, and the purity can be determined by gas chromatography (GLC) and active oxygen screening. The thermal decomposition behavior is determined by the decomposition rate constant and 1'1! Required by sincerity. The organic peroxide of the present invention has a lifespan of 1 to 20 hours, and exhibits a decomposition activity approximately equal to that of t-butylperxyisopropyl carbonate, a conventional polymerization initiator. It is a high temperature active peroxide. Regarding safety, like other peroxides, many of them decompose explosively, so they should not be used diluted in an organic solvent, in a water-containing form, in a water emulsion, or in a water-based emulsion. It can be left in a safe state for use. The quaternary peroxide of the present invention is useful as a radical polymerization initiator for unsaturated heavy substances having polymerization control ability. Specific unsaturated monomers include vinyl that can be radically polymerized or copolymerized with ethylene, vinyl chloride, vinyl acetate, acrylonitrinovinylidene chloride, acrylic ester, methacrylic acid varnish fAy, fumaric ester, and styrene. Type unsaturated! Examples include the 11@ body and the ethylenically unsaturated monomer. The amount of organic peroxide used in the present invention is 0.00005 mol to 0.2 mol per mol of unsaturated heavy substance,
It can be used to manufacture a wide range of polymers, from low molecular weight polymers called oligomers to high molecular weight polymers called plastics. Before use, if the amount is less than the above range, the effect of Use-11 will be small, and if it is too much, the effect will not change much and it is not economical. Polymerization and copolymerization using the organic peroxide of the present invention can be carried out by any of the currently known vinyl polymerization methods using radically active species, bulk polymerization, solution polymerization, or aqueous medium polymerization. In this case, other polymerization initiators, polymerization modifiers and/or other polymerization additives (,
It can also be used for 11. (Function) The organic peroxide-containing slow polymerization initiator of the present invention exhibits behavior that is significantly superior to conventional 111 polymerization initiators that do not satisfy the above-mentioned polymerization rate formula (2). At the same polymerization rate as when using a conventional polymerization initiator, a polymer with a significantly reduced degree of polymerization was obtained, and the mechanism of this effect is thought to be as follows. That is, when peroxyaryl carbonate, which is the organic peroxide of the present invention, is thermally decomposed, first according to formula (3),
Cleavage of the -0-0- bond occurs and two active radical species are initially formed which initiate the polymerization of the unsaturated heavy bodies. (In the formula, R,, R, R3, R4 and R3 are the same as in the above general ceremony date). ) Subsequently, a decarboxylation reaction according to equation (4) occurs, producing inert radical species that are too stable to initiate polymerization. Since conventional polymerization initiators do not generate inert radical species such as 1 and 2, the chain reaction is terminated by a terminating reaction between polymer radicals. However, if an inert radical species as described in 111 is present in the polymerization system, it reacts with the polymer radical as shown in formula (5) and terminates the chain reaction. Therefore, unlike the conventional reaction between polymer radicals, it is thought that the polymerization control ability is developed. (Effects of the Invention) Since the organic peroxide of the present invention has the ability to adjust polymerization based on the special mechanism of action described in Aii, it has several advantages as shown below. The first is that when the reaction rate is the same as that of conventional polymerization initiators, a polymer with a lower molecular weight is produced. The second is that even if the polymerization system has a high viscosity, rapid polymerization i
One degree of -L rise does not occur, and the gel effect can be prevented. Third, as a result of the second effect, the final polymer has a uniform molecular weight distribution and a low dispersion index. Fourth, since it has the ability to initiate polymerization, it can shorten the time to complete polymerization compared to conventional polymerization regulators. The fifth reason is that it is odorless and easy to handle. To give a more specific example of one of these, in the production of styrenic resin, the gel effect does not occur in the late stage of polymerization, making it easy to control the polymerization temperature, and the uniform molecular weight distribution makes it easy to mold and process. In addition, the polymerization completion time can be shortened by using it in combination with other polymerization initiators. Furthermore, in the production of methyl methacrylate syrup, syrups with appropriate viscosity and high polymer content can be stably produced, and the remaining amount of initiator, which causes gelation in subsequent processes, can be reduced. can be mentioned. Since the organic peroxide of the present invention has the above-mentioned excellent properties, it becomes an important polymerization modifier in the polymer chemical industry. (Example)' Next, examples of the present invention, comparison examples, and company comparison reference examples will be shown, but the present invention is not limited to these examples. (Manufacture of organic peroxide) Tianwanhuan] (Manufacture of 1-phthylberoxyphenyl carbonate) 28.4 g of t-butylberoxyphenyl carbonate ([], 2
200 g of petroleum ether was added to 22 mol, the separated water was removed, and the organic layer was dried with a small amount of magnesium sulfate. The solution was heated in a 500 ml container equipped with a stirring device at a temperature of 1.
