JPS6065065A - Production of chlorinated polymer - Google Patents

Abstract

PURPOSE:To increase an apparent specific gravity and to improve crushability, by spray-drying a chlorinated polyolefin polymer obtd. by a reaction in a solvent, adding a plasticizer thereto and crushing the mixture. CONSTITUTION:A polyolefin polymer such as natural rubber, polybutadiene, an ethylene (co)polymer or a propylene (co)polymer is dissolved in a chlorine-resistant solvent such as carbon tetrachloride or trichloroethylene. Chlorine is bubbled through the soln. in the presence of a catalyst or under ultraviolet light irradiation to chlorinate the polymer. The resulting soln. is sprayed through a nozzle into a hot-air oven to remove the solvent. 3-20pts.wt. plasticizer such as tributyl phosphate, dimethyl phthalate or bisphenol A epoxy resin is added to 100pts.wt. chlorinated polymer. The mixture is crushed by using a porcelain ball mill.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies to chlorinated polymers or chlorinated copolymers such as chlorinated rubber, chlorinated polypropylene, chlorinated polyethylene, etc., which are widely used today in paints, inks, adhesives, etc. It relates to methods of manufacturing things.

In general, the above chlorinated products are produced by dissolving the raw material in a chlorine-resistant solvent, such as carbon tetrachloride, trichloroethylene, or tetrachloroethane, and then adding a catalyst such as an organic degenerated product to the solution, or completely blowing in chlorine while fully irradiating it with ultraviolet rays. , chlorine substitution or addition by known methods.

The chlorinated polymer can be isolated from the reaction solution by pouring it into steam or hot water to remove the solvent, or by pouring it into a non-solvent that does not dissolve the chlorinated polymer at all, such as alcohol, to precipitate the resin. There are several methods such as separating the solvent and evaporating the solvent by spraying it into a hot air atmosphere.
・ Among these methods, a method of spraying in a hot air atmosphere is proposed in Japanese Patent Publication No. 36310/1973. However, in this method, the higher the degree of polymerization and viscosity of the chlorinated polymer, and the greater the amount of spraying, the worse the spray condition becomes, and the chlorinated polymer becomes bulkier. It is difficult to transport the product by air, and the product is inconvenient to transport and has low commercial value. These drawbacks can be improved to some extent by diluting or emulsifying the reaction solution and spraying it, but it is not sufficient.

Therefore, the present inventor investigated various methods for reducing the bulk of this spray-dried bulky solid material and improving the crushability. As a result, the present inventor added 5 to 20 parts by weight of a plasticizer to 100 parts by weight of the chlorinated polymer. By impregnating parts by weight of ene, the bulky powder first shrinks in volume and its apparent specific gravity increases slightly, and when it is further sent to the crushing process, the crushability is much improved compared to the case without additives. This discovery led to the present invention.

One of the reasons for the improvement in crushability is thought to be that the surface of the powder is covered with a plasticity filler, which increases frictional resistance and allows it to receive the impact of crushing more accurately.

Examples of the plasticizer used in the present invention include tributyl phosphate, tricresyl phosphate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, dibutylbenzyl phthalate, butyl oleate, glycerin monooleate, adipine butyl , butyl sebacate, diethylene glycol benzoate, butyl phthalyl butyl glycolate, chlorinated paraffin, epoxidized soybean oil, phenyl glycidyl ether, bisphenol A type epoxy resin, etc., which can impart plasticity to the chlorinated polymer can be used. be.

The reason why the amount of these substances added is 3 to 20 parts by weight per 100 parts by weight of the chlorinated polymer is that if it is less than 3 parts by weight, it will not be very effective in improving the apparent specific gravity, and if the amount exceeds 20 parts, it will increase the solid content. This is because the amount of material adhering to the surface is too large, causing adhesion to the container wall, which actually hinders the movement of objects.

