JPH0426325B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a peroxy group-containing unsaturated monomer,
A method of copolymerizing a peroxycarbonate group-containing copolymer with excellent storage stability using a specific unsaturated peroxycarbonate as a peroxy group-containing unsaturated monomer. Polymerization is possible over a particularly wide temperature range, and the resulting copolymer has peroxycarbonate groups with good storage stability, making it useful as an intermediate for the production of graft copolymers and as a polymer modification material. The present invention relates to a method for producing a containing copolymer. (Prior Art) Various methods are known for copolymerizing a peroxy group-containing unsaturated monomer and an unsaturated monomer. For example, British Pat. ) A method for copolymerizing fumarate and styrene is disclosed. Also, “Polymer Chemistry” No.
17, pp. 183-186 (1960) describes a method for copolymerizing t-butyl peroxycrotonate and vinyl acetate, and Japanese Patent Publication No. 57-42083 discloses a method for copolymerizing t-butyl peroxyallyl carbonate and vinyl chloride. A copolymerization method is disclosed. (Problems to be Solved by the Invention) However, when the above-mentioned peroxy group-containing unsaturated monomer was used for copolymerization, the following problems occurred. t-Butyl peroxy methacrylate, di(t-butyl peroxy) fumarate and t-butyl peroxy crotonate, all α-unsaturated peroxy esters, can be copolymerized with unsaturated monomers under normal conditions. When contained in a copolymer by
- The rate of thermal decomposition of the peroxyester group is significantly increased due to the change from a 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. Therefore, the storage stability of the obtained copolymer deteriorates. In order to have peroxyester groups present in the copolymer without the above drawbacks, it is necessary to lower the polymerization temperature and shorten the polymerization time. Generally, if the polymerization temperature is lowered or the polymerization time is shortened, industrially unfavorable phenomena occur, such as the polymerization rate becoming extremely low or the polymerization possibly not being completed. On the other hand, when t-butyl peroxyallyl carbonate is used, it is an unsaturated peroxycarbonate, but in this case, even if it is contained in the copolymer by copolymerization with vinyl monomer, the peroxycarbonate group is thermally However, since the copolymerizability of the unsaturated groups is non-conjugated, the copolymerizable unsaturated monomers are vinyl chloride and vinyl acetate. There was a problem that it was limited to. (Means for Solving the Problems) The present inventors have solved the drawbacks of the above-mentioned known methods, and the resulting copolymers have excellent storage stability and can contain a wide range of unsaturated monomers. As a result of research aimed at developing a method for copolymerization, it was discovered that the objective could be achieved by using a specific unsaturated peroxycarbonate as a peroxy group-containing unsaturated monomer, and the present invention was completed. That is, the present invention is based on 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. Substituted phenyl group; n is 1-
Indicates an integer of 2. ) and an unsaturated monomer copolymerizable with the unsaturated peroxycarbonate in the presence of a radical polymerization initiator. This is the manufacturing method. Specific examples of the unsaturated peroxycarbonate represented by the above general formula used in the present invention include t-butylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, 1,1,3 , 3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, p-isopropylcumylperoxyacryloyloxyisopropyl carbonate, t-amylperoxymethacryloyloxyisopropyl carbonate, 1,1,3, 3-Tetramethylbutylperoxymethacryloyloxyisopropyl carbonate, t-butylperoxy(ethyl)acryloyloxyisopropyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, cumylperoxy Acryloyloxyisopropoxyisopropyl carbonate, t
-butylperoxymethacryloyloxyisopropoxyisopropyl carbonate, t-amylperoxymethacryloyloxyisopropoxyisopropyl carbonate, cumylperoxymethacryloyloxyisopropoxyisopropyl carbonate, etc., preferably t-butylperoxymethacryloyloxyisopropyl carbonate, These include t-butylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxyisopropoxyisopropyl carbonate, t-butylperoxyacryloyloxyisopropoxyisopropyl carbonate, and the like. The reasons why they are preferable are that these unsaturated peroxycarbonates have good copolymerizability with various unsaturated monomers, high polymerization initiation efficiency of peroxycarbonate groups, and that they are easy to synthesize as unsaturated peroxycarbonates. Its advantages include high yield and ease of handling due to its chemical stability. 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-butyl Examples include 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 having 1 to 8 carbon atoms. 1 to 8 alkyl esters, styrene, nuclear-substituted styrene, and the like. 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, 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, which 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 (that is, the 10-hour half-life temperature) is appropriately selected from 10 to 130°C. Examples of polymerization initiators applicable to the above include dibenzoyl peroxide, dilauroyl peroxide, isobutyryl peroxide, acetylcyclohexylsulfonyl peroxide, t-butylperoxypivalate, cumylperoxyneodecanoate, t-butylperoxyacetate. , t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)cyclohexane, dicumyl peroxide, di-t-butylperoxide, azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvalero) nitrile), t-butyl hydroperoxide, cumene hydroperoxide, hydrogen peroxide, potassium persulfate, ammonium persulfate, etc. The amount of these polymerization initiators added is usually within the range of 0.01 to 10% by weight based on the total amount of unsaturated peroxycarbonate and unsaturated monomer charged for polymerization represented by the above general formula. It is preferable to use 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, the polymerization reaction will occur rapidly and runaway, which is undesirable from the viewpoint of safety. 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 known general polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, or by batch or continuous methods. It can be done.
