JP2931015B2 - Polymerization catalyst composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polymerization catalyst composition containing an organic peroxide.

[Prior Art] Organic peroxides have an -O-O- bond in the molecule, thermally decompose at a relatively low temperature, and easily generate free radicals. Therefore, as a radical source in radical polymerization, that is, as a polymerization initiator, It is well known that it is used. Generally, this compound is stable at normal temperature and is used for curing unsaturated polyesters in addition to polymerization and copolymerization of olefins and vinyl monomers. However, sparks, heating, friction, impact, impurities (acid or alkali) Has the disadvantage that it decomposes or explodes due to the incorporation of it, and is much more sensitive to this explosion than picric acid, TNT or the like. Because organic peroxides are dangerous to handle, Japanese Patent Publication No. 48-16715,
As shown in JP-A-54-160487, in the manufacturing process, dilute with dioctyl phthalate, dibutyl phthalate, etc., and during storage, dilute with pure products such as calcium sulfate, calcium carbonate, dibasic calcium phosphate, water and aliphatic hydrocarbons Has been used. However, in the polymerization catalyst composition thus obtained, peroxides gradually decompose over time, and not only good polymerization efficiency is not obtained, but also a diluent remains in the polymerization product, so that a high-purity product is obtained. Required further purification or drying of the polymerized product.

[Problems to be Solved by the Invention] An object of the present invention is to provide a polymerization catalyst composition which improves storage stability, polymerization efficiency and water repellency and does not require purification or drying of a polymer product.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that it is effective to mix a fluorine-based oil with an organic peroxide. Reached.

That is, the constitution of the present invention is a storage-stabilized radical polymerization catalyst composition containing an organic peroxide and a perfluoro-based oil as a storage stabilizer as main components.

The fluorinated oil used in the present invention is obtained by replacing hydrogen of a hydrocarbon oil with fluorine. Of these, perfluoro-based oils are more preferred. Hereinafter, examples of perfluoro-based oils and their physical properties are shown in a table.

The fluorinated oil is an odorless inert liquid having a high boiling point and a high flash point and contains no impurities such as acids and alkalis. Therefore, there is no danger of peroxide being decomposed or exploding by these fluorinated oils. Therefore, the storage stability of the peroxide can be remarkably improved. Also various polymerization methods,
For example, even in an exothermic reaction such as bulk polymerization, a polymer can be produced with high polymerization efficiency because it is well mixed with peroxide and appropriately controls the decomposition rate of radicals. Furthermore, since this aliphatic hydrocarbon does not remain in the polymerized product,
It has the advantage that purification or drying can be omitted.

On the other hand, as the organic peroxide, all conventionally used organic peroxides can be used. For example, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexane peroxide; 1,1-bis (t-butylperoxy) cyclohexane, n Peroxyketals such as -butyl-4,4-bis (t-butylperoxy) parylate; dialkyl peroxides; benzoyl peroxide, succinic peroxide, decanoyl peroxide, and 2,4-dichlorobenzoyl peroxide; Diacyl peroxide; 2,5-dimethyl-2,5-di (benzoyl peroxide) hexane, t-butylperoxymaleic acid,
t-butyl peroxyisopropyl carbonate, di-
Peroxyesters such as t-butyl diperoxyphthalate and the like can be mentioned.

In the composition of the present invention, the weight ratio of the organic peroxide / fluorinated oil is generally 30 to 90/70 for the above-mentioned purpose.
-10, preferably about 50-75 / 50-25. Further, the composition of the present invention can be applied to polymerization reactions such as emulsion polymerization, bulk polymerization and solution polymerization. In this case, usually 0.
Used from 05 to 2.0 wt%.

Note that the composition of the present invention contains other solvents, for example, toluene,
Xylene, higher alcohols, aliphatic hydrocarbons and the like can be added in an amount of about 20% by weight or less based on the total amount.

 Examples will be described below.

