JPH025772B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel diacyl type polymeric peroxide having a branched hydrocarbon group in the molecule, which is used as a free radical polymerization initiator for vinyl type monomers. BACKGROUND ART Diacyl-type polymeric peroxides obtained by polycondensation reaction of dibasic acid chlorides and sodium peroxide are conventionally known. That is, in Berichte der Deutschen Hemitschen Gesellschaft, Vol. 27, p. 1510 (11894), diacyl-type polymeric peroxides from phthalate chloride and sodium peroxide, and in Journal of the American Chemical Society. 68, p. 534 (1946), the corresponding diacyl-type polymeric peroxides were produced by the reaction of oxalate chloride with sodium peroxide, and also Chemical Abstracts, vol. 60, 5293d (1964) and vol. 10892e (1964). By the reaction of an aliphatic dibasic acid chloride with sodium peroxide, the following general formula (Here, n is 2 to 10, and X is 16 to 35.) A diacyl type polymeric peroxide represented by the following has been reported. Further, JP-A-53-149918 discloses a diacyl type polymeric peroxide having an ester bond obtained by reacting an acid chloride having an ester bond in the molecule with sodium peroxide. These diacyl polymer oxides are
It is also known that it is useful as a dielectric group polymerization initiator (hereinafter referred to as a polymerization initiator) for vinyl type monomers. For example, Chemical Abstracts Volume 67
54445a (1967), it was reported in Chemical Abstracts No. 84 that a polymer with twice the molecular weight was obtained when using benzoyl peroxide using the above-mentioned polymeric peroxide as a polymerization initiator.
Vol. 136120f (1976) found that when the aforementioned polymeric peroxide was used as a polymerization initiator for vinyl acetate, a polymer with a larger molecular weight and a lower degree of branching was obtained compared to when benzoyl peroxide was used. However, Koka Magazine Vol. 69, p. 718 (1966)
It has been reported that a styrene-methyl methacrylate graft polymer was obtained when poly(phthaloyl peroxide) was used in Although the known diacyl polymer peroxides are useful polymerization initiators, they have the following drawbacks. (1) Sensitive to shock and friction, explosive compound (Chemical Abstracts No. 59)
7651 (1963)). (2) It cannot be used industrially as a polymerization initiator because it has low solubility in organic solvents and is hardly or completely soluble in vinyl monomers (Kokagaku Zasshi Vol. 69, p. 718 (1966)) and Chemical Abstracts Vol. 64, 15989g (1968)). This is related to initiator efficiency; if the solubility is low, the initiator efficiency will be low when used as a polymerization initiator. The diacyl type polymeric peroxide having an ester bond in the molecule described above is excellent in improving the above two points, but has the following drawbacks. That is, the production of acid chloride having an ester bond in the molecule as a raw material consists of a two-step process,
Moreover, since it must be carried out under a stream of dry air or dry nitrogen, it is industrially disadvantageous in that it is a long process and requires special equipment. The present inventors have overcome these various drawbacks and developed a polymerization initiator that is useful as a polymerization initiator, is safe to manufacture and handle, rapidly dissolves in vinyl monomers, and has high initiator efficiency. As a result of research in search of industrially valuable diacyl-type polymeric peroxides, a novel diacyl-type polymeric peroxide having a branched hydrocarbon group introduced into the molecule was discovered, and the present invention was completed. It is a diacyl type polymeric peroxide consisting of the structural unit represented by () and having an average molecular weight of 1,400 to 16,000. The diacyl polymer peroxide of the present invention can be produced by the following method. That is, 7,12-dimethyl-7,
It can be easily obtained by adding 11-octadecadiene-1,18-dicarboxylic acid chloride little by little and reacting with stirring, and after the reaction is completed, separating it from the reaction waste liquid. The reaction conditions are the same as for ordinary dialperoxides, the reaction temperature is -10 to 40°C, preferably 0 to 15°C, and the reaction time is 0.25 to 5 hours, preferably 0.5 to 2 hours. The molar ratio of the raw material dichloride to the peroxidant is 1:0.7 to 3, and the concentration of the aqueous solution of the peroxidant is 1 to 15% by weight, preferably 2 to 10% by weight. The diacyl-type polymeric peroxide of the present invention produced as described above is a transparent viscous liquid, and is composed of the above-mentioned structural units, and the arrangement of the structural units is head-to-head and head-to-tail. It is a so-called random condensate with an average molecular weight of 1400~
16000. The diacyl polymer peroxide of the present invention has diacyl properties as determined by infrared absorption spectra.

