JPH0374408A - Radical polymerization initiator - Google Patents

Abstract

PURPOSE:To obtain the title polymerization initiator having a slight smell, providing processed products having improved hue, comprising tertiary octyl peroxyneononanoate as an active ingredient. CONSTITUTION:The objective polymerization initiator comprising tertiary octyl peroxyneononanoate as an active ingredient. In order to uniform polymerization reaction rate and to improve polymerization ratio, the polymerization initiator may be blended with 0-50wt.% another initiator such as diisopropyl peroxycarbonate, di(sec-butyl) peroxycarbonate, di(2-ethyl)hexyl peroxydicarbonate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a radical polymerization initiator, and the present invention relates to a radical polymerization initiator, and particularly relates to a radical polymerization initiator, which is a radical polymerization initiator, and is particularly applicable to vinyl chloride, or a monomer copolymerizable with vinyl chloride, among ethylenically non-malting monomers. WIA is used in aqueous suspension polymerization of a mixture of polyvinyl chloride and vinyl chloride, and the resulting vinyl chloride polymer is kneaded with a plasticizer etc. to produce processed products. This invention relates to an improved radical polymerization initiator.

For polymer manufacturers, it is possible to shorten the radical polymerization time, and at the same time, when kneading the obtained resin with a plasticizer etc. to produce processed products, there is less odor due to the decomposition products of the polymerization initiator.
There is a need for a polymerization initiator that also improves the hue of processed products.

[Prior Art] Many studies have been made to meet these requirements. For example, peroxydicarbonates such as diisopropyl peroxydicarbonate and di(2-ethyl)hexylberoxydicarbonate have low partial decomposition. Therefore, the polymerization time can be shortened by increasing the IA voltage, but if the WA voltage is increased, the hue of the processed product will be inferior. On the other hand, ta
r't-butylberoxypivalet), tart-butylperoxy-2-ethylhexanoate, tart-
Peroxy esters such as butylperoxyneodecanoate have less effect on the hue of processed products than peroxydicarbonates, but their decomposition rate is slow, so polymerization time is long. There were problems such as not having one. Recently, α-1-ruberoxyneodecanoate has been studied and it has been found that even in the order of peroxyesters, a polymerization time comparable to that of peroxydicarbonates can be obtained. However, in the case of a-ri 1 ruberoxy neodecanoate, although the color of the obtained polymer was excellent, it was found that a decomposition product producing a considerably strong odor was produced during processing into different products.

[Problems to be solved by the invention] Polymerization time is similar to that of peroxydicarbonates.

When kneading the resin obtained by polymerization with a plasticizer etc. to produce a processed imitation product, there is less odor due to the decomposition products of the polymerization initiator (a polymerization initiator that also improves the color of the processed product). As a result of extensive research, we have found a polymerization initiator that has a double polymerization time equivalent to that of peroxydicarbonates, has less odor from mono-decomposition products, and improves the color of processed products.The present invention has been completed.

[Means and effects for solving the problems] Namely, 2. The present invention is a radical heavy metal initiator containing tertiary octyl peroxy neononanoate as an active ingredient.

[Effects of the invention] By using the radical polymerization initiator system of the present invention, the heavy metal time is equivalent to that of peroxydicarbonates, and when the resulting resin is kneaded with a plasticizer etc. to create processed products. 2
There was less odor due to decomposition products of the polymerization initiator, and the color of processed products was also improved.

The aqueous layer opening method carried out in the present invention may be carried out by any conventional method, except for the use of a nuclear initiator.

For the purpose of uniformizing the polymerization reaction rate and improving the double unit ratio, the initiator may be used in combination with other initiators. Examples of initiators used in combination include diisopropyl peroxydicarbonate and diisopropyl peroxydicarbonate. (sea-butyl) peroxydicarbonate, di(2-ethyl)hexyl peroxydicarbonate, di(1-methyl)hexyl peroxydicarbonate, dioctyl peroxydicarbonate,
Peroxydicarbonates such as dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tart-butyl)cyclohexylperoxydicarbonate, dioctyl peroxydicarbonate, dioctyl peroxydicarbonate, dilauryl peroxydicarbonate, acetylcyclo Azo compounds such as hexylsulfonyl peroxide, acetyl-5O-hebutylsulfonyl peroxide, azobisisobutyronitrile, and azobisdimethylvaleronitrile.

t@rt-butyl peroxypivalate, t@rt-
butylperoxy-2-ethylhexanony), t'5
Peroxy esters such as rt-butyl peroxyneodecanoate, diisobutanoyl peroxide, di-n-
Nonanoyl peroxide.

di3.5.5-)limethylhexanoyl peroxide,
Examples include diacyl peroxides such as dilauroyl peroxide. However, in the present invention, two of the initiators used are
Preferably, 0 to 100% by weight i** initiator is included,
It is more preferable to use 50 to 100% by weight of the brass agent No. 11 in the aqueous suspended heavy metal method, and the amount of brass agent used is generally 0.001 parts by weight per 100 parts by weight of the monomer.
~3.0 parts by weight, particularly preferably 0.005 to 2.0 parts by weight. The amount of initiator used is 0.001 weight 11
If it is less than 11, it has no effect as an initiator (the polymerization reaction does not occur), and if it is above 3.0 mgA, the control of the polymerization reaction is 1.
m1I, and the degree of zero-order two polymerization, which also reduces the quality of the obtained polymer, is 25 to 75°C, preferably 40 to 60°C.
If the degree of polymerization is below 26°C, the polymerization reaction will be slow9.
Reaction time becomes longer.