(2) Add 15.8 g (0.20 mol) of pyridine to a Yotsuro fluff 11 while stirring at 5"C, then add 31.7 g (0.2 mol) of phenylchloroporme.
(mol) was added dropwise over a total of 30 minutes. After dropping, the reaction was
It lasted for a while and was completed. The reaction solution was diluted with 150ml of 5% aqueous hydrochloric acid solution, 1! once at 5℃
, 5 minutes), 10% hydroxide) IJ 1, aqueous solution 1 []
once with Omβ (5 °C, 5 min) and 2 times with 150 ml of water.
It was washed 1++1 (10°C, 5 minutes) and dried with a small amount of sodium sulfate. The solvent was then removed under reduced pressure to obtain a crude product with a yield of 30.5 g (70% yield) and a GLC (gas chromatography) purity of 94%. When this crude product was recrystallized using petroleum ether, white crystals with a melting point of 30°C were obtained, and the active oxygen content of this product was 7.51% (theoretical value 7.61%) and the GLC purity was 99%. . Characteristic absorption in the infrared absorption spectrum of this compound (
carbon tetrachloride solution) is 1808 cm-1 (νc = n),
1780cnr-' (C-〇), 1600cm-
' (benzene nucleus) and 1.5[]Ocm-' (
Benzene nucleus), and when the chemical shift of protons in nuclear magnetic resonance spectrum (carbon tetrachloride solution) is expressed as a δ value, the protons of three -C([:Its) groups are 1.4ρI
1m (9+1), benzene nucleus protons are 7.3ppm
Since a signal appeared at (511), it was confirmed that this compound was t-butylperoxyphenyl carbonate. Example 2 [Production of t-butyl peroxyphenyl carbonate] 48.0 g (0.30 mol) of phenyl chloroformate, 38.7 g (0.30 mol) of t-phthyl hydroperoxide
, 30 mol), chloride) 5. Og and water 1
06.0) Put the mixture consisting of i into a 500 m p four-meter flask equipped with a thermometer and a stirrer, and hydroxylate it to 50% with stirring at a temperature of 2 ° C.
The aqueous solution was added dropwise little by little over a period of 25 minutes. After the dropwise addition, the reaction solution was kept at 10° C., and the reaction was continued for an additional 1 hour to complete. The organic layer obtained by separating water from the reaction product liquid was heated at 20°C.
10% hydroxide (1 time with 30 g of aqueous solution, then 10% sulfuric acid)
Washed twice with
9% of 1--butylperoxyphenyl carbonate was obtained. Manufacture of t-amylperoxyphenyl carbonate-1 In Example 1, the reaction was carried out according to Example 1, using t-amyl hydroperoxide instead of 1-butylhydrober material oxide. As a result, a crude product was obtained in a yield of 47.5 g (yield 54%).This crude product was purified by recrystallization using methanol, and the active oxygen content was 6.79% (theoretical value 7.13%). A compound with a GLC purity of 95% was obtained, which was a colorless liquid at room temperature.Characteristic absorption in the infrared absorption spectrum of this compound (
liquid film)], 800 cm-' (νC=O), 1775
cm-' (C-〇), 1595cm' (benzene nucleus) and 1495c'1 (pentene nucleus), and the chemical shift of the proton in the nuclear magnetic resonance spectrum (deuterated chloroform solution) is expressed as a δ value. , -4:
)I, the proton of CH3 group is 1. , Ippm (311
), 'The proton of C(CH3)2- group is 1.3 ppm
(611), -CL, the proton of CH3 group is 1°7p
pm (2N) and benzene nucleus proton is 7.3 ppm
Since a signal appeared at (5H), it was confirmed that this compound was t-amylperoxyphenyl carbonate. n-Example] Preparation of 1-hexyl peroxyphenyl carbonate In a 500-meter flask equipped with a thermometer and a stirring device, 24 t-hexyl hydroperoxide,
3 g (0.20 mol), 15.8 g (0.20 mol) of pyridine
mol) and 200 g of petroleum ether were added and stirred at 18°C.
g (0.17 mol) and 30 g of petroleum ether were added dropwise over a period of 30 minutes. The reaction was continued for an additional 5 hours, and the precipitated pyridine hydrochloride was filtered off. Add 1.0 g (0,013 mol) of pyridine to the reaction product solution and 7.0 g (0
,058 mol) was added and the reaction was continued for 1 hour to complete. At 20°C, the reaction product solution was mixed with 300mj of water!
