JPH0367526B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing a copolymer consisting of a specific unsaturated peroxycarbonate and an unsaturated monomer copolymerizable with the peroxycarbonate, and in particular, the present invention relates to a method for producing a copolymer comprising a specific unsaturated peroxycarbonate and an unsaturated monomer copolymerizable with the peroxycarbonate. The present invention relates to a method for producing a peroxycarbonate group-containing copolymer which has good storage stability and is useful as an intermediate for producing a graft copolymer or as a polymer modifier. (Prior Art) Various methods are known for copolymerizing a peroxy group-containing unsaturated monomer and an unsaturated monomer. For example, British Patent No. 1041088 discloses a method for copolymerizing t-butylperoxymethacrylate and methyl methacrylate,
Japanese Patent Publication No. 46-34100 discloses a method for copolymerizing di(t-butylperoxy) fumarate and styrene. Also, "Polymer Chemistry" Volume 17,
183-186 (1960) describes a method for copolymerizing t-butyl peroxychronate and vinyl acetate, and Japanese Patent Publication No. 57-42083 describes a method for copolymerizing t-butyl peroxyallyl carbonate and vinyl chloride. A method is disclosed. (Problems to be Solved by the Invention) However, when the above-mentioned peroxy group-containing saturated monomer was used for copolymerization, the following problems occurred.
t-Butyl peroxy methacrylate, di(t-
Butylperoxy) fumarate and t-butylperoxycrotonate, which are all α-unsaturated peroxyesters, can be incorporated into copolymers by copolymerization with unsaturated monomers under normal conditions. (The peroxyester group changes from an α-substituted unsaturated carboxylic acid to a peroxyester group of a tertiary carboxylic acid, or from an unsaturated carboxylic acid to a peroxyester group of a secondary carboxylic acid, The rate of thermal decomposition of is significantly increased, and therefore the storage stability of the obtained copolymer is deteriorated.In addition, in order to ensure that the peroxyester group is present in the copolymer without the above-mentioned drawbacks, In order to achieve this, it is necessary to lower the polymerization temperature and shorten the polymerization time. Normally, lowering the polymerization temperature or shortening the polymerization time will significantly reduce the polymerization rate or slow down the polymerization. On the other hand, when t-butylperoxyallyl carbonate is used, this is an unsaturated peroxycarbonate, but in this case, it may not coexist with the vinyl monomer. Peroxycarbonate groups are thermally stable even when incorporated into copolymers through polymerization, so it is possible to polymerize them at relatively high temperatures; however, the copolymerizability of unsaturated groups is non-conjugated. Therefore, there was a problem that copolymerizable unsaturated monomers were limited to vinyl chloride and vinyl acetate.In view of the above-mentioned problems, the present inventors, as a result of long-term research, found that certain unsaturated peroxymonomers By copolymerizing carbonate and an unsaturated monomer copolymerizable with the peroxycarbonate, we confirmed that polymerization can be carried out over a wide temperature range and that the resulting copolymer has good storage stability. (Means and effects for solving the problems) That is, the present invention has the general formula (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; R ₂ is a linear alkyl group having 1 to 9 carbon atoms, a branched alkyl group, a phenyl group, or an alkyl group having 1 to 3 carbon atoms, or a substituted alkyl group having 1 to 3 carbon atoms. phenyl group; n is 1-
A peroxycarbonate group characterized by copolymerizing an unsaturated peroxycarbonate represented by (representing an integer of 2) and an unsaturated monomer copolymerizable with the unsaturated peroxycarbonate in the presence of a radical polymerization initiator. The present invention relates to a method for producing a containing copolymer. Specific examples of the unsaturated peroxycarbonate represented by the above general formula used in the present invention include t-butylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, 1,
1,3,3-Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-
Isopropyl cumyl peroxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxymethacryloyloxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxymethacryloyloxyethyl carbonate, cumyl Peroxymethacryloyloxyethyl carbonate, t-butylperoxy(ethyl)acryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl carbonate carbonate,
