JPH03197510A - Production of chlorinated polyolefin - Google Patents

Abstract

PURPOSE:To produce simultaneously a chlorinated polyolefin and a chlorinated paraffin by chlorinating a mixture of a (modified) polyolefin with a specified paraffinic hydrocarbon to a chlorine content in a specified range under a temperature at which the mixture is liquid. CONSTITUTION:A polyolefin (e.g. PE, PP or ethylene/propylene copolymer) or a polyolefin graft-modified with an unsaturated carboxylic acid [e.g. (meth) acrylic or maleic acid] is mixed with an 8C or higher paraffinic hydrocarbon (desirably a 10-35C n-paraffin), and the mixture is chlorinated to a chlorine content of 5-75% at a temperature at which the mixture is liquid. A chlorinated polyolefin and a chlorinated paraffin can be simultaneously produced. Because the reaction can be carried out at normal pressure according to the above process, the operation of chlorination is simple and the reaction apparatus is inexpensive.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel method for producing chlorinated polyolefins or chlorinated modified polyolefins that are soluble in organic solvents used in paints, inks, and the like. More specifically, the present invention relates to a novel manufacturing method that makes it possible to simultaneously manufacture the chlorinated polyolefins and chlorinated paraffins.

[Conventional technology]

Resins obtained by chlorinating polyolefins are industrially produced and used in a wide variety of fields because they dissolve in organic solvents and have excellent properties. Products with a high chlorine content are used as anticorrosion paints for outdoor buildings due to their excellent weather resistance, while those with a low chlorine content adhere to polypropylene and are used as inks for polypropylene films and primers for painting polypropylene molded objects. It is used in

Various methods are known for chlorinating polyolefins.
They can be roughly divided into suspension chlorination methods (for example,
(Japanese Patent Publication No. 36-4745), solution chlorination method (for example, Japanese Patent Publication No. 48-8856), and bulk chlorination method (for example, Japanese Patent Publication No. 46-737). The suspension chlorination method is carried out by making polyolefin into fine particles, suspending them in water, irradiating them with ultraviolet rays, or adding a radical generator and blowing chlorine gas into them. After chlorination is complete, the chlorinated product is separated from water and dried.

The solution chlorination method involves dissolving a polyolefin in a chlorine-based organic solvent that is inert to chlorine, such as carbon tetrachloride, chloroform, methylene chloride, trichloroethane, etc.
Chlorinate by irradiating with ultraviolet rays or adding a radical generator and blowing chlorine gas. The solvent is separated from the product to obtain the chlorinated polyolefin. The method of chlorinating by pulverization involves bringing powdered polyolefin into contact with chlorine gas in a fluidized bed or the like.

On the other hand, chlorinated paraffin is useful as a plasticizer for vinyl chloride, and is produced with a low chlorine content to about 70%. Chlorinated paraffin is produced by heating normal paraffin or paraffin wax to a temperature of around 100° C. to melt it, or by dissolving it in a chlorinated organic solvent such as carbon tetrachloride, and then chlorinating it by blowing chlorine gas into it.

[Problem to be solved by the invention]

The suspension chlorination method is a heterogeneous reaction, and chlorination proceeds from the outside of the raw material particles, making it difficult to chlorinate the inside, making it difficult to uniformly chlorinate the raw material unless it is made into fine particles of several microns or less. There is a drawback. Since pulverization requires a lot of effort, polyolefins with a size of 10 microns are usually used, but the chlorinated polyfins obtained in this case have poor solubility in organic solvents, and compared to the method of chlorination using a solution. It will not become soluble in organic solvents unless a large amount of chlorine is introduced, and even if it does dissolve, undissolved lumps often remain.

Although the method of chlorination in a solution is a homogeneous reaction and does not have the above-mentioned drawbacks, the chlorination reaction must be carried out under pressure because polyolefins are difficult to dissolve in chlorinated organic solvents at normal pressure, making the operation complicated. The disadvantage is that the equipment is also expensive. Furthermore, large amounts of chlorinated organic solvents, which are harmful to the human body and may have an adverse effect on the environment, must be used, and if they remain in the final product, not only will the performance be impaired, but the applications will be limited.

Bulk chlorination methods have the same drawbacks as suspension chlorination methods, as well as the difficulty in controlling the reaction.