(1 time with 2% hydroxide) IJ 1, aqueous solution 300ml
It was washed once with 300 mβ of water and then three times with 300 mβ of water, and dried with a small amount of sulfuric acid (IJ). The solvent was removed under reduced pressure to obtain (J
t32.0g (yield 55%), GLC purity 94
% of the compound which is a colorless liquid at room temperature was obtained. Characteristic absorption in the infrared absorption spectrum of this compound (
Carbon tetrachloride solution) is 1802 cm-' (νC=O)
, 1760 cm' (νc=o), 1600 cm
−' (pensen nucleus) talent. Yohi 1500 cm ' (benzene nucleus), and the chemical shifts of protons in the nuclear magnetic resonance spectrum (deuterated chloropol l, solution) are expressed as δ values: -, -
Cit, CI, basic level] ton (0.9ppm
(5N), -C(C,L3)2- group is 1.
4ppm (fill), -C(CH3)2C river, - group protons appear at 1.7ppm (211) and pentene nuclear protons 7, 3ppm (511), so this compound is (-hekynlupel). It was confirmed that Oquine phenyl carbon-1- - Using isopropylphenyl chloropormate, the reaction was carried out according to Example 1. As a result, yield @30
．． 9 g (yield: 54%) of a crude product with GT,C purity of 88% was obtained. This crude product was recrystallized using methanol,
A compound with a GLC purity of 95% was obtained, which was a colorless liquid at room temperature. The characteristic absorption in the infrared absorption spectrum of this compound (
Carbon tetrachloride solution) is 1810 cm-' (νc=o)
, 1780cm-1 (C-0), 1580cm'
(benzene nucleus) and 1500cm- (benzene nucleus), and when the chemical weight of protons in nuclear magnetic resonance spectrum (carbon tetrachloride solution) is expressed as δ value, -, -
, -CII (Cl) 2 group protons are 1.2 ppm (
611), -[(J:L): + group p[)ton is 1.4
ppm(911), -CH(Ct13) Since signals appear at 3.2prim(111) and pentene nuclear proton at 7.3ppm (4N), this compound is 1-butylper4quine 2-isopropyl. It is carbonate. The second one is definitely S and buko. Example 1 [Production of t-butylperoxy 2-sec-butylphenyl carbonate] In Example 1, using sec-butylphenyl chloroformate instead of phenyl chloroformate,
The reaction was carried out according to Example 1. As a result, the yield was 43.9.
g (yield 72%), a compound with a GLC purity of 88% was obtained, which was a colorless liquid at room temperature. Characteristic absorption in the infrared absorption spectrum of this compound (
carbon tetrachloride solution) is 1807 cm-' (νc=o),
1772cm-' (C-0), 1580cm', (
benzene nucleus) and 1495 cm' (benzene nucleus), and when the chemical shift of the proton in the nuclear magnetic resonance spectrum (carbon tetrachloride solution) is expressed as a δ value, -
C112U', river. The proton of the group is 0.9 ppm (3
11), the proton of -CHCH, group is 1.2 ppm (
3tl), -, 3 protons of C(CH,) are 1.4
ppm(911), -C1,, the proton of CH13 group is 1.7ppm (2N), -CI(CH3) (CH□
The proton of CH3) group is 2.91111m (111
) and benzene nuclear protons are 7.2 ppm (4 fl)
Since a signal appeared, it was concluded that this compound was t-butylper]xy secondary butylphenyl carbonate. Production of 3-methylphenyl carbonate [t-)' delperoxy] In Example 1, the reaction was carried out in accordance with Example 1, using 3-methylchloroformate instead of phenylchloroformate. As a result, we obtained 35.2g (yield: 73g).