t-butylperoxymethacryloyloxyethoxyethyl carbonate, t-amylperoxymethacryloyloxyethoxyethyl carbonate,
Cumylperoxymethacryloyloxyethoxyethoxyethyl carbonate, etc., preferably t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate, etc.
Butylperoxyacryloyloxyethoxyethyl carbonate and the like. The reasons why they are particularly preferable are that these unsaturated peroxycarbonates have good copolymerizability with unsaturated monomers, that the polymerization initiation efficiency of the peroxycarbonate group is high, and that they can be easily synthesized as unsaturated peroxycarbonates. This is because it has a high yield and is chemically stable, making it easy to handle. Examples of unsaturated monomers copolymerizable with the unsaturated peroxycarbonate represented by the above general formula include styrene and its derivatives, acrylic acid and acrylic esters, methacrylic acid and methacrylic esters, vinyl esters, halogen Examples include vinyl chloride, vinylidene halide, conjugated diene, and vinyl ether. Specifically, for example, styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, o-chlorostyrene, p-bromustyrene, p-methoxystyrene, acrylic acid, ethyl acrylate, n-acrylate Butyl, phenyl acrylate, cyclohexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate , methacrylic acid chloride, acrylic acid chloride, vinyl acetate, vinyl propionate, vinyl caproate, vinyl stearate, vinyl benzoate, vinyl chloride, vinylidene chloride, vinylidene fluoride, butadiene, isoprene, methyl vinyl ether, ethyl vinyl ether, n- Examples include butyl vinyl ether, phenyl vinyl ether, ethylene, propylene, tetrafluoroethylene, vinyl pyridine, vinyl imidazole, acrylamide, etc. Preferably, acrylic acid, methacrylic acid, alkyl ester of acrylic acid having 1 to 8 carbon atoms, and methacrylic acid These include alkyl esters having 1 to 8 carbon atoms, styrene, and nuclear-substituted styrene. These unsaturated monomers may be one or two types.
More than one type may be mixed and used. When copolymerizing the unsaturated peroxycarbonate represented by the above general formula and the unsaturated monomer in the present invention, the weight ratio of both is 1 part of the unsaturated monomer to 1 part of the unsaturated peroxycarbonate.
0.0001 to 10 is preferable, and even more preferable.
It is 0.001-1. If the ratio is less than 0.0001,
The proportion of peroxycarbonate groups contained in the copolymer is too small to make it a useful intermediate for producing graft polymers. Moreover, if it exceeds 10, the proportion of peroxycarbonate groups in the copolymer is too high, and there is a risk that rapid decomposition will occur during handling or heating. The copolymerization temperature in the present invention is preferably 0 to 120°C, more preferably 40 to 100°C. 0℃
At lower temperatures, the rate of polymerization is significantly slower, which increases the polymerization time and may not complete the polymerization. Temperatures higher than 120°C are not preferred because the peroxycarbonate groups contained in the copolymer will decompose and side reactions will occur. The radical polymerization initiators used in the copolymerization reaction in the present invention include organic peroxide initiators, azo compound initiators, and inorganic initiators that are polymerization initiators used in ordinary polymerization reactions. The temperature at which the time required for the concentration to reach half of the initial concentration, which is a guideline for the decomposition rate, is 10 hours (i.e.,
The 10-hour half-life temperature) is appropriately selected from those with a half-life temperature of 10 to 130°C. Examples of polymerization initiators applicable to the above include dibenzoyl peroxide,
dilauroyl peroxide, isobutyryl peroxide, acetyl cyclohexyl sulfonyl peroxide, t-butyl peroxypivalate, cumyl peroxy neodecanoate, t-butyl peroxy acetate, t-butyl peroxybenzoate, 1,1-bis(t- butyl peroxy)
Cyclohexane, dicumyl peroxide, di-t-
Examples include butyl peroxide, azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), t-butyl hydroperoxide, cumene hydroperoxide, hydrogen peroxide, potassium persulfate, ammonium persulfate, and the like. The amount of these polymerization initiators added is usually 0.01 to 10% by weight based on the total amount (total amount charged) of unsaturated peroxycarbonate and unsaturated monomer charged for the polymerization represented by the above general formula. It is preferable to use it within this range. If it is less than 0.01% by weight, the polymerization reaction will be extremely slow, which is not preferable. Moreover, if it exceeds 10% by weight, a polymerization reaction will occur rapidly.
