JPH0141641B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel radical polymerization initiator, particularly a radical polymerization initiator having a functional group, a polymer or copolymer obtained using the same as an initiator, and a method for producing the polymerization initiator. be. It is well known that various peroxides are useful as initiators for radical addition polymerization.
These are already widely used industrially. However, these peroxides are essentially
It is extremely unstable to heat, shock, light, etc., and its synthesis, especially industrial production, has been extremely difficult. Therefore, there are very few known examples of these peroxides, particularly peroxides that can be used as polymerization initiators, and those that can be obtained industrially are extremely limited. On the other hand, in industries such as plastics, rubber, paints, and adhesives, various peroxide-based polymerization initiators are in demand, and in recent years in particular, the properties of radical addition polymers or copolymers have The structure of the peroxide used as an initiator has become extremely important as it has become clear that it is significantly influenced by structure. However, as mentioned above, conventional methods for producing peroxides have various difficulties, and even more so,
In particular, it has been impossible to produce peroxides with functional groups. The present inventors synthesized a large number of peroxides by making full use of the method for easily producing peroxides under extremely mild conditions described below, and investigated their polymerization initiation function. As a result, the general formula () indicated by (R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ represent a hydrogen atom, a halogen atom, or an organic group. However, R ₁ = R ₂ = R ₃ = R ₄ = R ₅ = a hydrogen atom or a halogen atom) ) and has one or more functional groups in at least any one of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ . It was completed. The present invention will be explained in more detail below. The radical polymerization initiator referred to in the present invention is a compound that has the ability to generate radicals through thermal decomposition, photolysis, redox decomposition, etc., and has the ability to initiate radical addition polymerization of vinyl monomers. . Examples of vinyl monomers mentioned here include vinyl monomers in the narrow sense such as vinyl chloride, vinyl acetate, vinyl cabazole, and vinylpyrrolidone, and aromatic alkenyls such as styrene, p-methylstyrene, and vinylpyridine. Acrylic and methacrylic monomers such as acrylic acid, methyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, acrylonitrile, and methacrylamide, vinylidene monomers such as vinylidene chloride, vinylidene cyanide, etc. ethylene, olefinic monomers such as α-olefin, butadiene,
Examples include diene monomers such as isoprene and chloroprene. The functional groups referred to in the present invention are (a) chemically reactive, (b) hydrophilic, when a polymerization initiator represented by the general formula () is introduced into a polymer as an initiator fragment
(c), Water repellency, (d), Plasticity, (e), Impact resistance, (f),
A group that exhibits functions such as polymerization initiation, examples of which are (a) Chemical reactivity: carboxylic acid group, carboxylic acid base, sulfonic acid group, sulfonic acid group, phosphoric acid group, phosphoric acid group,
Amino group, amide group, lactone group, lactam group, epoxy group, acid anhydride group, hydroxyl group, thiol group, nitro group, nitrile group, isocyanate group, etc. (b) Hydrophilicity: carboxylic acid group, carboxylic acid base, sulfone Acid group, sulfonic acid group, phosphoric acid group, phosphoric acid group,
Amino groups, ammonium bases, ether groups, hydroxyl groups, etc. (c) Water repellency: Silyl groups, fluoroalkyl groups, etc. (d) Plasticity: Ether groups, ester groups, amide groups, number of carbon atoms
10-400 alkyl group, (e) Impact resistance: ether group, ester group, alkyl group having 10-400 carbon atoms, etc. (f) Polymerization initiation: Examples include azo group, peroxide group, etc. It will be done. In the general formula (), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ represent a hydrogen atom, a halogen atom, or an organic group,
The organic group may have a chain structure or a cyclic structure, or two or more of each organic group may be combined to form a cyclic structure. Although the radical polymerization initiator having a functional group represented by the general formula () can be synthesized by various methods in principle, it can be synthesized by the general formula () using singlet oxygen described below. The most preferred method is to oxidize the compound shown in . An example of a radical polymerization initiator having a functional group represented by the general formula () is: etc. In order to produce a radical polymerization initiator having such a functional group, it is most preferable to use singlet oxygen oxidation as described above. Here, singlet oxygen is one of the active oxygen species, and can be generated by various methods. For example, by reacting hydrogen peroxide with sodium hypochlorite, or by converting oxygen molecules into singlet oxygen molecules by microwave discharge. Examples include a method of converting oxygen molecules into singlet oxygen, and a method of converting oxygen molecules into singlet oxygen by irradiating visible light in the presence of a sensitizing substance. Most preferred is a method using light irradiation, the so-called photosensitized oxidation method. In such photosensitized oxidation reaction systems, dye compounds such as rose bengal, methylene blue, and tetraphenylporphine are used as sensitizing substances, and these may be used by being dissolved in a medium together with the oxidized material. Alternatively, such a sensitizing substance may be insolubilized on a carrier and used as a so-called heterogeneous sensitizer (Japanese Patent Application No. 1983-
No. 21829, patent application No. 1983-21830). In particular, if the latter method is used, it is extremely easy to separate the product and the sensitizer. As the visible light source, sunlight may be used, or an artificial light source such as a halogen lamp, sodium lamp, or tungsten lamp may be used.