%) with a GLC purity of 93%. This product was a colorless liquid at room temperature. Characteristic absorption in the infrared absorption spectrum of this compound (
Carbon tetrachloride solution) is 1808 cm-' (νC=O)
, 1780c+rr' (νc=o), 1600cm
' (benzene nucleus) and 1500cm ' (benzene nucleus), and when the chemical shift of the proton in the nuclear magnetic resonance spectrum (carbon tetrachloride solution) is expressed as a δ value, the proton of the three -C(tTt13) groups is 1.4ppm
(9N), -[': 1j-3 protons 2, 2p
pm (311) and the pentene nuclear proton is 7.2
Since a signal appeared at ppm (4 tl), this compound was confirmed to be t-butylperoxy 3-methylphenyl carbonate. Example 8 (Production of t-amylperoxy 2,4-dimethylphenyl carbonate) In Example 1, t-butyl hydroperoxide and phenylchloroformate t-amyl hydroperoxide and 2,4-dimethylphenylcarbonate were prepared. ] Using ropolmate, the reaction was carried out according to Example 1. As a result, the yield was 35.7 g (yield 65%).
) to obtain a compound with a purity of 92%. This was a colorless liquid at room temperature. The characteristic absorption (carbon tetrachloride solution) in the red evening one-line absorption spectrum of this compound is 1808cnr-' (C=O
), 1780cm' (νc=o), 160f1cm
-' (benzene nucleus) and 1500 cm-' (benzene nucleus), and when the chemical shifts of protons in the nuclear magnetic resonance spectrum (deuterated chlorocopol l, solution) are expressed as δ values, -CI, CI+ 3 The protons of the group are 1.1111]m(3H), C((”, tl 3
) The proton of the 2-group is 1.311T]m (6 old, -C
The proton of H2[':)I3 group is 1.7 ppm (21
1), -C13 group proton is 2.2 ppm (611)
Since a signal appeared at 7.2 ppm (3 tl) for the benzene nuclear proton, it was confirmed that this compound was t-amylperoxy 2,4-dimethylphenyl carbonate. - Example 1 [Production of t-butylperoxy 4-chlorophenyl carbonate] In Example 1, 4-chlorophenylcroto 1 formate was used instead of phenylac V]ropolme). The reaction was carried out according to the following conditions: 30.9 g (yield: 58%) and active oxygen amount: 5°91)% (
It is a compound Gf5 with a theoretical value of 6.54%). This compound was a white crystal with a melting point of 119-41°C. The characteristic absorption in the infrared absorption spectrum of this compound (
carbon tetrachloride solution) is 1805 cm' (νc=n),
1780cm-' (C-〇), 15!150m'
(pensene nucleus) and 1490 cm ' (pensene nucleus), and the chemical shift of the proton in the nuclear magnetic resonance spectrum (carbon tetrachloride solution) is expressed as a δ value.
-CE++ Yes. The proton of the group is 1.4 ppm (9N)
and the proton of the benzene nucleus is 7.2 ppm (4H, 4
Since a signal appeared on the symmetrical 4-ton line due to the O group substituted at the - position, it was confirmed that this compound was t-butylperoquine 4-chlorof-, nyl carbonate. Husband - Vehicle weight - 1! l! [Manufacture of 2,5-dimethyl-2,5-di(phenoquinecarbonylperxoxy)hexane] 2,5-dimethylhexane-2,5- in a 1P quartz tank equipped with a thermometer and a stirring device] Dihydroberoquinto 44.6g (
0.25 mol), 39.6 g (0.50 mol) of pyridine, and 500 g of petroleum ether, and stirred at 5°C.
In, phenylchloroporme) 6 (1.6 g
A mixture of (0.38 mol) and petroleum ether 2 (Ig) was added dropwise over 30 minutes. After the addition, the reaction was continued for 2 hours to complete, and the reaction product was dissolved in 500 ml of a 5% aqueous hydrochloric acid solution.