Example 1 500 g of 2,4-dichlorobenzoyl chloride and 200 g of perfluorocyclohexane were placed in a four-necked flask and mixed. Then, after adding 4 g of monoethanolamine and reacting at 80 ° C. for 2 hours, 100 g of hydrogen peroxide was added dropwise over 5 hours, and further reacted at 80 ° C. for 10 hours to convert 2,4-dichlorobenzoyl chloride to hydrogen peroxide. Oxidation. This was washed with water in a separating funnel, and then water was decomposed to obtain a polymerization catalyst composition (peroxide concentration: 70.60%) comprising 2,4-dichlorobenzoyl peroxide and perfluorocyclohexane.

Further, as Comparative Example 1, a polymerization catalyst composition was obtained in the same manner as in Example 1 except that perfluorocyclohexane was omitted, and washing was performed with water, followed by drying under reduced pressure.

Next, the results of measuring the peroxide content and the active oxygen content of these compositions immediately after preparation and after storage at room temperature for 6 months are shown in Table 1.

As can be seen from Table 1, the product of the present invention has less change over time in the peroxide content and the amount of active oxygen than the comparative product, and thus has excellent storage stability. The product of the present invention did not show any risk of explosion.

Example 2 500 g of benzoyl chloride and 200 g of perfluorobutyltetrahydrofuran are placed in a four-necked flask and mixed. 1 g of pyridine was added thereto, and the mixture was reacted at 85 ° C. for 4 hours. Then, 200 g of hydrogen peroxide was added dropwise over 8 hours, and the mixture was further reacted for 5 hours to oxidize benzoyl chloride with hydrogen peroxide. This was washed with water in a separatory funnel, and water was separated to obtain a polymerization catalyst composition comprising benzoyl peroxide and perfluorobutyltetrahydrofuran (peroxide concentration: 82%).

On the other hand, as Comparative Example 2, benzoyl peroxide having a purity of 98% was prepared.

The compositions were then tested for explosiveness. First, eight beakers (5 volumes) each containing 500 g of the product of the present invention and 850 g of comparative products were prepared, and a far-infrared heater heated to 700 ° C. was brought close to each beaker. Exploded at the same time,
None of the products of the present invention exploded.

Examples 3 to 8 In Example 1, the peroxide and the fluorinated oil or those shown in Table 2 were used as diluents, respectively, to obtain polymerization catalyst compositions having the same peroxide concentrations as shown in Table 2. These active oxygen contents are shown in Table-8.

As can be seen from Table 3, the compositions of Examples 3 to 8 also have excellent storage stability.

Further, a polymerization reaction was carried out using each polymerization catalyst composition obtained as described above. First, isooctane 30 was placed in a three-necked flask (2 volumes) equipped with a stirrer, thermometer, and cooling device.
Take 0 g and heat to 90 ° C. Next, each composition containing 150 g of methyl methacrylate, 20 g of methacrylic acid, and 8 g of peroxide was mixed and polymerized dropwise in the flask over 1 hour. Table 4 shows the polymerization results.

[Effects of the Invention] As described above, the polymerization catalyst composition of the present invention is excellent in storage stability, and can improve polymerization efficiency and water repellency of a polymer obtained thereby.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hidemi Uematsu 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd. (56) References JP-A-46-5243 (JP, A) JP-A Sho 46-7287 (JP, A) JP-A-48-96678 (JP, A) JP-A-49-14407 (JP, A) JP-A-49-74291 (JP, A) JP-A-49-90787 (JP, A) A) JP-A-49-118789 (JP, A) JP-A-49-125490 (JP, A) JP-A-51-41086 (JP, A) JP-A-51-132294 (JP, A) JP-A Sho 52 JP-A-8-887 (JP, A) JP-A-55-139357 (JP, A) JP-A-58-139210 (JP, A) JP-A-61-152652 (JP, A) JP-A-61-152653 (JP, A) JP-A-61-291676 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/00-4/82

Claims (1)

(57) [Claims] 1. A storage-stabilized radical polymerization catalyst composition comprising an organic peroxide and a perfluoro-based oil as a storage stabilizer as main components.