The reaction temperature is usually around room temperature, and there is no need for special heating.If necessary, the reaction can proceed sufficiently even under cooling conditions, making it extremely useful as a means of synthesizing particularly thermally unstable peroxides. It's advantageous. The most important feature is that the peroxide produced under such reaction conditions does not undergo any secondary decomposition, which is essentially different from peroxide synthesis by other oxidation methods. It is possible to set ideal production conditions that naturally result in high conversion and high yield. This greatly shortens the process of separating and purifying peroxides, which poses fatal difficulties in peroxide synthesis, especially in the synthesis of peroxides with complex functional groups, and in many cases, after the reaction, It becomes possible to use it as it is as a polymerization initiator without any particular purification. Due to these advantages, the present inventors synthesized an extremely large number of peroxides and discovered a radical polymerization initiator having a large number of useful functional groups. The radical polymerization initiator of the present invention can be used in the same manner as for ordinary initiators. That is, polymerization can be easily initiated by decomposition by methods such as thermal decomposition, redox decomposition, and photodecomposition. As mentioned above, monomers that can be used include vinyl monomers, aromatic alkenyl monomers, acrylic and methacrylic monomers, vinylidene monomers, olefin monomers, and diene monomers. , and any other monomers that can be radically polymerized or radically copolymerized can be used.
When a radical polymerization initiator having such a functional group is used, these decomposed products are mainly introduced into the end groups of the polymer or copolymer as initiator fragments, and the introduction efficiency depends on the type of initiator and polymerization. Although it varies depending on the conditions, it is usually in the range of 1% to 100%. The polymer or copolymer obtained using the polymerization initiator of the present invention has an initiator fragment containing a functional group at the end group as described above, and It exhibits significantly different properties compared to polymers or copolymers. The degree of the effect is greater as the introduction efficiency is higher, but even if the introduction efficiency is low, the effect is sufficiently exhibited. By selecting the type of functional group used, arbitrary properties can be imparted to the polymer or copolymer. ) It is extremely useful because it can impart properties such as water repellency, (d) plasticity, (e) impact resistance, and (f) polymerization initiation. The specific effects are as follows: (a) Chemical reactivity For example, when the polymer having a terminal reactive group of the present invention is blended with another polymer having a group capable of reacting with the reactive group, there is a significant compatibility. It has improved solubility and is extremely useful as a material for reactive blends, which is expected to enable various polymer blends that were previously impossible. (b) Hydrophilicity For example, the polymer having a hydrophilic group of the present invention exhibits the effects of improving self-emulsifying property, water dispersion stability, dyeing property, and adhesion property. (c) Water repellency For example, when the polymer having a water repellent group of the present invention is used as a film or other molded product, effects such as non-staining properties are exhibited. (d) Plasticity For example, the polymer having a plasticity group of the present invention has been found to have significantly improved flow properties, lowering the heat distortion temperature, and
Excellent effects are found in terms of plasticizer migration, etc. (e) Impact resistance For example, the polymer having an impact resistant group of the present invention can improve impact resistance without impairing transparency, compared to the conventional means of improving impact resistance by blending rubber-based polymers. It improves performance and is extremely useful. (f) Polymerization initiation properties For example, the polymer having a polymerization initiating group of the present invention can be used to obtain a novel block type copolymer by polymerizing different types of monomers, and it is possible to obtain a new block type copolymer by polymerizing different types of monomers. Compared to copolymer manufacturing methods, a wide range of combinations are possible, and
It is possible to employ industrially easy processes such as radical polymerization, and is extremely useful. As mentioned above, the polymerization initiator and polymer of the present invention have various properties not found in conventional initiators and polymers, and are extremely useful industrially. The present invention will be explained in more detail below with reference to Examples. Examples 1 to 19 Among the compounds illustrated in Table 1, compound number No. 1,
4, 5, 7, 9, 10, 11, 12, 13, 14, 15, 16,
Each of the compounds 17, 18, 19, 20, 21, 22, 23,
The solution was dissolved in 100 parts of toluene containing 15 parts of tetraphenylporphine and 0.01 part of tetraphenylporphin, and placed in an internal irradiation type photoreactor (light source 400W metal halide lamp, manufactured by Toshiba), and heated to 100,000 lux on the surface of the container while being aerated at 20°C. By irradiating for 5 hours, peroxide numbers No. 1, 4, and
5, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17,
A polymerization initiator containing 18, 19, 20, 21, 22, and 23 as main components was obtained. The amount of active oxygen was measured from the above reaction solution by the acetic acid-potassium iodide method, and the results are shown in Table 3. Table 3 also shows the half-life times measured from the thermal decomposition rate at 90°C. Examples 20 to 23 Among the compounds listed in Table 1, compound number No.
15 parts each of compounds 2, 3, 6, and 8, 400 parts water
Porous resin (Amberlite XAD-
7 (manufactured by Rohm & Haas), as well as an internal irradiation type photoreaction device (light source: 400W metal halide lamp,
(manufactured by Toshiba) and irradiated the container surface with 100,000 lux for 6 hours while aerating at 20°C. After irradiation, the peroxide No. 2 shown in Table 2 was separated.
A polymerization initiator containing 3, 6, and 7 as main components was obtained. The amount of active oxygen was measured from the above reaction solution by the acetic acid-potassium iodide method, and the results are shown in Table 3. Table 3 also shows the half-life times measured from the thermal decomposition rate at 90°C.