[Formula] bond and C—O bond and --O—O— bond of peroxide were confirmed, and nuclear magnetic resonance spectroscopy showed that --CH ₃ , --CH ₂ --, --CH= and

It was identified by clarifying the structure of [Formula], its constituent units were determined, and VPO
method (using a Corona Denki model 117 molecular weight measuring device)
The average molecular weight is determined by Furthermore, the amount of active oxygen is determined by iodometric titration. The diacyl polymeric peroxides of the present invention have a number of advantages, including: (1) It is insensitive to impact and friction, has low explosiveness, and is safe to manufacture and handle. (2) Compared to conventional diacyl-type polymeric peroxides, organic solvents such as aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, cyclic ethers such as dioxane and tetrahydrofuran, and methyl ethyl ketone, etc. Solubility in ketones, chloroform, carbon tetrachloride, etc. is significantly improved. Therefore, when it is added to a vinyl monomer as a polymerization initiator, it is rapidly dissolved in the monomer, resulting in a significant improvement in workability during industrial use. (3) High efficiency at the start of polymerization. That is, compared to the conventional diacyl type polymeric peroxide, the value of the present invention is about twice as large. (4) Since the diacyl-type polymeric peroxide of the present invention has many peroxide groups in one molecule, it has specific properties that are not limited to ordinary monofunctional peroxides when polymerizing vinyl-type monomers. Polymerization reactions can be carried out. For example, compared to polymerizing styrene using benzoyl peroxide or lauyl peroxide, the use of the diacyl polymeric peroxide of the present invention provides polystyrene with a molecular weight approximately twice as high. Vinyl type monomers that can be polymerized with the diacyl type polymeric peroxide of the present invention are:
In addition to styrene, examples include vinyl acetate, acrylic ester, methyl methacrylic ester, acrylonitrile, vinylidene chloride, vinyl chloride, and ethylene. (5) A so-called block copolymer can also be obtained by polymerizing two types of vinyl monomers using the diacyl polymer peroxide of the present invention. For example, in the first step, styrene is polymerized with this peroxide to introduce one or more peroxide groups into the polystyrene, and in the second step, a different vinyl type monomer such as methyl methacrylate is added to the peroxide group-containing polystyrene. A block copolymer can be obtained by polymerizing. In particular, when the diacyl type polymer peroxide of the present invention is used for this purpose, the block copolymer production efficiency is improved.
The reason for this is that, as mentioned above, it has extremely good solubility in vinyl monomers. In the first stage of polymerization, when conventional diacyl polymer peroxides with low solubility in vinyl monomers are used, polymerization starts only on the surface of the partially dissolved or undissolved portions, so the polymer chain The proportion of peroxide groups contained therein is relatively small, and the proportion of unreacted diacyl type polymeric peroxide remaining is large. Therefore,
When this mixture is used in the second stage of polymerization, a homopolymer of vinyl type monomers will of course be produced as a by-product, and the efficiency of producing the block copolymer will be reduced. To avoid this, there is a method to purify the peroxide group-containing polymer by separating unreacted diacyl-type polymer peroxide at the end of the first-stage polymerization, but the separation operation is difficult and the process is long, making it difficult to manufacture industrially. disadvantageous to
In addition, the remaining unreacted diacyl-type polymeric peroxide will not be effectively utilized.
This will result in a loss of raw materials. Needless to say, the types of vinyl type monomers that can be subjected to block copolymerization using the diacyl type polymeric peroxide of the present invention are not limited to the above-mentioned examples, but also vinyl type monomers that can be polymerized with the peroxide of the present invention. Any combination is possible as long as it is a mercury. As described above, the diacyl-type polymeric peroxide of the present invention is safe to manufacture and handle, and when added to a vinyl-type monomer as a polymerization initiator, it dissolves quickly and has excellent efficiency as a polymerization initiator. Therefore, its industrial value is extremely high. The invention will now be explained in more detail by way of example. Example 1 In a four-neck flask equipped with a stirrer and a thermometer, 137 g (0.24 mol) of a 7% aqueous sodium hydroxide solution