If the temperature exceeds 75°C, the life of the initiator will be short (the activity as an initiator will be lost and the heavy metal reaction rate will not increase).

Among the ethylenically unsaturated monomers used in the present invention, styrene is used as a monomer in addition to @vinyl.

** Vinyl, vinyl propionate, acrylic acid and its esters, methacrylic acid and its esters, vinylidene chloride, vinyl compounds such as alkyl vinyl ethers, olefins such as ethylene, propylene, 1-butene, 1-pentene, etc. etc. are exemplified.

[Examples] Next, examples, reference examples, and comparative examples will be given and explained, but all of them are for illustrative purposes and the present invention is not limited to them.

[Example 1] (Ceremony for tertiary octyl peroxy neononanoate) 30 g of a 30% by weight potassium hydroxide aqueous solution (0
, 16 mol) and 20 g (0° 13 mol) of 95% by weight tertiary octyl hydroperoxide were added, and while keeping the temperature of the reaction liquid in the flask at 20°C, neononanoic acid chloride distilled under a 23g (0,
13 mol) was added dropwise over 1 hour. After that, continue stirring for 4 hours to see if the reaction solution has finished (after stopping the stirring).

The oil layer and reaction waste water were separated by liquid separation. Further oil layer,
21 with 100g of 30% by weight aqueous potassium hydroxide solution! 31 with 100g of ion exchange water after washing! l Washed with water. Finally, it was dehydrated with anhydrous magnesium sulfate to obtain a 31.7 g oil layer. The obtained sample was measured by infrared absorption spectrum. Carbonyl group absorption was observed in IJf & 1750 Kaiser, and weak peroxy group absorption was observed in 800 Kaiser.

Next, an elemental analysis of this sample was carried out.
．． It was 2% by weight. *** is carbon 71°28% by weight
, 11.96% by weight of hydrogen and 16.76% by weight of oxygen. Nu,! -The amount of active l11A determined by the tometry method was 5.53% by weight. Gang.

Coral bottle is 5.59% by weight. From the above results, it was confirmed that the oil layer obtained was tertiary octyl peroxy neononanoate. Further, the half-life of this peroxyester in benzene for 10 hours was 41.8°C. This pith is a common peroxydicarbonate, di(
44 of 2-ethyl)hexyl peroxydicarbonate
．． The temperature is lower than 6℃.

7 indicates that the initiator is a lower temperature decomposable initiator.

[Reference Example 1] (Polymerization of Ix vinyl monomer) 180 g of deionized water in an autoclave equipped with a stirrer,
After charging 100 g of polyvinyl alcohol and 0.04 g of tertiary octyl peroxyneophanoate as a radical polymerization initiator and sufficiently purging with nitrogen, @vinyl monomer was charged and polymerization was carried out for 8 hours at a jacket temperature of 43°C.

After the polymerization, unreacted monomers were removed and the slurry of the two polymers was dried to give 90 g of polymer.100 m of zero-order polymer and 15011 dioctyl phthalate were obtained. 3 parts of calcium stearate and 5 m of stearic acid a#ao were blended and kneaded for 6 minutes on a roll at 160°C to obtain a 1 mm thick sheet. During roll kneading, no strange odor was detected and the operator did not feel uncomfortable. The color of the sheet was clear white, and no coloring such as pale yellow was observed.

[Comparative Example 1] Polymerization was carried out in the same manner as in Reference Example 1, except that an equimolar number of α-reperoxy neodecanoate was used instead of tertiary octyl peroxy neononanoate as a radical polymerization initiator, and 89 g of polymerization was obtained. Obtained union. In addition, when a sheet was prepared using the same method, the color of the sheet by visual inspection was similar to that of the sheet obtained in Example 1, but during roll kneading,
The odor of acetophenone caused discomfort to workers.

[Comparative Example 2] Polymerization was carried out in the same manner as in Reference Example 1, except that the same mole number of di(2-ethyl)hexyl peroxydicarbonate was used instead of tertiary octyl peroxy neononanoate as a radical polymerization initiator. 'g of polymer was obtained.

Further, when a sheet was prepared by the method of Oka et al., the hue of the sheet was visually observed to be pale yellowish compared to the sheet obtained in Example 1.

[Comparative Example 3 Reference Example 1 except that an equimolar number of tart-butylperoxyneodecanoate was used instead of tertiary octylperoxyneonanoate as a coradical polymerization initiator.
This is because 0 polymer, which was polymerized in the same machine and obtained a 60C polymer, has few advantages.

It was found that no polymerization occurred. Further, when a sheet was prepared using the same method, the color of the sheet visually observed was the same as that of the sheet obtained in the reference example process, and the odor during roll kneading was at a level that did not cause discomfort to the operator.

Claims (1)

[Claims] 1. A radical polymerization initiator containing tertiary octyl peroxy neononanoate as an active ingredient.