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[Table] Percentage divided by molecular weight.
Example 24 The polymerization initiator of peroxide number No. 14 synthesized in Example 10 was used as an initiator at the following charging ratio.

[Table] When emulsion polymerization was carried out at 20°C, it was completed in 6 hours and the polymerization rate was 99%. The polymer obtained above was purified by reprecipitation using a methylene chloride-methanol system, and the weight average molecular weight and number average molecular weight were determined by gel permeation chromatography (Shodex column). Further, the amount of epoxide in the polymer was determined by the hydrochloric acid-dioxane method. The results are shown in Table 4.

[Table] From the results in Table 4, it is clear that the initiator fragments were introduced into the polymer at a rate of 95%, and were introduced into almost all of the main chain. Example 25 At the following charging ratio, the polymerization initiator with peroxide number No. 15 synthesized in Example 11 was used as an initiator.

[Table] When suspension polymerization was carried out at 60°C, the polymerization rate was 99% in 12 hours. The polymer obtained above was purified by reprecipitation using a methylene chloride-acetone system, and the weight average molecular weight and number average molecular weight were determined by gel permeation chromatography (Shodex column). In addition, the amount of acid anhydride in the polymer is 1800 cm ^-1
It was determined using an infrared absorption spectrophotometer based on the characteristic absorption of carbonyl acid anhydride at 1750 cm ^-1 . The results are shown in Table 5.

[Table] From the results in Table 5, it is clear that the initiator fragments were introduced into the polymer at a rate of 96%, and were introduced into almost all of the main chain. Example 26 At the following charging ratio, the polymerization initiator with peroxide number No. 3 synthesized in Example 21 was used as an initiator.