once with 300 ml of IJum aqueous solution (5° C., 5 minutes) with 500 ml of water
Wash twice (5℃, 10 minutes) with a small amount of sulfuric acid)
It was dried in a humidifier. When 45.0 g of the crude product from which the solvent was removed was recrystallized using methanol, 10.0 g of the compound was obtained as white crystals with a melting point of 53°C. The amount of active oxygen was 7.57% (theoretical value 7.65%). Characteristic absorption in the infrared absorption spectrum of this compound (
Carbon tetrachloride solution) is 18000 m-' (νC=-O)
, 1780cm-1 (νc=o), 1595cn+-'
(benzene nucleus) and 1495 cm-' (benzene nucleus), nuclear magnetic resonance spectrum (carbon tetrachloride solution)
Expressing the chemical shift i・ of po ) in terms of δ value,
-C-1±3)J, T-,1) is 1.3ppm
(611), -CH2, - group proton is 1.7pp
m(411) and benzene nucleus protons are 5.2 ppm
Since a signal appeared in (ION), it was confirmed that the 1,- compound was 2°5-dimethyl-2,5-di(phenoxycarbonylperoquine)hexane. Comparative Examples 1 and 2 [cumylperoxyphenylcarboun-) (D ”J
4) In Example 1, cumyl hydroperoxide was used in place of t-butyl human v1 peroxide, and the reaction was carried out according to the same procedure as in Example 1. As a result, although rapid heat generation was observed, the reaction product It was not possible to isolate and confirm cumyl peroxyphenyl carbonate as (
Comparative example 1). In Example 2, a reaction was carried out according to Example 2 using cumyl hydroperoxide instead of t-butylhydroberoquinde.As a result, rapid heat generation was observed, but cumyl was produced as a reaction product. Peroxyphenyl carbonate could not be removed (Comparative Example 2). :3() According to Comparative Examples 1 and 2, in the known method using an alkali or a tertiary amine, the above-mentioned Belgian Patent No. 66
It can be seen that the di-aralkyl peroxyaryl carbonate contained in the above-mentioned general formula (1) in Publication No. 0383, in which R is a 5th-class aralkyl group and R' is an aryl group, cannot be easily synthesized. Ichijibo Weekly, '1, 19. -Reference Ij 1:L-
[Decomposition rate constant and t-life of peroxyaryl carbonate] The thermal decomposition of the organic peroxides obtained in Examples 1 to 10 at 0802 mol/1 in cumene was followed at 100 °C, Degradation rate constants and half-lives were determined. The obtained results are shown in Table 1 together with t-butylperoxyisopropyl carbonate and t-butylperoxybenzoate, which are common polymerization initiators, and are shown in Examples 11 to 19 and Reference Example 1 and 2. And so. From Table 1, it can be seen that peroxyaryl carbonate exhibits decomposition characteristics comparable to that of peroxyisopropyl carbonate, which is a common polymerization agent. Number of peroxides at 1st surface °C and half-life (polymerization with peroxycarbonate) Reference example 3? ! - Leeshi 7, Hiki J Shishonoshi L5 [Comparison of t-butylperoxyphenyl carbonate and t-butylperoxyisopropyl carbonate in the polymerization properties of styrene] Example 1 The t-butylperoxyphenyl carbonate and styrene obtained in step 1 were weighed to prepare a styrene solution or a styrene/benzene mixed solution. 5 ml of this solution was placed in each glass ampoule, degassed by the freeze-thaw method, and sealed under vacuum. Each glass ampoule was placed in a constant temperature bath at 100°C for polymerization, and samples were taken at predetermined intervals.
The polymerization rate and number average degree of polymerization were determined using the 02^ type. The polymerization rate and number average degree of polymerization were determined in advance using a calibration curve using a standard sample, and the polymerization rate and number average degree of polymerization were calculated using a polymerization rate of 10.
% or less. The obtained results are shown in Table 2, and these were designated as Reference Examples 3 to 7. Similarly, 1-butylberoxyisopropyl carbonate, which is a common polymerization initiator, and styrene were weighed to have the concentrations shown in Table 3 to prepare a methylene/benzene solution or a styrene/benzene mixed solution. after that,
A glass ampoule was prepared in the same manner as in Reference Example 3, polymerization was carried out, and the polymerization rate and number average degree of polymerization were determined. The obtained results are shown in Table 3, and these were designated as Comparative Examples 3 to 5. As is clear from the comparison between Reference Examples 4 and 5 and Comparative Examples 3 and 4, when t-butyl peroxyphenyl carbonate is used, the polymerization rate is about 20% when compared at the same polymerization rate.
It can be seen that the degree of polymerization of the polymer is decreasing. In addition, in the case of t-butylperoxyisopropyl carbonate, the value of Rp2/(C][:M:l2 is approximately 2 However, t-butylperoxyphenyl carbonate does not satisfy the above formula (2), and Rp2/
It can be seen that the value of (C) CM)' decreases as the value of [C]/[M] increases. This means that berxialyl carbonate exhibits a unique polymerization behavior that is different from conventional polymerization initiators, and that
) indicates that it participates in the polymerization reaction. Kazutoyo = 16, Comparison Reference 8)
Polymerization of styrene (polymerization rate and degree of polymerization)] In Reference Example 3, instead of 0.013 mol/I) and 11 degrees t-butyl peroxyphenyl carbonate, the concentration of 0.05 mol/β shown in Table 4 was used. Using each peroxide of
Bulk polymerization of styrene at 100°C was carried out according to Reference Example 3.