To explain the present invention in detail, first, a polyolefin polymer is chlorinated in a chlorine-resistant solvent, and the solution is 1% in diameter.
After the solvent and chlorinated polymer are completely separated by being injected into a hot air oven under pressure from an injection nozzle equipped with many injection holes, air spray, airless spray, shower, etc. The above plasticity imparting agent is a chlorinated polymer 100%
It is dispersed in an amount of 5 to 20 parts by weight, and then pulverized.

The chlorinated polymer used in the present invention is not particularly limited, but includes natural rubber, polyisoprene, polyethylene, polypropylene, ethylene propylene copolymer, ethylene acetate copolymer, ethylene propylene terpolymer, polybutadiene, etc. A chlorinated product having a chlorine content of 55 to 75 parts by weight.

Example-1 Polyisoprene rubber (MW = 4
00
Add f and stir well.

Next, gaseous chlorine is blown into the reactor from the bottom to carry out a chlorination reaction. At 6.5 hours after the start of the reaction, a portion of the reaction solution was poured into dimethanol for solid-liquid separation and then dried. The dried product was dissolved in 20 titolene and the viscosity at 25°C [
When measured, it was 23 cps.

The above reaction solution was concentrated to 15 parts by weight and sprayed into a hot air oven at 130°C to obtain a dry powder. The apparent specific gravity of this powder was 0.028, and it was chewed with a bulky substance. After spraying and impregnating an amount equivalent to 0,510.15 parts by weight of this powder SOt@Tori Toyo Barax A40 (Toyo Tsudani Industry ■ product, chlorinated paraffin) with a total airless sprayer, the volume was 1.
0.15° 30.45, 60, with a porcelain ball mill containing 5 tons of porcelain balls with a diameter of 20 to 25IIIN+.
75. Milled for 90 minutes.

Table 1 shows the results of measuring the apparent specific gravity of this pulverized product.

Table 1 Example-2 Toyobarax A4 (L Ebiol p) used in Example 1
The same procedure as in Example 1 was carried out except that (NOF ■ product phenylglycidyl) was used.

Example-3 1.50/cti, 105°C using the apparatus of Example-1
A polypropylene having a melt index of 7 r710 minutes was similarly chlorinated under the conditions of 7 to 10 minutes to obtain a polypropylene with a degree of chlorination of 67.8% and a viscosity of 15 cps.

This chlorinated polypropylene/carbon tetrachloride liquid gold solid content 1
It was concentrated to 8% and then sprayed into a hot air oven at 130°C to obtain a dry powder. The apparent specific gravity of this powder is 0.
It was bulky at 034. This powder 50tf and Quavo Tote YD127 (Tobu Kasei epoxy resin) t-0
, 5', 8.12 parts by weight equivalent was sprayed with air spray, and then 0.15, 30, 4
5. Milled for 60 minutes.

Results of all measurements of the apparent specific gravity of this pulverized material are shown in Table 3. Procedures (spontaneous) October 19, 1981 1. Indication of the incident 1988 Patent Application No. 172714 2. Name of the invention Chlorinated polymer Manufacturing method 3, relationship with the elderly case to be amended Patent applicant address 1-4-5 Marunouchi, Chiyoda-ku, Tokyo Name (2)
34) Sanyo Kokusaku Pulp Co., Ltd. 4, Agent Address: Kanda Kita Vehicle, Chiyoda-ku, Tokyo! ! Address 1116
101 English Building 3rd floor 5, Section 6 of the detailed description of the invention in the specification subject to amendment, Contents of amendment

Claims (1)

[Claims] (1) A chlorinated polymer obtained by dissolving a polyolefin polymer or its copolymer in a chlorine-resistant solvent and chlorinating it is sprayed into hot air to solidify it, and then 100 parts by weight of the chlorinated polymer 1. A method for producing a chlorinated polymer, which comprises adding 3 to 20 parts by weight of a plasticizing agent to a chlorinated polymer and pulverizing the mixture.