JPH0912617A - Novel polymerization initiator composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride polymer having good properties such as heat stability at good efficiency by using a polymerization initiator composition prepared by mixing two specified peracid esters with each other in a specified ratio in the polymerization of vinyl chloride. SOLUTION: This polymerization initiator composition is used for the polymerization of a vinyl chloride monomer and prepared by mixing peracid esters (A) and (B) of the formula [wherein R1 to R3 are each a 1C or higher alkyl; R4 is a phenyl; the total number of carbon atoms of R1 to R3 in the compound A is 7; and the total number of carbon atoms of R1 to R3 in the compound B is 11] with each other in an A/B weight ratio of 70/30 to 90/10 as the effective component. When this composition is used in the polymerization of vinyl chloride monomers (other copolymerizable monomers may be included), it can give a vinyl chloride polymer having good properties in high yields. These peracid esters are obtained by reacting the corresponding acid chlorides with cumyl hydroperoxide in the presence of a catalyst such as NaOH. Their examples include cumylperoxy-2,2,3-trimethyl hexanoate and cumylperoxy-2,2,8,8- tetramethyl nonanoate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization initiator composition of a vinyl-based monomer comprising a novel peroxyester, and particularly to a vinyl chloride monomer or a monomer copolymerizable with a vinyl chloride monomer. Polymer (hereinafter abbreviated as vinyl chloride monomer)
The present invention relates to a polymerization initiator composition.

[0002]

2. Description of the Related Art In polymerizing vinyl chloride monomers,
Tertiary butyl peroxypivalate and tertiary butyl peroxy neodecanoate as polymerization initiators.
It has been already known that bisphenol, di-2-ethylhexyl peroxy dicarbonate and the like are used. The 10-hour half-life temperature of these polymerization initiators (the temperature at which a 0.1 molar solution in benzene halves the concentration in 10 hours) is 40-
It falls within the range of 60 ° C. In recent years, manufacturers of vinyl chloride resin manufacturers are actively reducing the polymerization time in order to streamline the production. In order to satisfy these requirements, the above-mentioned polymerization initiator having a 10-hour half-life temperature of 40 to 60 ° C. must be used in a considerably large amount. However, when the amount used is increased, the thermal stability of the obtained polymer is deteriorated, and further there is an economical problem.

In order to solve the above problems and to shorten the polymerization cycle and enhance the productivity, a lower temperature active polymerization initiator having a 10-hour half-life temperature of 40 ° C. or less was developed. It is used in combination with agents.
That is, a low-temperature active polymerization initiator having a 10-hour half-life temperature of 40 ° C. or lower is used as a fast-acting polymerization initiator exhibiting a large reaction rate in the initial stage of polymerization, and a conventional polymerization initiator is used in the latter stage of the polymerization. Is used in combination as a slow-acting polymerization initiator to reduce the polymerization cycle.

A diisobutyryl peroxide (hereinafter referred to as IB) is used as a polymerization initiator having a 10-hour half-life temperature of 40 ° C. or lower.
O), acetylcyclohexyl sulfonyl peroxide (hereinafter abbreviated as ACSP), α-cumylperoxy neodecanoate (hereinafter abbreviated as CND), and the like.

As the slow-acting polymerization initiator which has been used conventionally, t-octyl peroxy neodecanoate,
t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate (ND), t-butyl peroxypivalate (TBPP), di-2-ethylhexyl peroxy dicarbonate (OPD), etc. There is.

[0006]

SUMMARY OF THE INVENTION The polymerization cycle is shortened by the combination of the fast-acting polymerization initiator and the slow-acting polymerization initiator and the adjustment of the amount used. The low-temperature activity of the agents was not sufficient, and the effect of shortening the polymerization cycle by the combined use was small. Moreover, it was necessary to adjust the combination and the amount to be used for each polymerization temperature.

[0007] Recently, along with such improvement in productivity, the quality of the polymer has been emphasized, and not only the polymerization activity but also the
There is a desire for a polymerization initiator that improves the quality of the polymer.

For example, when IBO is used, the polymer obtained by polymerization has many fish eyes when it is used as a soft resin molded product. In ACSP, the thermal stability of the polymer is poor and the polymer is colored.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when a peracid ester having a specific structure is mixed in a specific ratio,
The inventors have found that the above problems can be solved and completed the present invention. That is, the weight ratio of (A) peracid ester represented by the general formula 3 to (B) peracid ester represented by the general formula 4 is (A) / (B) = 70/30 to 90/10. A polymerization initiator composition of a vinyl chloride-based monomer, characterized in that a mixture is used as an active ingredient.