This was done for 20 minutes. The resulting polymerization rates, number average degrees of polymerization, and polymerization rates are shown in Table 4, and are designated as Reference Examples 8 to 16, respectively. Polymerization was carried out according to Reference Example 8 using ordinary polymerization initiators t-butylperoxyisopropyl carbonate and t-butylperoxybenzoate, and the results are similarly shown in Table 4, and each is compared with Comparative Reference Example 1 and 2. From the results in Table 4, it is clear that peroxyaryl carbonates give polymers with a significantly lower number average degree of polymerization at the same polymerization rate than conventional polymerization initiators. Table 4 100 t' using various peroxides:
Results of bulk polymerization of styrene in 120 minutes 1) Equivalent concentration of 0.025 mol/f! was used. Reference Example 17, Comparative Reference (Example 3) [Manufacture of styrene resin (comparison with other peroxides)] In Reference Example 3, instead of 0.013 mol/β1 degree of 1-butyl peroxyphenyl carbonate, Polymerization was carried out according to Reference Example 3 using 0.05 mol/p of t-butylperoxyphenyl carbonate, t-butylperoxyisopropyl carbonate, and t-butylperoxybenzoate, and each of them was used as Reference Example 1.
7 and Comparative Reference Examples 3 and 4. The resulting polymerization rate curve is shown in Figure 1, and the GPC of the final polymer is shown in Figure 1.
(gel permeation chromatography) curve
Shown in the figure. From the polymerization rate curve in FIG. 1, when the usual polymerization initiators shown in Comparative Reference Examples 3 and 4 are used, a rapid increase in the rate due to the gel effect is observed in the late stage of polymerization, but Reference Example 17 No gel effect was observed with the organic peroxides shown in Figure 2, indicating that polymerization can be more easily controlled. Further, the number average molecular weight and dispersion index (represented by the number average molecular weight and weight average molecular weight) determined from the GPC curve in Figure 2 are 90,000 and 2.4 in Reference Example 17.
, in Comparative Reference Example 3, it was +20,000 and 2.8, and in Comparative Reference Example 4, it was 140,000 and 3.0. These results indicate that when t-butylperoxyphenyl carbonate is used, a polymer with excellent moldability can be obtained because it does not contain a polymer with a very high molecular weight and has a uniform molecular weight distribution. ing. Reference Example 18, Comparative Reference Examples 5 and 6 [Production of styrene resin (comparison with other polymerization regulators)] In Comparative Reference Example 4, 0.05 mol/IU degree of t-butyl peroxyphenyl carbonate, n-dodecyl Mercaptan or α-methylstyrene dimer was additionally added and polymerization was carried out according to Comparative Reference Example 4, and these were designated as Reference Example 18 and Comparative Reference Examples 5 and 6, respectively. The resulting polymerization rate curve is shown in FIG. 3, and the GPC curve of the final polymer is shown in FIG. 4. From the polymerization rate curve in Figure 3, it can be seen that t-butyl peroxyphenyl carbonate was Reference Example 18 using the above polymerization had a shorter polymerization completion time and better linearity, which indicates that the polymerization is more efficient and easier to control. Further, the number average molecular weight and dispersion index obtained from the GPC curve in FIG. 4 are 74,000 and 2 in Reference Example 18.
．． 4, Comparative Reference Example 5 has a value of 60,000 and 4.8, and Comparative Reference Example 6 has a value of 44,000 and 2.5. It can be seen that the uniformity of the molecular weight distribution of the polymer obtained using t-butyl peroxyphenyl carbonate is equal to or higher than that of conventional polymerization regulators. In the case of n-dodecyl mercapcun, which has a large chain transfer constant of 13, the non-uniformity of the molecular weight distribution is significant, and in the case of α-methylstyrene dimer, which has a small chain transfer constant of 0.3, a large amount remains in the polymer. becomes a problem. 1 reference - reference I touge fu G in j, 22. -Kawaken Reference-Reference-(Da1
η-) 1 Prefecture - [Production of methyl methacrylate syrup] In Reference Example 3, instead of 0.013 mol Zpa degree of t-butylperoxyphenyl carbonate and styrene, 0. According to Reference Example 3, using t-butylper4xyphenyl carbonate and methyl methacrylate at old mol/p concentrations, 90° 120, 140
Then, the polymerization rate, number average degree of polymerization, dispersion index, and initiator residual rate were determined after 160 minutes of polymerization, and the results are shown in Table 5, and the results are designated as Reference Examples 19 to 22. Similarly, in Reference Example 3, 0.013 mol/! According to Reference Example 3, instead of t-butylper4xyphenyl carbonate and styrene at a concentration of 0.01 mol/p, t-butylperoxyisopropyl carbonate and methyl methacrylate were used.