This is not desirable from a safety point of view, as it may cause the vehicle to run out of control. In normal polymerization operations, the polymerization reaction is preferably completed in 1 to 20 hours by appropriately selecting the polymerization temperature and the amount of polymerization initiator. The copolymer of the present invention can be produced by a known general polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, or by a batch method or a continuous method. I can do it. In addition, during polymerization, by adding molecular weight regulators such as aldehydes, halogenated hydrocarbons, mercaptans, lower fatty acids, alcohols, and lower fatty acid esters at a ratio of 0.01 to 5% by weight based on the total amount charged, The molecular weight can be adjusted over a wide range. The average molecular weight of the copolymer of the present invention obtained in this way is usually 2000 to 2000.
It's in the 800,000 range. The chemical structure of the copolymer obtained by the production method of the present invention can be determined by confirming the presence of peroxycarbonate groups and other unsaturated monomer groups in the copolymer by measuring the infrared absorption spectrum and the amount of active oxygen. The composition ratio in the polymer is determined by measuring the amount of active oxygen and nuclear magnetic resonance spectrum. Further, the average molecular weight of the copolymer is given from the value of the intrinsic viscosity. (Effect of the invention) Since the unsaturated peroxycarbonate represented by the above general formula has good copolymerizability with a wide range of unsaturated monomers, by varying the charging ratio of the two to be copolymerized over a wide range, It is possible to obtain a peroxycarbonate group-containing polymer having a polymerization ratio depending on the purpose and properties of the copolymer. Furthermore, since the polymerization operation can be carried out over a wide temperature range, the time required for polymerization can be shortened, and the degree of polymerization can be easily adjusted.
Furthermore, the copolymer obtained by the method of the present invention is
It has excellent storage stability and is suitable as a polymer modifier, an intermediate for glass copolymerization, etc. (Example) Hereinafter, the present invention will be specifically explained by reference examples, examples, and application examples. Reference Example (Synthesis of unsaturated peroxycarbonate) t-Butylperoxymethacryloyloxyethyl carbonate was synthesized by a method according to the specification of Soviet Patent No. 374284. That is, 336.6 g (1.2 mol) of an aqueous potassium hydroxide solution with a concentration of 20% by weight was placed in a four-neck flask equipped with a stirrer, a thermometer, and a dropping funnel.
At 20° C., 154.5 g (1.2 moles) of a 70% by weight aqueous solution of t-butyl hydroperoxide was added into the flask. Next, 207.1 g of methacryloxyethyl chloroformate with a purity of 93% by weight was added dropwise over 30 minutes while stirring vigorously and maintaining the temperature at 20°C. After that, stirring was continued for 2 hours. After that, the reaction solution was transferred to a separatory funnel, the aqueous phase was removed, and the organic phase was washed with cold water at 5℃.
Washed twice with 300ml and dried over magnesium sulfate. After drying, the organic phase was separated to obtain 206.0 g of a colorless and transparent solution. The amount of active oxygen in this solution was determined to be 6.24% by iodometry. In addition, infrared absorption spectrum measurements revealed that the absorption of the carbonyl group of the methacrylic acid ester group was 1720.
cm ^-1 , and absorption of the carbonyl group of peroxycarbonate group was observed at 1790 cm ^-1 . From the above, it was confirmed that t-butylperoxymethacryloxyethyl carbonate was produced. Further, the purity calculated from the amount of active oxygen was 96%, and therefore the yield was 80.3 mol%. In addition, this was dissolved in benzene at a concentration of 0.05 mol/cm, and the thermal decomposition rate was measured. As a result, the 10-hour half-life temperature was 104°C. Table 1 shows the molecular weight, amount of active oxygen (theoretical value), purity, yield, and absorption of carbonyl group by infrared absorption spectrum of other unsaturated peroxycarbonates represented by the above general formula synthesized by a method similar to this method. The wave number and 10-hour half-life temperature are shown, respectively.