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In the mixing ratio of (A) the perester represented by the general formula 3 and (B) the perester represented by the general formula 4, the weight ratio (A) / (B) is 90/10. When it becomes large, the polymerization activity at the initial stage of polymerization is not sufficiently obtained, and when the weight ratio of (A) / (B) becomes smaller than 70/30, the polymerization activity does not continue in the latter stage of polymerization.

In the polymerization initiator composition of the present invention, (A) the peracid ester represented by the general formula 5 and (B) the peracid ester represented by the general formula 6 are (A) / (B) = 70. / 30-9
A polymerization initiator composition of a vinyl chloride-based monomer, characterized in that an active ingredient is mixed in a weight ratio of 0/10.

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[Chemical 6]

Specific examples of the perester represented by the general formula 5 are cumylperoxy-2,2,3, trimethylhexanoate and cumylperoxy-2,2.
4,4-tetramethylpentanoate, cumylperoxy-2,2,4-trimethylhexanoate, cumylperoxy-2-ethyl-2,4-dimethylpentanoate
G, cumylperoxy-2,2-dimethylheptanoa
, Cumylperoxy-2-methyl-2-n-propylpentanoate, cumylperoxy-2,2,3,4-
Tetramethyl pentanoate, cumyl peroxy-2-
Ethyl-2,3,3-trimethylbutanoate, cumylperoxy-2-isopropyl-2,3-dimethylbutanoate, cumylperoxy-2-ethyl-2,3-dimethylpentanoate, Cumylperoxy-2-ethyl-2-methylhexanoate, cumylperoxy-2,
2-diethylpentanoate, cumylperoxy-2,
2,3,3-tetramethylpentanoate and the like, and specific examples of the peracid ester represented by the general formula 6 include cumylperoxy-2,2,8,8-tetramethyl. Nonanoate, cumylperoxy-2-isopropyl-2,2,6-trimethylheptanoate, cumylperoxy-2-ethyl-2,7,7-trimethyloctanoate and the like can be mentioned.

The perester of the present invention is synthesized as follows. That is, the acid chlorides of the corresponding acids are used alone or as a mixture thereof and cumyl hydroperoxide as a catalyst with sodium hydroxide or potassium hydroxide,
It can be obtained by reacting under the same reaction conditions as for ordinary peroxyesters. Also, use aromatic hydrocarbons (eg, toluene, ethylbenzene) or aliphatic hydrocarbons (eg, hexane, octane, mineral spirits, isoparaffin, etc.) as a diluent, or use after diluting after synthesis. Can be done.

The acid chloride used in the present invention is obtained by adding a chlorinating agent such as phosphorus trichloride, phosphorus oxychloride, thionyl chloride and phosgene to the corresponding acid alone or in a mixture, and then reacting the acid chloride from the reaction mixture. The product can be isolated and made.

The polymerization initiator composition containing the perester of the present invention is mainly used for the polymerization of vinyl chloride type monomers.
Examples of other vinyl monomers copolymerizable with the vinyl chloride monomer include ethylene, vinyl acetate, vinylidene chloride, styrene, acrylic acid esters, and methacrylic acid esters.

Further, the polymerization initiator composition containing the peracid ester of the present invention is not limited to other organic peroxide-based polymerization initiators such as tar.
Shabutyl Peroxy Neodecanoate, Territory
Amyl peroxypivalate, tert-sharpyl amyl peroxy neodecanoate, tert-shayl-hexyl peroxypivalate, ta-shari-hexyl peroxy neodecanoate, tert-octyl peroxypivale -To, tertiary-octyl peroxyneodecanoa-
Peroxy ester such as peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, peroxy dicarbonate such as di-1-methylheptyl peroxy dicarbonate, dioctanoyl peroxide, diisononano It can also be used as a mixture with diacyl peroxides such as ylperoxide and dilauroyl peroxide.

[0017]

The present invention using a specific polymerization initiator composition has the following features. That is, compared with the conventional method in the system using a polymerization initiator, a polymer can be obtained in good yield,
Moreover, the physical properties of the obtained polymer are good.