[Table] When polymerization was carried out at 20°C, it was completed in 8 hours and the polymerization rate was 99%. The polymer obtained above was mixed with tetrahydrofuran-(methanol-water).
The product was purified by reprecipitation, and the weight average molecular weight and number average molecular weight were determined by gel permeation chromatography. In addition, the sodium sulfonate groups in the polymer were quantified by methylene blue staining. The results are shown in Table 6.

[Table] From the results in Table 6, it is clear that the introduction rate of the initiator fragment into the polymer was 93%, and it was introduced into almost all the main chains. Furthermore, the obtained polymer was stable in an aqueous solution even in the absence of an emulsifier, and exhibited self-emulsifying properties. Example 27 At the following charging ratio, the polymerization initiator with peroxide number No. 23 synthesized in Example 19 was used as an initiator.

[Table] When suspension polymerization was carried out under pressure at 50°C, the polymerization rate was 85% in 20 hours. The polymer obtained above was purified by reprecipitation using a dimethylformamide-toluene system, and its weight average molecular weight and number average molecular weight were determined by gel permeation chromatography. In addition, the amount of alkyl groups in the polymer is 1230cm
It was quantified using an infrared absorption spectrophotometer based on the characteristic absorption based on the alkyl group appearing in ^-1 . The results are shown in Table 7.

[Table] From the results in Table 7, it is clear that the introduction rate of the initiator fragment into the polymer was 93%, and that it was introduced into almost all the main chains. Example 28 At the following charging ratio, the polymerization initiator with peroxide number No. 9 synthesized in Example 5 was used as an initiator.

[Table] When solution polymerization was carried out at 70℃, in 15 hours,
The polymerization rate was 80%. The polymer obtained above,
Purification by reprecipitation with methylene chloride-methanol system and gel permeation chromatography (Shodex)
column) to determine the weight average molecular weight and number average molecular weight. Also, the amount of polyether groups in the polymer is 1750
It was quantified using an infrared absorption spectrophotometer based on the characteristic absorption of the carbonyl of the ester, which appears at cm ^-1 . The results are shown in Table 8.

[Table] From the results in Table 8, it is clear that the introduction rate of the initiator fragment into the polymer was 88%, and that it was introduced into almost all the main chains. Example 29 At the following charging ratio, the polymerization initiator with peroxide number No. 17 synthesized in Example 13 was used as an initiator.

[Table] When emulsion polymerization was carried out at 10°C, it was completed in 10 hours and the polymerization rate was 99%. The polymer obtained above was purified by reprecipitation using a methylene chloride-methanol system, and the weight average molecular weight and number average molecular weight were determined by gel permeation chromatography (Shodex column). In addition, the amount of azo groups in the polymer is
It was determined using an infrared absorption spectrophotometer based on the characteristic absorption of the carbonyl of the ester appearing at 1750 cm ^-1 . The results are shown in Table 9.

[Table] * Azo group content Calculated from the theoretical value () number average molecular weight Calculated from the theoretical value () Calculated from the amount of initiator charged From the results in Table 9, the introduction rate of initiator fragments into the polymer is 96%, which is approximately It is clear that it is introduced into all main chains. Example 30 The polymer () polymerized in Example 24 was mixed with ethylene-acrylic acid copolymer (acrylic acid content 3%) in the following ratio.

[Table] As a result of kneading at 220°C, a semitransparent and uniform kneaded product was obtained. When unreacted polymer (1) was extracted from the kneaded product using xylene as a solvent, 6% of polymer (1) was recovered based on the initial amount charged. Comparative Example 1 When commercially available polymethyl methacrylate and the above ethylene-acrylic acid copolymer were kneaded under the same conditions as in Example 30, the color was white and the polymethyl methacrylate and ethylene-acrylic acid copolymer had undergone phase separation. A kneaded product was obtained. When xylene extraction was performed from this kneaded product under the same conditions as in Example 30, 99% of polymethyl methacrylate was recovered. Example 31 Polymer (2) obtained in Example 25 and OH-terminated polybutadiene (molecular weight 4000, manufactured by Nippon Soda Co., Ltd.)
As a result of kneading NISSO-PBG) at 210℃ in the following ratio,