In addition, during polymerization, molecular weight regulators such as aldehydes, halogenated hydrocarbons, mercabutanes,
By adding lower fatty acids, alcohols, -lower fatty acid esters, etc. 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.
It's in the range of 800,000 to 800,000. The chemical structure of the copolymer obtained by the production method of the present invention can be confirmed by the infrared absorption spectrum and measurement of the amount of active oxygen, and the peroxycarbonate groups and unsaturated monomer groups in the copolymer can be confirmed. The composition ratio of 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) The unsaturated peroxycarbonate represented by the above general formula has good copolymerizability with a wide range of unsaturated monomers, so 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. In addition, since polymerization can be performed over a wide temperature range, the time required for polymerization can be shortened.
It also has the effect of making it easier to adjust the degree of polymerization. Furthermore, the copolymer obtained by the method of the present invention has excellent storage stability and is suitable as a polymer modifier or an intermediate for graft copolymerization. (Example) Hereinafter, the present invention will be specifically explained by reference examples, examples, and application examples. Reference Example (Synthesis of unsaturated peroxycarbonate) t-Butylperoxymethacryloyloxyisopropyl carbonate was synthesized by a method according to Soviet Patent No. 374284. That is, 336.6 g (1.2 mol) of a 20% by weight aqueous potassium hydroxide solution was placed in a four-necked flask equipped with a stirrer, a thermometer, and a dropping funnel, and then 70% by weight of t- Butyl hydroperoxide aqueous solution
154.5 g (1.2 mol) was added into the flask. Next, 225.8 g of methacryloyloxyisopropyl chloroformate with a purity of 91.5% 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. The reaction solution was then transferred to a separatory funnel to remove the aqueous phase, and the organic phase was washed twice with 200 ml of cold water at 5°C and dried over magnesium sulfate. After drying, the organic phase was separated to obtain 218.3 g of a colorless and transparent solution. The amount of active oxygen in this solution was determined to be 6.15% 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-butylperoxymethacryloyloxyisopropyl carbonate was produced. Further, the purity calculated from the amount of active oxygen was 95.5%, and therefore the yield was 80.1 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 wavenumber 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 (Structure of peroxycarbonate group-containing copolymer obtained by suspension polymerization) Internal volume 1 equipped with a stirrer, thermometer, Zimrod cooler, nitrogen gas introduction 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 ℃. BPMPC (purity
A mixed solution containing 2.1 g (95.5% by weight) and 4.04 g of diisopropyl peroxycarbonate (purity 99.0% by weight) as a polymerization initiator was prepared.
Under stirring while introducing nitrogen gas at 50°C, incubate for 10
It was dripped in minutes. After that, stirring was continued for 10 hours to obtain a suspension. Next, from the suspension obtained, styrene and
A white bead-like solid, which was recognized as a copolymer with BPMPC, was separated, washed with water, and then dried under reduced pressure. Its weight was 185.5g. 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
BPMPC in copolymer at 1710 and 1790 cm ^-1 respectively
Absorption of the carbonyl group of the ester group and peroxycarbonate group of the structural unit was observed. In the proton nuclear magnetic resonance spectrum, 6.4~
7.4ppm, hydrogen of benzene ring of styrene constituent unit in copolymer, 4.7-5.3ppm, 3.4-4.4ppm, 1.2
~1.4ppm of isopropyl group of BPMPC constituent unit

The hydrogen spectra of [Formula], −CH ₂ and −CH ₃ were observed, and from their integral values,
The calculation revealed that the proportion of BPMPC structural units in the copolymer was 0.98%. That is, it is clear that the white bead-like solid is a peroxycarbonate group-containing copolymer. Moreover, the intrinsic viscosity number in a benzene solution at 25°C was 0.16. Table 3 shows the results regarding the 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 BPAPC as unsaturated peroxycarbonate
(purity 94.0% 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 than the conditions such as the amount of each charge, copolymerization temperature, and copolymerization time shown in Table 3, 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
2.15 g of BPMPPC (purity 93.1% by weight) and diisobutyryl peroxide (purity
50.0% by weight) 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. Immerse the autoclave in a constant temperature water bath kept at 40℃.