On the other hand, chlorinated paraffins can be reacted in equipment similar to the equipment used to chlorinate polyolefins in solution.
It was not possible to chlorinate polyolefins and paraffins simultaneously.

The present invention solves the problems of the suspension chlorination method and the solution chlorination method, and makes it possible to produce chlorinated polyolefins with excellent solubility in organic solvents with simple operations. The object of the present invention is to provide a highly productive manufacturing method that can simultaneously produce chlorinated polyolefins and chlorinated paraffins.

[Means to solve the problem]

As a result of intensive research to achieve the above object, the present inventors have found that by mixing a polyolefin or a polyolefin graft-modified with an unsaturated carboxylic acid and a paraffin hydrocarbon having a carbon number of more than 8, the mixture is heated at a temperature where the mixture is liquid. They have invented a method for producing chlorinated polyolefin, which is characterized by chlorinating the chlorine content to a chlorine content of 5 to 75%. That is, the present invention mixes a polyolefin or a polyolefin graft-modified with an unsaturated carboxylic acid and a paraffinic hydrocarbon having a carbon number of more than 8,
By heating the mixture to melt it and performing the chlorination reaction by blowing chlorine gas into the mixture in a temperature range where the mixture can maintain a uniformly mixed liquid state, the reaction apparatus and reaction operation are simple, It was discovered that the chlorination reaction progresses uniformly, and not only can chlorinated polyolefins with excellent solubility in aromatic organic solvents be produced, but also chlorinated paraffins can be produced at the same time.

In the present invention, polyolefin refers to polyethylene.

Polypropylene, polybutene, its low carbon number α of 5 or more
-Polymer of olefin, poly(4-methylpentene-1)
), ethylene-propylene copolymer, propylene-butene copolymer, ethylene-butene copolymer, ethylene-propylene-butene terpolymer, other α-olefin copolymers, α-olefin and 50% or less Examples of copolymers with other monomers include ethylene-vinyl acetate copolymers,
It refers to ethylene-ethyl acrylate copolymer, ethylene-maleic anhydride copolymer, ethylene-ethyl acrylate-maleic anhydride terpolymer, and the like. Moreover, the polyolefin graft-modified with an unsaturated carboxylic acid refers to a polyolefin obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof to the polyolefin by a known method. Examples of unsaturated carboxylic acids or derivatives thereof include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid or their alkyl esters, unsaturated dicarboxylic acids such as maleic acid and itaconic acid, their acid anhydrides, or their alkyl esters. . The graft copolymerization method uses a radical generator such as an organic peroxide as a catalyst, heat-melts the polyolefin, and reacts it with an unsaturated carboxylic acid or its derivative in the bulk state, or reacts it with an organic solvent such as xylene. Heat to dissolve and react. The unsaturated carboxylic acid or its derivative is preferably graft copolymerized in an amount of 01 to 20% by weight. There is no equivalent restriction on the molecular weight of the polyolefin or the polyolefin obtained by graft copolymerizing an unsaturated carboxylic acid, and the form thereof may be any of blocks, pellets, and powder.

Paraffinic hydrocarbons having a carbon number greater than 8 are saturated chain hydrocarbons represented by the general formula C, H2, 2. If the number of carbon atoms is 7 or less, the boiling point is low and it is difficult to produce a chlorinated polyolefin. More preferred is normal paraffin having 10 to 35 carbon atoms, and chlorinated paraffin produced simultaneously with chlorinated polyolefin has great industrial value. Normal paraffin is a straight-chain paraffin hydrocarbon, and the produced chlorinated paraffin has good stability. Number of carbons is 10 to 1
Those having 6 carbon atoms are liquid at room temperature, and those having 17 to 35 carbon atoms are wax-like solids at room temperature and are also called paraffin wax, but both can be used in the present invention. Further, a mixture of paraffin hydrocarbons having different carbon numbers may be used.

Polyolefins or polyolefins graft-modified with unsaturated carboxylic acids and paraffinic hydrocarbons having a carbon number of more than 8 are compatible, and when heated and melted, they mix in any proportion to form a uniform liquid state. This state can be achieved at a temperature several tens of degrees Celsius lower than the melting point of the polyolefin or polyolefin graft-modified with an unsaturated carboxylic acid by lowering the melting point by dissolving or plasticizing the polymer. The chlorination reaction can be carried out as many times as required as long as the temperature allows the mixture to maintain its liquid state, but at high temperatures the dechlorination reaction is likely to occur at the same time as the chlorination reaction, which may result in coloring, so it is preferable to carry out the reaction at the lowest possible temperature. .