5 and 6 (polymerization was carried out for 1 minute, and the polymerization rate, number average degree of polymerization, dispersion index, and initiator residual rate were determined. In Tables 5 and 6, the initial polymerization rates are 0.32%/min and 0.87%/min, respectively.From this, if peroxyaryl carbonate is used, the same polymerization rate can be obtained. It is clear that when methyl methacrylate is bulk polymerized with a common polymerization initiator, a polymer with a lower degree of polymerization can be obtained than with a common polymerization initiator. , the polymerization rate increased from 39 to 96% in 15 minutes, and the number average degree of polymerization increased to 2900.
It can be seen that the polymerization rate rapidly changes from 38% to 67% (l O).On the other hand, as shown in Table 5, when peroxyaryl carbonate is used, the polymerization rate remains from 38% to 61% even after 40 minutes. However, the number average degree of polymerization is also 250.
Since there is no change from 0 to 350 OL and the residual rate of initiator is lower, it can be seen that it is suitable for the production of methyl methacrylate syrup, which requires delicate control of polymerization.

[Brief explanation of the drawing]

Figures 1 and 3 are graphs showing the relationship between polymerization rate and polymerization time according to reference examples and comparative examples of the present invention, and Figures 2 and 4 are graphs showing the relationship between reference examples and comparative examples of the present invention. This is a GPC curve of a polymer obtained by In both figures, the solid line is a reference example, and the broken line is a comparative reference example. Patent Applicant I” Hon Yushi Co., Ltd. Procedures Supplement 11:, Book 1988
August 21, 2015 Commissioner of the Japan Patent Office Kuro
Buto-organic peroxide: (Relationship with the amended person's case Patent use [9n name (4:14) nhon Yushi Co., Ltd. 4, attorney's specification 1-Claims' 1 Details of the invention Explanation-
1. Title of the invention 6. Contents of amendment (as attached) 1. Specification page 1, line 4 to page 3, line 17 fi %
Correct as below. 2. Claim 1: General formula (wherein R1 and R2 are one or two substituents selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a chlorine atom) and R3 and R2
represents a lower alkyl group having 1 to 4 carbon atoms, and R3 is p
When p is 2, the alkyl group having 1 to 12 carbon atoms is
When -C-C- group or m is an integer from 2 to 4 (CD2), no group is shown. ), an organic peroxide having the ability to adjust the polymerization of an unsaturated qlmer. 2, p is 1, R1 and R12 are hydrogen atoms, and R
3. The organic peroxide according to claim 1, wherein R4 and R5 are methyl groups. 3. The organic peroxide according to claim 1, wherein 1 is 1, R1 and R2 are hydrogen atoms, R and R1 are methyl groups, and 115 is ethyl group. 4. The organic peroxide according to claim 1, wherein β is 1, R, and 1 are a hydrogen atom, R3 and R1 are a methyl group, and R5 is a propyl group. 5. The organic peroxide according to claim 1, wherein β is 1, R1 is a hydrogen atom, ](2 is an isopropyl group substituted at the 2-position, and R3, R4, and R1 are a methyl group. 6. l is 1.1, 1 is hydrogen atom -r, 1 (2 is 2-
position-substituted secondary butyl group, and [13, R4 and R1
Claim 1 or 2 in which is represented by a methyl group
I-Haku - Doshu Shinshu as described in the section. 7. The organic peroxide according to claim 1, wherein p is 1, R1 is a hydrogen atom, R2 is a 3-substituted methyl group, and R3, R4, and R5 are methyl groups. 8, p is 1, and R2 is 2- and :3-, respectively
position-substituted methyl group, R3 and R4 are methyl groups, and l
1) The organic peroxide according to claim 1, wherein <5 is an ethyl group. 9 p is 1, R1 is a hydrogen atom, 17° is a 4-substituted chlorine W1, and R,, R4 and ]( are methyl groups. 10 , p is 2.1, and R7 is a hydrogen atom., 173
and R4 is a methyl group, and R5 is an ethyl group -(
An organic peroxide according to claim 1. 2. Formulas (1) and (2) on page 5 of the specification are respectively corrected as follows. +11 3, J k t rMk L on the 5th line from the bottom of the 500th row
r+ and kLr 8j, "ktrx kLr+ and ni, rAJi" is corrected, and in the 13th line from the bottom of the 500th line, the "stanza -1 to [-" is corrected to [-], the bottom of the same page. In the third line from 1 to 1, " is corrected to [1-+. 4. On the 6th page, line 7 from the bottom, 1-initiator" is corrected to read "modifier." rkL, 8/ on page 6, line 4, J is 1-ktrA
kpJ5, corrected. 6. On page 10, lines 8 to 16 are corrected as shown in 0) below. [Hydroperoxide and phenol, 2-methylphenol, 3-methylphenol, 214-dimethylphenol, 2,6 dimethylphenol, 2-isopropylene τ7
Pyrphenol 2-, -B-butylphenol, 4
-"nary butylphenol, 4- (1,!, 3.3
-tetramethylphthyl)phenol, 2-chlorophenol, 3-dimethylphenol, 4-chlorophenol, 2,4-dimethylphenol, 2-tetramethylphthyl-4-methylphenol, and "7, page 11, line 3, 1 hexane" is corrected to [-hexane 1. 8. On page 11 of the same page, under the formula (TV), 1-(in the formula, R, ,
Il. R3 and! is the same as in the general formula (1) above.