By stirring at 32 revolutions per minute for 12 hours
BPMPC and vinyl chloride monomer were copolymerized.
Thereafter, the autoclave was cooled, opened, unreacted vinyl chloride monomer was removed, and the powder was taken out. This white powder was washed with water and dried under reduced pressure. Yield: 82.0g
It was hot. 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-butyl peroxyallyl carbonate (BPAL, purity 70.0% by weight) was used as the unsaturated peroxide in place of BPMPC. 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 Example 2 except that t-butyl peroxyacrylate (BPA, purity 70.0% by weight), which is an unsaturated peroxyester, was used instead of BPAPC.
The copolymerization reaction was carried out according to the method described in . The resulting white solid was insoluble in toluene and tetrahydrofuran. Also, the amount of active oxygen is 0.11%
It was hot. The reaction conditions, analysis results of the reaction products, and results regarding storage stability are shown in Tables 3 and 7, respectively.

[Table] *1 All unsaturated monomers were purified and used by conventional methods.
*2 BPO: dibenzoyl peroxide
IPP: Diisopropyl peroxycarbonate
LPO: dilauroyl peroxide
AIBN: Azobisisobutyronitrile
IBPO: Diisobutyryl peroxide *3 Unsaturated monomer is vinyl acetate: 30℃ acetone solution
〃 Vinyl chloride: 25℃ tetrahydrofuran solution
〃 Others: 25°C benzene solution Example 9 (Production of peroxycarbonate group-containing copolymer by bulk polymerization) 2.09 g of BPMPC (purity 95.5% by weight), 8.0 g of purified styrene, and benzoyl peroxide in a glass ampoule with an internal volume of 20 ml. (purity 99.8% by weight) and 0.1 g were charged, followed by nitrogen purging and then melted. this ampoule
It was immersed in a constant temperature oil bath adjusted to 100°C for 1 hour. Then remove the ampoule, cool it, open it, and release the product.
It was dropped into 500 ml of methanol for precipitation. The white solid was separated and dried under reduced pressure. The yield was 6.3g. In addition, the amount of active oxygen was 1.3%. In addition, as a result of measuring the infrared absorption spectrum, 1725 cm ^-1 ,
Absorption of carbonyl group was observed at 1795 cm ^-1 and characteristic absorption of 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. Table 4 shows the copolymerization conditions and the analysis results of the obtained copolymer, and Table 7 shows the results of the storage stability of the copolymer. 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] Example 15 (Production of peroxycarbonate group-containing copolymer by solution polymerization) BPMPC ( 2.1 g of purified styrene (purity 95.5% 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 set to 100°C.
Adjusted to. 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. Copolymerization conditions and the analysis results of the obtained copolymer, and
The storage stability results 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, analysis results and storage stability results of the obtained copolymers are shown in Tables 5 and 7, respectively. Comparative Examples 6 to 8 Each type and amount of unsaturated peroxide and unsaturated monomer, type and amount of solvent,
Copolymerization was attempted in the same manner as in Example 15, except that the type and amount of initiator added, polymerization temperature and time were changed. 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] 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 BPMPC (purity) prepared separately.
20 g of a mixed solution containing 5.2 g (95.5% 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. then every 30 minutes
A mixed solution of BPMPC and styrene, an aqueous potassium persulfate solution, and an aqueous sodium bisulfite solution were each added in five portions into the flask. 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 0.30%, 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 benzene solution at 25℃ (100ml/g)
was 0.21. 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, the results of analysis of the obtained copolymer, and the results of storage stability were
It is shown in Table and Table 7. 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] 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 the peroxycarbonate groups did not dissociate during the polymerization process, preventing side reactions such as crosslinking reactions, 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 BPMPC 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. Using a mold laboplasto mill, 200℃
The mixture was kneaded for 10 minutes. After that, take out the kneaded material,
The mixture was fractionated 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 74.2%. The surface properties of the molded styrene-grafted polyethylene were better than that of the original polyethylene.

Claims (1)

[Claims] 1. In a method of copolymerizing a peroxy group-containing unsaturated monomer and an unsaturated monomer, the peroxy group-containing unsaturated monomer 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. Substituted phenyl group; n is 1-
Indicates an integer of 2. ) A method for producing a peroxycarbonate group-containing copolymer with excellent storage stability, which comprises copolymerizing an unsaturated peroxycarbonate represented by the following formula in the presence of a radical polymerization initiator. 2. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxymethacryloyloxyisopropyl carbonate. 3. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxymethacryloyloxyisopropyl carbonate. 4. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxymethacryloyloxyisopropoxyisopropyl carbonate. 5. The method for producing a peroxycarbonate group-containing copolymer according to claim 1, wherein the unsaturated peroxycarbonate is t-butylperoxyacryloyloxyisopropoxyisopropyl 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.