JPH03255065A - Organic peroxide, polymerization initiator and crosslinking agent composed of the same oxide - Google Patents

Abstract

NEW MATERIAL:An organic peroxide expressed by the formula (R is H or methyl). EXAMPLE:tert-Hexyl peroxybenzoate. USE:Useful as an active component of a polymerization initiator for vinyl monomers and crosslinking agent for polymers. The peroxide is added in an amount of 0.00001-0.01mol, preferably 0.001-0.005 mol when used as the polymerization initiator at 80-150 deg.C polymerization temperature and in an amount within the range of normally 0.1-10wt.%, preferably 1-3wt.% based on the polymers to be crosslinked (e.g. polyethylene) when used as the crosslinking agent. PREPARATION:tert-Hexyl hydroperoxide is made to react with the corresponding benzoyl chloride in the presence of an alkali compound to afford the compound expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel organic peroxide, and a polymerization initiator for vinyl monomers and a crosslinking agent for polymers comprising the peroxide.

<Prior art> Conventionally, as alkyl peroxybenzoate, t-
Butylperoxybenzoe-1., t-butylperoxy-m-methylbenzoate, and the like were known. These organic peroxides are used in the polymerization of vinyl monomers or as crosslinking agents for polymers.

<Problems to be Solved by the Invention> The above-mentioned organic peroxides are useful as polymerization initiators or crosslinking agents, but they have some problems depending on the purpose of use. That is, it has a relatively low vapor pressure and is easy to volatilize, has a relatively high solubility in water, and has a large power when decomposed. In addition, in the suspension polymerization of certain vinyl monomers, solidification due to aggregation of polymerized oil droplets,
There were also problems such as scale adhesion to the reaction vessel.

<Means for Solving the Problem> As a result of long-term research in order to solve the problems of the above-mentioned known organic peroxides, the present inventors have discovered an organic peroxide that does not have these problems. They discovered this and completed the present invention.

That is, the present invention provides an organic peroxide represented by -Funzo (in the formula, R represents hydrogen or a methyl group), a polymerization initiator of a vinyl amine compound containing the same peroxide as an active ingredient, and a crosslinking of a polymer. It is a drug.

Specifically, the organic peroxides of the present invention include t-hexylperoxybenzoate, t-hexylperoxy-p-methylbenzoate, t-hexylperoxy-m-methylbenzoate, t-hexylperoxy-〇- It is medyl benzoate.

The organic peroxide of the present invention is a new compound, and the compound was identified as shown in the Examples.

The organic peroxide of the present invention is synthesized by reacting t-hexyl hydroperoxide and the corresponding benzoyl chloride in the presence of an alkali compound.

Examples of vinyl monomers for which the organic peroxide of the present invention is used as a polymerization initiator include styrene, α-methylstyrene, chlorostyrene, paramethylstyrene, t-butylstyrene, acrylonitrile, acrylic esters, and methacrylic acid. These include esters, maleic esters, fumaric esters, maleimides, butadiene, and the like. In addition to these monomers, various chain transfer agents, rubber components, or blowing agents such as pentane may be added.

When used as a polymerization initiator, the amount added varies depending on the type of monomer used for polymerization, but is 0.00001 to 0.01 mole per mole of monomer charged to AQ, preferably 0. ．． QOOI is ~0.005 mol.

If the amount is less than 0.00001 mol, the polymerization rate tends to be slow. Moreover, even if the amount exceeds 0.01 mol, the effect commensurate with the added amount cannot be obtained and it is not economical.

As the polymerization method used in the present invention, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method are employed.

Further, the polymerization temperature when using the polymerization initiator of the present invention is usually 80 to 150°C, preferably 100 to 130°C. At temperatures below 80°C, the polymerization rate tends to decrease, and at temperatures above 150°C, it becomes difficult to control polymerization in bulk polymerization, and in suspension polymerization and emulsion polymerization, the pressure in the reaction tank increases due to water vapor. I don't like it.

It is also possible to carry out the polymerization at a constant temperature or at a relatively low temperature at the beginning of the polymerization, and then increase the temperature in stages as the polymerization progresses.

The polymer crosslinked with the organic peroxide of the present invention includes:
For example, polyethylene, ethylene brobylene copolymer (
EPM), ethylene brobylene diene cohomer (E
PDM), ethylene vinyl acetate copolymer (EVA),
Chlorinated polyethylene, polybutene-1, polyisobutyne, ethylene vinyl acetate copolymer, polybutadiene, polyisoprene, polychloroprene, butadiene styrene copolymer, natural rubber, polyacrylate rubber,
butadiene acrylonitrile copolymer, acrylonitrile)
- Examples include lylbutadiene styrene ternary copolymer, silicone rubber, polyurethane, and polysulfide.

The organic peroxide is generally added to the polymer to be crosslinked in an amount ranging from 0.1 to 10% by weight, preferably from 1 to 3% by weight.

The polymer to be crosslinked can also contain various additives commonly used in crosslinking processes, such as crosslinking coagents, antioxidants, pigments, UV stabilizers, fillers, plasticizers, and the like.