[Table] The unsaturated peroxides used in the comparative examples are also shown in Table 2.

[Table] Example 1 (Production of peroxycarbonate group-containing copolymer by suspension polymerization) Internal volume 1 equipped with a stirrer, thermometer, Dimroth condenser, nitrogen gas inlet pipe and dropping funnel
Pour 400 ml of 0.2% by weight polyvinyl alcohol (saponification degree 89%) aqueous solution into a four-necked flask,
The temperature was adjusted to ℃. Separately, 198.0g of styrene purified by conventional methods
BPMC (purity
A mixed solution containing 2.08 g (96.0 wt%) and 4.04 g of diisopropyl peroxycarbonate (purity 99.0 wt%) as a polymerization initiator was prepared, and this was stirred at 50°C while introducing nitrogen gas.
It was added dropwise over 10 minutes. After that, stirring was continued for 10 hours to obtain a suspension. Next, white bead-like solids recognized as a copolymer of styrene and BPMC were separated from the resulting suspension, washed with water, and then dried under reduced pressure. Its weight was 170.5g. A part of this was dissolved in toluene-methanol system,
The precipitate was washed repeatedly. Various measurements were performed on this product. As a result, the amount of active oxygen was 0.06
It was %. Also, in the infrared absorption spectrum
Absorption by the ester group and the carbonyl group of the peroxycarbonate group of the constituent unit of BPMC in the copolymer was observed at 1710 and 1790 cm ^-1 , respectively. In the proton nuclear magnetic resonance spectrum, 6.4~
The spectrum of hydrogen of the benzene ring of the styrene constituent unit in the copolymer was observed at 7.4 ppm, and the hydrogen of the ethylene group of the BPMC constituent unit was observed at 3.4 to 4.4 ppm, and from the integral value, it was calculated that
It was found that the proportion of BPMC constituent units was 0.98%. That is, it is clear that the white bead-like solid is a peroxycarbonate group-containing copolymer. In addition, the intrinsic viscosity of a benzene solution at 25℃ is
It was 0.16. Table 3 shows the results regarding the above polymerization raw materials, polymerization conditions, and copolymers. Furthermore, in order to examine the storage stability of the obtained copolymer, the amount of active oxygen was measured after it was placed in a thermostat at 50° C. for one month. As a result, no decrease in active oxygen was observed. The results are shown in Table 7. Examples 2 to 6 As shown in Table 3, the type and amount of unsaturated peroxycarbonate, the type and amount of unsaturated monomer, the type and amount of polymerization initiator, and the copolymerization temperature and copolymerization time. Copolymerization was carried out in the same manner as in Example 1, except that . Table 3 shows the copolymerization conditions and the results of analysis of the obtained peroxycarbonate group-containing copolymer. Table 7 also shows the storage stability of the copolymer measured by a method similar to Example 1. Example 7 BPAC as unsaturated peroxycarbonate
(purity 94.5% by weight), methyl methacrylate was used as the unsaturated monomer, 0.04 g of sodium lauryl sulfate in 200 ml of water as a suspension dispersion,
A solution of 0.53 g of sodium polyacrylate and 1.62 g of sodium sulfate was prepared and used, and other conditions such as the amount of each charge, copolymerization temperature, and copolymerization time shown in Table 3 were also used. Copolymerization was carried out in the same manner as in Example 1. The analysis results and storage stability of the obtained peroxycarbonate group-containing copolymer are shown in Tables 3 and 7, respectively. Example 8 In a stainless steel autoclave with an internal volume of 400ml
0.1% by weight polyvinyl alcohol (saponification degree 89
%) as unsaturated peroxide with 200ml of aqueous solution
2.13 g of BPMC (purity 94.0% by weight) and diisobutyryl peroxide (purity 50.0%) as a polymerization initiator.
Weight%) 0.4g was charged and cooled to -30°C. 98.0 g of vinyl chloride monomer was charged therein, the space in the autoclave was purged with nitrogen, and the autoclave was tightly stoppered. By immersing the autoclave in a constant temperature water bath kept at 40℃ and stirring at 32 revolutions per minute for 12 hours,
BPMC and vinyl chloride monomer were copolymerized.
Thereafter, the autoclave was cooled, the autoclave was opened, unreacted heavy vinyl chloride was removed, and a white powder, which was a reaction product, was taken out. This white powder was washed with water and dried under reduced pressure. The yield was 84.0g. This white powder is a copolymer containing peroxycarbonate groups. The copolymerization conditions, analysis results and storage stability of the copolymer are shown in Tables 3 and 7, respectively. Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that t-butylperoxyallyl carbonate (BPAL, purity 70.0% by weight) was used instead of BPMC as the unsaturated peroxide. As a result, a white solid was obtained, but the amount of active oxygen was 0%, and an infrared absorption spectrum was measured, but no absorption of carbonyl groups was observed. Therefore, a peroxycarbonate group-containing copolymer could not be obtained.
Table 3 shows the reaction conditions and analysis results of the reaction products. Comparative Example 2 In place of BPAC, t-butylperoxyacrylate (BPA,
A copolymerization reaction was carried out in the same manner as in Example 2, except that 70.0% by weight (purity: 70.0% by weight) was used. The resulting white solid was insoluble in toluene and tetrahydrofuran. In addition, the amount of active oxygen was 0.11%. The reaction conditions, analysis results of reaction products, and storage stability results are shown in Tables 3 and 7, respectively.
Shown in the table.