and 8.2 g (0.12 mol) of 50% hydrogen peroxide,
A sodium peroxide aqueous solution was prepared. Next 7,12
-dimethyl-7,11-octadecadiene-1,
A solution of 40.3 g (0.1 mol) of 18-dicarboxylic acid chloride and 40 g of benzene was added little by little at a temperature of 0 to 5° C. while stirring. After stirring at this temperature for 30 minutes, the mixture was neutralized to pH 7 with dilute hydrochloric acid. The oil layer was then taken out, washed twice with water, and then dried over anhydrous magnesium sulfate. Solid matter was removed by filtration, and then benzene was distilled off under reduced pressure to obtain 30.6 g of a clear viscous liquid. The active oxygen content of this viscous liquid was determined to be 4.19% by the usual iodometry method. The characteristic absorption wavelengths in the infrared absorption spectrum of this viscous liquid are 1780 cm ^-1 , 1800 cm ^-1 (C=0),
1060cm ^-1 (C-O) and 880cm ^-1 (O-0),
The δ value and intensity of the nuclear magnetic resonance spectrum are 1.32ppm (12H) 1.48ppm (10H) 1.68ppm (8H) 2.32ppm (4H) 5.10ppm (2H). It was confirmed that it was a peroxide. The average molecular weight of this peroxide is the normal VPO
When measured by the method, it was 7600. Next, the safety level of this peroxide is determined by "safety engineering".
It was determined by the test method described in Vol. 4, No. 2, p. 181 (1965), and the results are shown in Table 1 below. Next, various solvents of this peroxide at 25℃
The amount dissolved in 100g was measured and the results are shown in Table 2 below. Example 2 The reaction, separation, and purification were carried out in the same manner as in Example 1 except that the amount of 50% hydrogen peroxide was changed to 5.5 g (0.08 mol) to obtain 26.4 g of a transparent viscous liquid. The active oxygen content of this viscous liquid was determined in the same manner as in Example 1, and was found to be 3.48%. In addition, this product has the same characteristic absorption wavelength of the infrared absorption spectrum and the δ value and intensity of the nuclear magnetic resonance spectrum as those of Example 1, so it is the same as the diacyl type polymer peroxide obtained in Example 1. It was confirmed that it consists of constituent units. The average molecular weight of this peroxide was then measured in the same manner as in Example 1 and found to be 1,800. Example 3 7% sodium hydroxide aqueous solution 137g (0.24mol)
134.7g (0.24mol) of 10% potassium hydroxide aqueous solution
6.8g (0.10mol) of 50% hydrogen peroxide
Reaction was carried out in the same manner as in Example 1 except that
After separation and purification, 31.9 g of a clear viscous liquid was obtained. The active oxygen content of this viscous liquid was determined in the same manner as in Example 1, and was found to be 4.37%. In addition, this product has the same characteristic absorption wavelength of the infrared absorption spectrum and the δ value and intensity of the nuclear magnetic resonance spectrum as those of Example 1, so it is the same as the diacyl type polymer peroxide obtained in Example 1. It was confirmed that it consists of constituent units. The average molecular weight of this peroxide was then measured in the same manner as in Example 1 and found to be 14,200. Comparative Example 1 Adipic acid chloride and sodium peroxide were reacted to produce a known solid diacyl polymer peroxide. This peroxide is determined by the following formula from the characteristic absorption wavelength of the infrared absorption spectrum and the δ value and intensity of the nuclear magnetic resonance spectrum. It was confirmed that it is a peroxide with . Furthermore, the average molecular weight was 940 as determined by the VPO method. Next, the safety and solubility of this peroxide were determined in the same manner as in Example 1, and the results are shown in Tables 1 and 2 below. Comparative Example 2 A known solid diacyl polymer peroxide was produced by reacting dodecanedioic acid chloride with thorium peroxide. This peroxide is determined by the following formula from the characteristic absorption wavelength of the infrared absorption spectrum and the δ value and intensity of the nuclear magnetic resonance spectrum. It was confirmed that it is a peroxide consisting of the following structural units. Furthermore, the average molecular weight was 1620 as determined by the VPO method. The safety and solubility of this peroxide were determined by the same method as in Example 1, and the results are shown in Tables 1 and 2.