In the present invention, the temperature at which the polymer and organic peroxide are mixed is generally 25 to 110°C, and the temperature for subsequent crosslinking is generally 110 to 200°C, preferably 130 to 180°C.
is used.

<Effects of the Invention> The organic peroxide of the present invention has the following characteristics. That is, the vapor pressure is relatively high and it is difficult to volatilize, the solubility in water is relatively low, the decomposition force is small, and the adhesion of scale to the container during suspension polymerization is suppressed.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

The vinyl monomer used was a commercially available product which had been sufficiently substituted with nitrogen. In addition, the abbreviations for organic peroxides mean the following compounds.

HZ; t-hexylperoxybenzene-1・HM
T;1;-hexylperoxy-m-methylbenzoate HOT: t-hexylperoxy-0-methylbenzoate 1 (P T t-hexylperoxy-p-methylbenzoate BZ; t-butylperoxybenzoate 1. The polymerization conversion rate of the product obtained by polymerization was determined by quantitative determination of the residual vinyl monomer by gas chromatography.

Example 1 [Preparation of H2] 30.9 g of a 40% aqueous potassium hydroxide solution (0,
22 mol) of t-hexyl hydroperoxide, and while cooling with ice and stirring at 5 to 10°C, 23.6 g (0
, 2 mol) was added thereto, and the reaction was then continued at 10°C for 30 minutes. Then add 25.3 g of benzoyl chloride (0,1
8 mol) was added over 30 minutes. Thereafter, the reaction was continued for 1.5 hours at 10°C. Separate the oil layer from this reaction mixture,
After washing once with 5% sodium hydroxide and then twice with water, it was dried over anhydrous magnesium sulfate to obtain 37.7 g of liquid. The result of determining the amount of active oxygen using the iodine method is 6
．． The purity was 95.9%. The obtained liquid is N
It was confirmed by MR that it was t-hexyl peroxybenzoate based on the data below. δ (ppm):
0.90 (t, CHx, 3tl), 1.32
(s, (:Ha, 6H) 1..70 (m
, GHz.

4H), 7.4-'7.7 (m, C:H, 3
H), 8°0-8.2 (m, CH, 2H) A 0.1 mol #benzene solution of the obtained organic peroxide was sealed in an ampoule, and 100. 110. 120℃
Thermal decomposition was carried out at each temperature, the thermal decomposition rate at each temperature was measured, and the temperature at which the 10-hour half-life occurred was calculated. The results were as shown in Table 1.

In addition, 1 g of organic peroxide was added to 100 g of water, stirred at 20°C for 1 hour, the aqueous phase was separated, and n-hexane 3 was added to the aqueous phase.
Extracted at 0g. The n-hexane phase was analyzed by gas chromatography to quantify the amount of dissolved organic peroxide. The results were as shown in Table 1.

In addition, as a volatilization test, 50 g of the sample was placed in a beaker with a diameter of 75 mm and a height of 70 mm, and the temperature was kept in a constant temperature bath at 50° C. for 1 hour, and the amount of volatilization was measured. The results were as shown in Table 1.

We also conducted a pressure vessel test to test the power of disassembly.

A 5 g sample was placed in a stainless steel container with an internal volume of 200 cc, which had an aluminum rupture plate of 10 kg/cm2 on the top and an orifice with a predetermined hole on the side, and was heated and decomposed, causing the aluminum plate to break. The minimum orifice diameter that does not occur was determined. The results were as shown in Table 1.

Example 2 [Production of HMT] In Example 1, 27.8 g of m-methylbenzoyl chloride was used instead of 25.3 g of benzoyl chloride (0
, 18 mol) was used, but the same operation as in Example 1 was carried out. 39.3g of liquid was obtained. The amount of active oxygen is 6.53%
The purity was 96.5%. The obtained liquid was confirmed to be t-hexylberoxy-m-methylbenzoate from the following NMR data.

δ (ppm): 0.90 (t,
CH,, 3H), 1. ．． 32 (S.

CH,, 6H) 1.70 (m, CL
, 4H), 2.46 (sC
113, 311), 7.5 -7.8
(m, (:H, 211), 8
．． 08.3 (m, Ca1l,
2H) The obtained organic peroxide was subjected to the 10-hour half-life temperature, water solubility, volatilization test, and pressure vessel test using the same test methods as in Example 1. The results were as shown in Table 1.

Example 3 [Production of HOT] In Example 1, 27.8 g of 0-methylbenzoyl chloride (0,
The same operation as in Example 1 was performed except that 1.8 mol) was used. 39.0 g of liquid was obtained. The amount of active oxygen is 6.49
The purity was 95.9%. The obtained liquid is NMR
From the data below, it was confirmed that it was t-hexylperoxy-〇-methylbenzoate.

δ (1) pm): 0.92 (t, Ctl,
, 3H), 1.30 (S.

C1+3.611) , ], , 70 (m, f';
H□, 4H), 2.64 (S.

G11a, 2t(), 7.4 7.
8 (m, CH, II+), 8.3-8
．． 5 (m, ell, 311) The same test as in Example 1 was conducted on the obtained organic peroxide. The results were as shown in Table 1.