[0018]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

[0019]

Example 1 Synthesis Example 1 (Synthesis of neononanoic acid chloride) 158 g of neononanoic acid (using neononanoic acid from Exxon Corporation) was placed in a 500 ml four-necked flask equipped with a thermometer and a cooling tube with a drying tube at room temperature with stirring. Thionyl chloride (143 g) was added, the liquid temperature was raised to 60 ° C., and the reaction was continued for 4 hours. Then, unreacted thionyl chloride was distilled off under reduced pressure to obtain 171 g of neononanoic acid chloride. The chlorine content of this product is 20.
It was 0%, and the calculated purity was 99.5%. This is used for the synthesis of peroxyesters below.

Synthetic Example 2 (Synthesis of Neotridecanoic Acid Chloride) 158 g of neononanoic acid of Synthetic Example 1 was replaced with 214 g of neotridecanoic acid (using Exeacid 13 from Idemitsu Petrochemical), and otherwise, Synthetic Example 1
The same procedure as above was performed to obtain 231 g of neotridecanoic acid chloride. The chlorine content of this product was 15.2%, and the calculated purity was 99.8%. This is used for the synthesis of peroxyesters below.

Synthesis Example 3 (Synthesis of Mixed Acid Chloride of Neononanoic Acid and Neotridecanoic Acid) The same procedure as in Synthesis Example 1 was performed except that 158 g of neononanoic acid in Synthesis Example 1 was replaced with 158 g of (Neoacid 913 manufactured by Exxon Co.). Incidentally, neoacid 913 manufactured by Exxon Co. is commercially available as a mixed acid of 85% neononanoic acid and 12% neotridecanoic acid. Mixed acid chloride of neononanoic acid and neotridecanoic acid (hereinafter abbreviated as 913 acid chloride) 1
72 g were obtained. It was confirmed by gas chromatography that the ratio of the neononanoic acid component to the neotridecanoic acid component of this 913 acid chloride was the same as that of the raw material acid.

Synthetic Example 4 (Synthesis of cumyl percinecineonanoate) 41.7 g of 35% aqueous hydroxide solution was placed in a 200 ml four-necked flask equipped with a stirrer while keeping the liquid temperature at 15 ° C. under stirring.
41.8 g of% cumyl hydroperoxide is added.
Further, while maintaining the liquid temperature at 15 ° C., 35.3 g of neononanoic acid chloride obtained in Synthesis Example 1 is added dropwise. 15 ° C
After continuing the reaction for 3 hours, 50 ml of cold water is added and the solution is allowed to stand still for liquid separation. The oil layer is washed with 70 g of a 5% aqueous sodium hydroxide solution and then washed three times with water. Anhydrous magnesium sulfate was added to the obtained oil layer, and the mixture was stirred and dried, and then filtered to obtain 55.0 of a pale horizontal transparent liquid, cumylperoxyneonanoate (CNN). The amount of active oxygen was 4.65%, the purity was 85%, and the yield was 80%.

Synthesis Example 5 (Synthesis of cumyl peroxyneotridecanoate) 35.3 g of neononanoic acid chloride in Synthesis Example 4 was replaced with 46.7 g of neotridecanoic acid chloride, and the same procedure as in Synthesis Example 4 was repeated. Peroxyneo tridecanoate (CN
T) 60.8 g was obtained. The amount of active oxygen was 3.95%, the purity was 83%, and the yield was 75%.

Synthetic Example 6 (Synthesis of mixed peroxyester of neononanoic acid and neotridecanoic acid) Neononanoic acid chloride of Synthetic Example 4 35.
3 g was replaced with 36.3 g of 913 acid chloride, and the same procedure as in Synthesis Example 4 was repeated except that mixed peroxy ester (CNM) was used.
54.6 g was obtained. The weight ratio of neononanoic acid peroxyester to neotridecanoic acid peroxyester in the mixed peroxyester is (neononanoic acid peroxyester / neotridecanoic acid peroxyester) = (89
/ 11). The amount of active oxygen was 4.52%, the purity was 85%, and the yield was 77%.

Polymerization Example 1 Partially saponified polyvinyl alcohol in a 5 liter stainless steel autoclave equipped with a stirrer.
1 g and ion-exchanged water 3000 g are charged and dissolved by stirring. Next, CNM 1.0g (pure product equivalent) and 1500g
While charging the vinyl chloride monomer of, and stirring, the internal temperature 45
Polymerization was performed at a temperature of 5 ° C. for 5 hours. The polymerized slurry was taken out, filtered and dried. The polymerization rate was 85%.