Add 1. 9. Correct “gas chromatography” in line 9 of page 12 to “-gas liquid chromatography”10.
Same number +3rr line 19 [before use]
,,,I i: ii+'F zuro. 11 Same number +5pr 4 lines from the bottom [1 rR+, L,
R3, R4 and (pass 1 IR,, I+., R3,
There are 51 cities in IR4, IR5 and pl. 12, page 24, line 11 (]) [-]bu V] pinot 1 carb fu-1-1 蓓I bropyrufuegol f) -ho♀, -
To,, I to Il' i to-t-ro. 1:3. In the same 2uc line 17, [instead of 2nd grade -] is corrected by 61 to 1 - 2 in place of 2nd grade - 1. 14, the same No. 25 is corrected to "("ki/Grade 2-1 in line 1.1 is 1 year old"-n 2-2nd v!,").

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (However, R_1 and R_2 in the formula are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, and chlorine atoms. One or two substituents selected from the group and R_3 and R_4 represent a lower alkyl group having 1 to 4 carbon atoms,
When l is 1, R_5 represents an alkyl group having 1 to 12 carbon atoms, and when l is 2, it represents a -C≡C- group or a -(CH_2)-_m group where m is an integer of 2 to 4. ) An organic peroxide having the ability to adjust the polymerization of unsaturated monomers. 2, l is 1, R_1 and R_2 are hydrogen atoms, and R
The organic peroxide according to claim 1, wherein _3, R_4 and R_5 are methyl groups. 3. The organic peroxide according to claim 1, wherein l is 1, R_1 and R_2 are hydrogen atoms, R_3 and R_4 are methyl groups, and R_5 is ethyl group. 4. The organic peroxide according to claim 1, wherein 1 is 1, R_1 and R_2 are hydrogen atoms, R_3 and R_4 are methyl groups, and R_5 is a propyl group. 5. The organic peroxide according to claim 1, wherein 1 is 1, R_1 is a hydrogen atom, R_2 is an isopropyl group substituted at the 2-position, and R_3, R_4 and R_5 are methyl groups. 6. Polymerization initiation according to claim 1 or 2, wherein l is 1, R_1 is a hydrogen atom, R_2 is a 2-position substituted secondary butyl group, and R_3, R_4 and R_5 are methyl groups. agent. 7. The organic peroxide according to claim 1, wherein 1 is 1, R_1 is a hydrogen atom, R_2 is a 3-substituted methyl group, and R_3, R_4 and R_5 are methyl groups. 8, l is 1, R_1 and R_2 are respectively 2- and 3-position substituted methyl groups, R_3 and R_4 are methyl groups,
Claim 1 in which R_5 is an ethyl group
Organic peroxides as described in section. 9. The organic peroxide according to claim 1, wherein 1 is 1, R_1 is a hydrogen atom, R_2 is a 4-substituted chloro group, and R_3, R_4 and R_5 are methyl groups. 10, l is 2, R_1 and R_2 are hydrogen atoms, R_3
The organic peroxide according to claim 1, wherein R_4 is a methyl group and R_5 is an ethylene group. 11. The organic peroxide according to claim 1, wherein the unsaturated monomer is styrene. 12. The organic peroxide according to claim 1, wherein the unsaturated monomer is methyl methacrylate.