JPH0240083B2 - JUGOKAISHIZAI - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polymerization initiator containing a diacyl polymer peroxide as an active ingredient, and particularly to a polymerization initiator with high initiator efficiency. Traditionally, diacyl-type polymeric peroxides have not been used as polymerization initiators for ordinary vinyl-type monomers, or as ordinary monofunctional peroxides because they have multiple peroxide groups in one molecule. It is known that it can be used as a polymerization initiator in unique polymerization reactions that cannot be carried out. For example, it is known that when a diacyl polymer peroxide is used as a polymerization initiator, a polymer with a higher molecular weight can be obtained than when a normal monofunctional peroxide is used (Chemical Abstracts, Vol. 67, 54445a (1967) and Chemical Abstracts, Volume 84, 136120f
(1976)). It is also known that a so-called block copolymer can be obtained by polymerizing two types of vinyl monomers using a diacyl polymer peroxide (Kokagashi Vol. 69, p. 718). (1966)). There have been several reports regarding diacyl polymer peroxides, which are useful polymerization initiators. Namely, diacyl-type polymeric peroxides (Berichte der Deutschen Hemitschen Gesellschaft, Vol. 27, p. 1510 (1894)) are formed from phthalic acid chloride and sodium peroxide, but also formed from oxalic acid chloride and peroxide. By reaction with sodium, the corresponding diacyl-type polymeric peroxide (Journal of the American Chemical Society, Vol. 68, p. 534 (1946)) is produced.
Furthermore, by the reaction of the aliphatic dibasic acid chloride and sodium peroxide, the following general formula () is obtained. (Here, n is 2 to 20, and x is 16 to 35.) (Chemical Abstracts, Vol. 60, 5293d)
(1964) and volume 10892e (1964)) are known. However, these known diacyl type polymeric peroxides have the disadvantage of low initiator efficiency. For example, if the initiator efficiency is low, the amount of peroxide used will increase even when producing block copolymers and high molecular weight polymers, which are one of the uses of diacyl type polymer peroxides as mentioned above. There was a problem that the production rate of block copolymers and high molecular weight polymers decreased. Another drawback of these diacyl type polymeric peroxides is that they have little or no solubility in organic solvents and vinyl type monomers. Chemical Abstracts, Vol. 64, 15989g (1968)). Furthermore, these peroxides pose problems in handling because they are sensitive to shock and friction and are explosive compounds (Chemical Abstracts, Vol.
59, 7651 (1963)). Therefore, the present inventors conducted research in search of a diacyl-type polymeric peroxide that eliminates these various drawbacks and has a particularly high initiator efficiency. The inventors have discovered that the initiator has extremely high initiator efficiency, and its peroxide exhibits excellent solubility in organic solvents, and is a very safe compound.The present invention has been developed as an industrially useful polymerization initiator. completed. That is, the present invention provides the following general formula () (In the formula, X is

[Formula] -CH ₂ -CH=CH (CH ₂ ) ₂ CH=CH-CH ₂ -,

[Production of diacyl-type polymeric peroxide and measurement of safety and solubility]

137 g (0.24 mol) of 7% aqueous sodium hydroxide solution in a four-necked flask equipped with a stirrer and thermometer.
and 8.2 g (0.12 mol) of 50% hydrogen peroxide were mixed to prepare a sodium peroxide solution. Next, 0.1 mol of each of the various dibasic acid chlorides in the amounts shown in Table 1 were added little by little at a temperature of 0 to 5°C. at this temperature
After stirring for 30 minutes, the contents were washed with water and then dried to produce each diacyl type polymer peroxide. The constituent units of these peroxides are determined from the characteristic values of the infrared absorption spectrum and the τ value and intensity of the nuclear magnetic resonance spectrum, and the average molecular weight is measured by the VPO method.
The value was divided by the molecular weight of the structural unit to obtain n. Next, for each diacyl type polymeric peroxide, the amount of active oxygen was measured by the usual iodometry method, and the 10-hour half-life temperature (0.1 mol/benzene) was measured by the usual method, and the results are shown in Table 2. It was shown to. Next, the safety degree of these peroxides was determined by the method described in "Safety Engineering" Vol. 4, No. 2, p. 181 (1965), and various solvents (100
g), and the results are shown in Tables 8 and 4.
Shown in the table. Comparative Examples 1 and 2 [Manufacture and measurement of safety and solubility of known polymerization initiators] Example 1 except that adipic acid chloride or dodecanedioic acid chloride was used as the dibasic acid chloride.
Diacyl-type polymer peroxides, which are known polymerization initiators, were produced by methods similar to those in 5 to 5. Using the same method as in Examples 1 to 5, determine each structural unit, n, amount of active oxygen, and 10-hour half-life temperature,
The results are shown in Table 2. Also, regarding safety and solubility, Examples 1 to 5
The results are shown in Tables 8 and 4.

【table】

【table】

[Table] Mixture of tadecadienyl

【table】

[Table] Reference Examples 1 to 5 0.02 mol of each diacyl polymer peroxide produced in Examples 1 to 5 was added to 1 mol of styrene.
5 ml of the prepared sample was sealed in a glass ampoule with an inner diameter of 12 mm, and bulk polymerization was carried out at 60°C.
Measurements of each initiator efficiency were made. The results are shown in Table 5. The measurement of initiator efficiency is as follows:
“Vinyl Polymerization Experimental Method” (Kyoritsu Shuppan Co., Ltd.) No.
It was measured based on the method described on page 256. Reference Example 6 Using the diacyl polymer peroxide produced in Example 1, replacing styrene with methyl methacrylate as the vinyl monomer, polymerization temperature 60°C
Bulk polymerization of methyl methacrylate was carried out according to Reference Examples 1 to 5, except that the temperature was changed to 50°C. Initiator efficiency was measured in the same manner as in Reference Examples 1-5. The results are shown in Table 5. Reference Example 7 Bulk polymerization of methyl methacrylate was carried out in accordance with Reference Example 6, except that the diacyl type polymer peroxide produced in Example 1 was replaced with that produced in Example 2. Initiator efficiency was measured in the same manner as in Reference Examples 1-5. The results are shown in Table 5. Reference Examples 8 and 9 Reference Examples 1 to 9 except that the diacyl polymer peroxide produced in Example 1 was replaced with the known ones produced in Comparative Examples 1 and 2, respectively.
Bulk polymerization of styrene was carried out according to 5. Initiator efficiency was measured in the same manner as in Reference Examples 1-5. The results are shown in Table 5. Reference Example 10 Bulk polymerization of methyl methacrylate was carried out in accordance with Reference Example 6, except that the diacyl type polymer peroxide produced in Example 1 was replaced with a known one produced in Comparative Example 1. Reference examples 1 to 5
The initiator efficiency was measured in the same manner as. The results are shown in Table 5.

【table】

[Table] Reference example of octadecadienyl mixture 11 300g of distilled water in a stainless steel autoclave,
Polyvinyl alcohol 0.45g, vinyl chloride 100g
Then, 0.1 g of the diacyl type polymeric peroxide produced in Example 1 was added, and polymerization was carried out at 60°C for 10 hours. The polymerization conversion rate after 10 hours was 86%.

Claims (1)

[Claims] 1 General formula () (In the formula, X is [formula] -CH ₂ -CH=CH(CH ₂ ) ₂ CH=CH-CH ₂ -,
[formula] or _-CH2 -CH=CH- _CH2- , n is an integer from 3 to 40). A polymerization initiator containing a diacyl-type polymeric peroxide represented by the following as an active ingredient.