Polymerization Example 2 Polymerization was carried out in the same manner as in Polymerization Example 1 except that the internal temperature during polymerization in Polymerization Example 1 was changed to 52 ° C.
The polymerization rate was 87%.

Polymerization Example 3 CNM of Polymerization Example 1 1.0 g
(Purity equivalent) CNM 0.8g (pure equivalent) and cumylperoxyneotridecanoate (CNT) 0.2g
Polymerization was carried out in the same manner as in Polymerization Example 1 except for the (pure product equivalent amount). The polymerization rate was 84%.

Polymerization Example 4 1.0 g of CNM of Polymerization Example 2
(Purity equivalent) CNM 0.8g (pure equivalent) and cumylperoxyneotridecanoate (CNT) 0.2g
Polymerization was carried out in the same manner as in Polymerization Example 2 except for the (pure product equivalent amount). The polymerization rate was 87%.

[0029]

Comparative Example 1 1.0 g of CNM of Polymerization Example 1 (equivalent amount of pure product)
Cumyl Perchiocineonanoart (CNN) 1.0
Polymerization was carried out in the same manner as in Polymerization Example 1 except that g (pure product equivalent amount) was replaced. The polymerization rate was 74%.

[0030]

[Comparative Example 2] 1.0 g of CNM in Polymerization Example 1 was replaced with 1.0 g of cumylperoxyneotridecanoate (CNT) (converted to a pure product), and the internal temperature was changed from 45 ° C to 52 ° C. Polymerization was carried out in the same manner as in. The polymerization rate was 75%.

[0031]

Comparative Example 3 1.0 g of CNM of Polymerization Example 1 (equivalent amount of pure product)
Cumyl Perchiocineonenonate (CNN) 0.7
Polymerization was performed in the same manner as in Polymerization Example 1 except that g (pure product equivalent amount) and t-butylperoxyneodecanoate (ND) 0.3 g (pure product equivalent amount) were used. The polymerization rate was 73%.
As can be seen from the above results, the object of the present invention cannot be achieved by the combination of CNN and ND.

[0032]

[Comparative Example 4] CNM of Polymerization Example 2 1.0 g (equivalent amount of pure product)
Cumyl Perchiocineo Tridecanoate (CNT)
Polymerization was carried out in the same manner as in Polymerization Example 1 except that 0.7 g (pure product equivalent amount) and t-butylperoxyneodecanoate (ND) 0.3 g (pure product equivalent amount) were used. The polymerization rate was 76%. As can be seen from the above results, the object of the present invention cannot be achieved by the combination of CNT and ND.

[0033]

[Comparative Example 5] CNM of Polymerization Example 1 1.0 g (equivalent to pure product)
0.5 g (pure product equivalent amount) of t-butylperoxyneodecanoate (ND), which is a conventional polymerization initiator, and ACSP
Polymerization was carried out in the same manner as in Polymerization Example 1 except that the amount was changed to 0.5 g (pure product equivalent amount). The polymerization rate was 75%.

[0034]

Comparative Example 6 1.0 g of CNM of Polymerization Example 1 was added to t-butylperoxy neodecanoate (N
D) Polymerization was performed in the same manner as in Polymerization Example 2 except that 0.7 g (pure product equivalent) and ACSP 0.3 g (pure product equivalent) were used.
The polymerization rate was 73%.

[Coloring Test] Vinyl Chloride Polymer 100
g, dibutyltin maleate 2.5 g, dioctyl phthalate
50 g of the sheet was mixed and kneaded with a roll at 160 ° C. for 7 minutes, and the coloring of the sheet was visually observed. The test results are shown in Table 1.

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Eiji Fujikawa 2-10-6 Miyanishi, Harima-cho, Kako-gun, Hyogo Sanken Kako Co., Ltd.

Claims (1)

[Claims] 1. A (A) peracid ester represented by the general formula 1 and (B) a perester represented by the general formula 2 are (A)
/ (B) = 70/30 to 90/10 mixed in a weight ratio as an active ingredient, a polymerization initiator composition of a vinyl chloride monomer. Embedded image Embedded image