【table】

[Table] Example 9 (Production of peroxycarbonate group-containing copolymer by bulk polymerization) BPMC (purity
96.0% by weight) 2.08g, purified styrene 8.0g and benzoyl peroxide (purity 99.8% by weight) 0.1g,
After replacing with nitrogen, it was sealed. 100 of this ampoule
It was immersed in a constant temperature oil bath adjusted to ℃ for 1 hour. Then take out the ampoule, cool it, open it, and collect the product at 500ml.
ml of methanol for precipitation. The white solid was separated and dried under reduced pressure. The yield was 5.8g.
In addition, the amount of active oxygen was 1.20%. In addition, as a result of measuring the infrared absorption spectrum, 1725 cm ^-1 and 1795 cm
Absorption of the carbonyl group was observed at ^-1 , and characteristic absorption of the benzene ring was observed below 1600 cm ^-1 . From this result, it was confirmed that this white solid was a copolymer consisting of styrene structural units and peroxycarbonate structural units. Copolymer conditions and analysis results of the obtained copolymer are shown in Table 4, and results of storage stability of the copolymer are shown in Table 7. Examples 10 to 14 A method according to Example 9 except that the type and amount of unsaturated peroxycarbonate, the type and amount of unsaturated monomer, the type and amount of initiator added, the copolymerization temperature, etc. were changed. Copolymerization was carried out using The copolymerization conditions and the analysis results and storage stability results of the obtained copolymers are shown in Tables 4 and 7, respectively. Comparative Example 3 Copolymerization was carried out in the same manner as in Example 9, except that BPAL was used as the unsaturated peroxide.
The result of measuring the amount of active oxygen in the obtained white solid was 0.
It was %. In addition, in the measurement of infrared absorption spectra,
No carbonyl group absorption was observed between 1700 and 1800 cm ^-1 . Therefore, a peroxy group-containing copolymer could not be obtained. Table 4 shows the reaction conditions and analysis results of the reaction products. Comparative Examples 4-5 BPA or DBPF as unsaturated peroxide
Copolymerization was carried out in the same manner as in Example 9 under the conditions shown in Table 4, including the use of unsaturated monomers, the type and amount of unsaturated monomers, and the type and amount of initiators added.
The analysis results and storage stability results of the obtained copolymer are shown in Tables 4 and 7, respectively.

【table】

[Table] Example 15 (Production of peroxycarbonate group-containing copolymer by solution polymerization) BPMC (purity 96.0 % by weight), 98.0 g of purified styrene, and 200 g of ethylene glycol monobutyl ether (abbreviated as butyl cellosolve) as a solvent were charged, and the flask temperature was adjusted to 100°C. Next, 1.0 g of BPO (purity 99.0% by weight) was added as an initiator into the flask, and copolymerization was carried out for 5 hours while stirring under nitrogen gas flow. Thereafter, the reaction solution was added dropwise to cold methanol in Step 3, and the precipitated white solid was dried under reduced pressure. Its weight was 82.0g. The amount of active oxygen in this white solid is
As a result of measuring the infrared absorption spectrum, carbonyl group absorption was observed at 1710 and 1790 cm ^-1 . The intrinsic viscosity (100ml/g) of the benzene solution at 25°C was 0.22. The copolymerization conditions and the analysis results and storage stability results of the obtained copolymer are shown in Tables 5 and 7, respectively. Examples 16-20 The type and amount of unsaturated peroxycarbonate, the type and amount of unsaturated monomer, the type and amount of solvent, the type and amount of initiator, copolymerization temperature, copolymerization time, etc. Copolymerization was carried out in the same manner as in Example 15, except for the following changes. The copolymerization conditions and the analysis results and storage stability results of the obtained copolymers are shown in Tables 5 and 7, respectively. Comparative Examples 6 to 8 Example 15 except that the types and amounts of unsaturated peroxide and unsaturated monomer, the type and amount of solvent, the type and amount of initiator, polymerization temperature and time were changed. Copolymerization was attempted using a method similar to . Tables 5 and 7 show the polymerization conditions, analysis results of the obtained polymers, and storage stability measurements of the polymers containing active oxygen, respectively.