Example 4. [Production of HPT 1 In Example 1, 27.8 g of p-methylbenzoyl chloride (0,
The same operation as in Example 1 was performed except that 1.8 mol) was used. 39.8 g of liquid was obtained. The amount of active oxygen is 6.45
The purity was 95.3%. The obtained liquid is NMR
It was confirmed that it was t-hexylperoxy-p-methylbenzoate from the following data.

δ (ppm): 0.94 (t, CH3,
3H), 1.33 (s.

C11,,611), 1.75(m, (:
l+2, 41(), 2.88(s.

CHs, 3t(), 7.2 7.5
(m, Ctl, 21(), 8.1
-8.3 (m, C1l, 2H) The same test as in Example 1 was conducted on the obtained organic peroxide. The results are shown in Table 1 and were ■1.

Comparative Example 1 For comparison, using BZ, the 10-hour half-life temperature, water solubility, volatilization test, and pressure vessel test were conducted using the same test methods as in Example 1. The results were as shown in Table 1.

As is clear from Table 1, H2,! (MT, HOT, HP
It can be seen that T has lower water solubility and lower volatility than BZ, and also has less power during decomposition.

Examples 5 to 6 and Comparative Example 2 [Use as polymerization initiator 2] Partially saponified polyvinyl alcohol (saponification degree 88% polymerization degree 2) was placed in a stainless steel autoclave with a capacity of 500 mN.
400) /Hydroxypropylmethylcellulose (2
Viscosity of 2% aqueous solution at 0°C 100CP) = 1/1
Prepare 200 - of an aqueous solution containing 0.3% of the mixture of
Next, 70 g of styrene, 30 g of acrylonitrile, and the organic peroxide (polymerization initiator) shown in Table 1 were added as peroxy bonds in an amount of 0.02 mol based on the total monomers. /( was added. The space in the autoclave was sufficiently replaced with nitrogen gas, and then the autoclave was sealed. Then, the rotation was performed at 11,000 rpm.

Polymerization was carried out at 110° C. for 3 hours while stirring. After polymerization, the mixture was cooled, dehydrated, and dried to obtain granular resin.

The polymerization conversion rate of this resin was measured. Furthermore, the degree of scale adhesion inside the autoclave was observed, and the weight of the coalesced particles was measured. Scale adhesion is caused by the polymer on the side of the polymerization tank.
The 4th condition was shown, and those that were almost unchanged from the state before the reaction were rated as ``almost absent'', and those that appeared as white bands were rated as ``present''. Furthermore, the proportion of coalescing particles had the same tendency as the number 1 on the scale, and these results were evaluated together. The results were as shown in Table 2.

1.) As is clear from Table 2, the polymerization ratio of particles that did not pass through the 1.00 mesh sieve, H2 and HMT were B
It can be seen that compared to Z, the scale is smaller and the proportion of coalesced particles is also smaller.

Examples 7 to 8 and Comparative Example 3 [Use as a polymerization initiator] Using the same equipment as in Example 5, partially saponified polyvinyl alcohol (saponification degree 88% polymerization degree 2000) / hydroxypropyl cellulose (20% at 20°C) % aqueous solution viscosity 500CP) = 1. Pour 200 mfi of an aqueous solution containing 0.3% of a mixture of
, α-methylstyrene 50g, acrylonitrile 30g
An organic peroxide (polymerization initiator) shown in Table 3 was added as a peroxy bond in an amount of 0.02 mol/e based on the total monomers. After replacing the nitrogen gas with stirring at 11,000 rpm,
Polymerization was carried out for 5 hours while continuously raising the temperature from 10°C to 130°C. After polymerization, it was cooled, dehydrated, and dried to obtain a granular resin. The polymerization conversion rate of this resin was measured. The degree of scale adhesion inside the autoclave was also observed and the weight of the coalesced particles was measured.The results are shown in Table 3.

As is clear from Table 3, it can be seen that in the styrene/α-methylstyrene/acrylonitrile copolymerization, H2, HMT has less scale than BZ and also has a smaller proportion of coalesced particles.

Examples 9 to 10 and Comparative Examples 4.5 [Use as a crosslinking agent] Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, Tsuru l-
2 g of the organic peroxide (crosslinking agent) shown in Table 4 was kneaded into 100 g of Helix 625) at a roll temperature of 60° C. for 20 minutes. This sheet was heated at 160° C. for 5 minutes to cause crosslinking, and then JIS K63013 dumbbells were prepared and subjected to a tensile test. The results were as shown in Table 4.

6 As is clear from Table 4, H2, HMT has crosslinking performance.

Claims (3)

[Claims] (1) An organic peroxide represented by the general formula (numerical formula, chemical formula, table, etc.) (in the formula, R represents hydrogen or a methyl group). (2) Polymerization initiator for vinyl monomers whose active ingredient is an organic peroxide represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents hydrogen or a methyl group.) (3) A crosslinking agent for polymers whose active ingredient is an organic peroxide represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents hydrogen or a methyl group.)