【table】

[Table] It is clear from Table 1 that the diacyl type polymeric spectral oxide of the present invention has significantly higher safety than the known diacyl type polymeric peroxides. It is also clear from Table 2 that the diacyl polymer peroxide of the present invention is significantly superior in solubility in various solvents compared to known diacyl polymer peroxides. Reference Example 1 Styrene polymerization (bulk polymerization) and measurement of average molecular weight. Styrene 1 and diacyl polymer peroxide prepared in Example 1 as a polymerization initiator 0.1
5 ml of the sample prepared by dissolving the moles was sealed in a glass ampoule with an inner diameter of 12 mm, and polymerization was carried out at 70°C for 7 hours. Thereafter, the reaction solution was taken out, dissolved in 50 ml of benzene, and unreacted styrene monomer was quantified by gas chromatography using an internal standard method to determine the polymerization conversion rate. Then, pour it into 500ml of methyl alcohol,
A white precipitate of polystyrene was precipitated. After drying this white precipitate, the average molecular weight of the polystyrene was determined by GPC (High Performance Liquid Chromatograph Model HLC-802UR manufactured by Toyo Soda Industries). For comparison, the polymerization conversion rate and average molecular weight of polystyrene were determined by performing the same procedure using ordinary lauroyl peroxide instead of diacyl type polymeric peroxide. These results are shown in Table 3.

[Table] As is clear from Table 3, the diacyl-type polymeric peroxide of the present invention can increase the average molecular weight of polystyrene by about twice that of the conventionally used lauroyl peroxide.
This shows that it is an excellent polymerization initiator. Reference Example 2 Styrene polymerization (bulk polymerization) and measurement of initiator efficiency. 5 ml of a sample prepared by dissolving 0.02 mol of the diacyl polymer peroxide produced in Example 1, Comparative Examples 1 and 2 as a polymerization initiator in each 1 styrene was sealed in a glass ampoule with an inner diameter of 12 mm, and heated to 60°C. Polymerization was carried out using the following methods, and the initiator efficiency was determined for each polymerization initiator. The initiator efficiency was measured based on the method described in "Vinyl Polymerization Experimental Method" (published by Kyoritsu Shuppan Co., Ltd.), page 256. The results obtained are shown in Table 4.

[Table] As is clear from Table 4, the initiator efficiency of the diacyl-type polymeric peroxide of the present invention is approximately twice as high as that of known diacyl-type polymeric peroxides, indicating that it is excellent as a polymerization initiator. ing. Although the present invention has been described with reference to specific examples, without departing from the broader spirit and scope of the invention,
Of course, various changes and modifications are possible.

Claims (1)

[Claims] Linear formula It consists of the structural unit represented by and has an average molecular weight of 1400.
A diacyl-type polymeric peroxide characterized by a molecular weight of ~16,000.