[Table] A nearly transparent kneaded product was obtained. A test piece for the Izot impact test was made from the above kneaded material by pressure molding, and the Izot impact value was determined to be 26Kg-cm/
It was cm. Comparative Example 2 Commercially available polystyrene (molecular weight 300,000) and the above-mentioned OH-terminated polybutadiene were kneaded under the same conditions as in Example 31, and a white kneaded product was obtained. This kneaded material was pressure-molded under the same conditions as in Example 31, and the Izot impact test value was determined to be 1.3Kg-
It was cm/cm. Example 32 The melt flow index of the polymer (4) obtained in Example 27 was measured at 190° C. and a load of 5 kg, and was found to be 3.8. Comparative Example 3 Commercially available unplasticized vinyl chloride polymer (molecular weight
100000) Example 27
When measured under the same conditions, it was 0. Example 33 The polymer (5) obtained in Example 28 was pressure molded at 200°C, and the Izot impact value was determined to be 3.0 kg.
- cm/cm, and the molded specimen showed wetting properties. Comparative Example 4 Example using commercially available polystyrene (molecular weight 300000)
Pressure molding was performed under the same conditions as No. 33, and the Izot impact value was determined to be 1.4 kg-cm/cm. Example 34 The polymer (6) obtained in Example 29 was dissolved in toluene and mixed in the following proportions, and heated at 70°C to decompose the azo group.

[Table] When solution polymerization was carried out, 75% of methyl methacrylate monomer was polymerized in 10 hours. The polymer obtained above was purified by reprecipitation in a toluene-methanol system, and the purified product was purified using cyclohexane as a solvent.
When extracted at 60°C, 8% of the polymer (6) was recovered based on the initial charge. Furthermore, when the polymerized product after extraction was pressure-molded, a nearly transparent test piece was obtained, and the absorption of methacrylic acid ester was also confirmed in the infrared absorption spectrum. Comparative Example 5 Polymethyl methacrylate with a molecular weight of 50,000 and polystyrene with a molecular weight of 50,000 were dissolved in toluene,
When the mixture reprecipitated with methanol was extracted with cyclohexane under the same conditions as in Example 34, the result was 99%.
of polystyrene was recovered.

Claims (1)

[Claims] 1. An initiator for radical polymerization represented by the general formula (). (In the general formula (), R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 100 carbon atoms, a substituted alkyl group, an allyl group, or a substituted allyl group. .
However, this excludes the case where R ₁ = R ₂ = R ₃ = R ₄ = R ₅ = hydrogen atom or halogen atom. and at least any of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ includes a carboxylic acid group, a carboxylic acid base, a sulfonic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid group, an amino group, ammonium base, ether group, ester group, amide group, lactone group, lactam group, epoxy group, acid anhydride group, hydroxyl group, azo group, peroxide group, thiol group, nitro group, isocyanate group,
It has one or more functional groups selected from the group consisting of nitrile groups and alkyl groups having 10 to 100 carbon atoms. ) 2 The compound represented by the general formula () A polymerization initiator represented by the general formula () by oxidation using a photosensitized oxidation method. How to manufacture. (In general formulas () and (), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are hydrogen atoms, halogen atoms, alkyl groups having 1 to 100 carbon atoms, substituted alkyl groups, allyl groups, or substituted allyl groups) Indicates the group.
However, this excludes the case where R ₁ = R ₂ = R ₃ = R ₄ = R ₅ = hydrogen atom or halogen atom. and at least any of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ includes a carboxylic acid group, a carboxylic acid base, a sulfonic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid group, an amino group, ammonium base, ether group, ester group, amide group, lactone group, lactam group, epoxy group, acid anhydride group, hydroxyl group, azo group, peroxide group, thiol group, nitro group, isocyanate group,
It has one or more functional groups selected from the group consisting of nitrile groups and alkyl groups having 10 to 100 carbon atoms. )