【table】

[Table] Example 21 (Production of peroxycarbonate group-containing copolymer by emulsion polymerization) 1.0 g of sodium dodecyl sulfate was placed in a 500 ml four-necked flask equipped with a thermometer, stirrer, dropping funnel, and nitrogen introduction tube. an aqueous solution of
Add 200g of BPMC (purity) prepared separately.
20 g of a mixed solution containing 5.2 g (96.0% by weight) and 95.0 g of purified styrene was added. The liquid in the flask was heated to 50°C under nitrogen gas flow, and then an aqueous solution 15 in which 0.6 g of potassium persulfate was dissolved was added.
ml and 15 ml of an aqueous solution in which 0.6 g of sodium bisulfite was dissolved, and 1.5 ml of each solution was prepared.
was added into the flask. After that, every 30 minutes,
A mixed solution of BPMC and styrene, an aqueous potassium persulfate solution, and an aqueous sodium bisulfite solution were each added to the flask in five portions. After the entire amount was added, stirring was continued for another hour. Thereafter, the emulsion was cooled, and the emulsion obtained was added to 1 part of a 0.5 mol/concentration aqueous sodium sulfate solution for salting out.
The solid was washed twice with water and dried to obtain 62.3 g of a white solid. The amount of active oxygen in this product is 0.31%, and the results of measuring the infrared absorption spectrum are 1710 and 1790 cm ^-1
Absorption of carbonyl groups was observed in each case. Also, the intrinsic viscosity of 25% benzene solution (100ml/g)
was 0.22. The copolymerization conditions, the results of the analysis of the obtained copolymer, and the results of the storage stability of the copolymer are shown in Tables 6 and 7, respectively. Examples 22 to 23 Copolymerization was carried out in the same manner as in Example 21, except that the types and amounts of unsaturated peroxycarbonate and unsaturated monomer and the copolymerization conditions were changed. The copolymerization conditions and the results of analysis and storage stability of the obtained copolymers are shown in Tables 6 and 7, respectively. Comparative Examples 9 to 10 Same as Example except that the type and amount of unsaturated peroxide and unsaturated monomer and copolymerization conditions were changed.
Copolymerization was carried out according to the method described in 21. The results of analysis and storage stability of the obtained copolymer are shown in Tables 6 and 7, respectively.

【table】

【table】

【table】

[Table] From the above examples and comparative examples, the unsaturated peroxycarbonate represented by the above general formula has good copolymerizability with a wide range of unsaturated monomers;
It has been found that copolymers containing peroxycarbonate groups in a wide range of proportions can be easily produced, and that the polymerization reaction can be carried out efficiently because the peroxycarbonate groups are stable at relatively high polymerization temperatures. Furthermore, it was found that there was no cleavage of the peroxycarbonate groups during the polymerization process, and side reactions such as crosslinking reactions could be prevented, and that the storage stability of the peroxycarbonate groups in the obtained copolymer was good. Application example (grafting of polystyrene to polyethylene) 30 g of the copolymer of BPMC and styrene produced in Example 1 (active oxygen content 0.06%) and 100 g of low density polyethylene (degree of polymerization 3300) were mixed and mixed in a Banbury mixer. 200℃ using type Labo Plastomill
The mixture was kneaded for 10 minutes. After that, take out the kneaded material,
Fractionation was performed using a xylene-acetone solvent to separate polystyrene grafted polyethylene chains, and the grafting efficiency was determined from the weight. The result is
It was 77.2%. The surface properties of the molded styrene-grafted polyethylene were better than that of the original polyethylene.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; R ₂ is a linear alkyl group having 1 to 9 carbon atoms, a branched alkyl group, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Substituted phenyl group: n is 1
A peroxycarbonate characterized by copolymerizing an unsaturated peroxycarbonate represented by (representing an integer of ~2) and an unsaturated monomer copolymerizable with the unsaturated peroxycarbonate in the presence of a radical polymerization initiator. Method for producing group-containing copolymer. 2. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxymethacryloyloxyethyl carbonate. 3. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxyacryloyloxyethyl carbonate. 4. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxymethacryloyloxyethoxyethyl carbonate. 5. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxyacryloyloxyethoxyethyl carbonate. 6 The unsaturated monomer is acrylic acid, methacrylic acid,
C1-8 alkyl ester of acrylic acid,
The method for producing a peroxycarbonate group-containing copolymer according to claim 1, which is an alkyl ester having 1 to 8 carbon atoms of methacrylic acid, styrene, and nuclear-substituted styrene. 7. The method for producing a peroxycarbonate group-containing copolymer according to any one of claims 1 to 6, wherein the temperature of the copolymerization reaction is 0 to 120°C. 8. When copolymerizing the unsaturated peroxycarbonate and the unsaturated monomer, the weight ratio of the unsaturated monomer to the unsaturated peroxycarbonate is 1:0.0001 to 10. 8. A method for producing a peroxycarbonate group-containing copolymer according to any one of Item 7.