More preferably a temperature range of 50 to 140°C,
14 [At temperatures above 1°C, coloration becomes significant and the appearance of the obtained chlorinated product is impaired. On the other hand, if the temperature is below 50°C, the reaction rate of chlorination is slow and chlorination takes time, which is not preferable.

There is no particular restriction on the mixing ratio of polyolefin or polyolefin graft-modified with unsaturated carboxylic acid and paraffinic hydrocarbon having more than 8 carbon atoms, but in order for the reaction to proceed efficiently, polyolefin or unsaturated carboxylic acid The weight ratio of polyolefin graft-modified with acid to paraffinic hydrocarbon with a carbon number greater than 8 is 951.
It is preferable to set it as 5 to 1/99. If the proportion of paraffinic hydrocarbons is less than 5, the reaction must be carried out at high temperature or high viscosity, which is undesirable because coloring tends to occur. If the proportion of polyolefin or polyolefin graft-modified with unsaturated carboxylic acid is less than 1, a large amount of chlorinated paraffin products will be produced, which is disadvantageous for industrial production. Further, the viscosity of the mixture of both is preferably 3000 cps or less at the temperature at which chlorination is carried out. 3
If it exceeds 000 cp+, the local chlorination reaction may proceed violently and the resin may be carbonized, which is not desirable. 3000
cps or less can be adjusted by changing the ratio of polyolefin or polyolefin graft-modified with unsaturated carboxylic acid to paraffinic hydrocarbon having a carbon number of more than 8, or by changing the temperature.

The amount of chlorine introduced by chlorination is 5 to 75% (wt%, hereinafter the same). Generally, polyolefins do not dissolve in organic solvents such as toluene and xylene, but as chlorine is introduced, the crystal structure of the polymer collapses and it becomes soluble in organic solvents.

However, if the chlorine content is less than 5%, the chlorinated product will not dissolve in organic solvents such as toluene and xylene, so there is no point in implementing it industrially. If it exceeds 75%, the reaction efficiency of chlorination decreases and it becomes uneconomical. In addition, when a mixture of polyolefin or unsaturated carboxylic acid grafted polyolefin and paraffinic hydrocarbon is chlorinated, both are chlorinated.
Depending on the raw material, the chlorine content of paraffinic hydrocarbons will be slightly higher, but the chlorine content of each will be approximately the same.

When performing chlorination by blowing chlorine gas, it is preferable to irradiate ultraviolet rays or use a radical generator such as an organic peroxide or an azo compound as a catalyst to promote the reaction efficiently, but chlorination is possible even without these. The reaction proceeds. Chlorine gas may be blown directly into the chlorine, but it may also be diluted with an inert gas such as nitrogen or hydrogen chloride gas. In this case, there are advantages that the reaction can be easily controlled and that the temperature of the system can be prevented from rising due to reaction heat.

The apparatus for carrying out the chlorination reaction can be a reaction tank whose inner surface is lined with glass and is equipped with a stirrer, a chlorine blower, a by-product waste gas treatment apparatus, and a heating jacket. If necessary, install an ultraviolet lamp inside the tank.

In order to proceed with the reaction uniformly, it is desirable that the stirring be performed strongly. In order to increase reaction efficiency, it is preferable to adopt a structure in which chlorine gas is blown from the bottom of the reaction tank.

After the reaction, the product is separated into chlorinated polyolefin or chlorinated unsaturated carboxylic acid grafted polyolefin and chlorinated paraffin using an organic solvent that is a non-solvent for chlorinated polyolefin and a good solvent for chlorinated paraffin. be able to. Examples of such solvents include isopropyl alcohol and hexane.

The chlorinated polyolefin or chlorinated unsaturated carboxylic acid grafted polyolefin from which the chlorinated paraffin has been separated is obtained in solid state and pelletized by known methods or prepared in toluene.

It is made into a product by dissolving it in an aromatic organic solvent such as xylene. The separated chlorinated paraffin is obtained as a liquid or a waxy solid depending on the chlorine content when the solvent is removed by distillation.

[For production]

In the method for producing chlorinated polyolefins of the present invention, the mixture of polyolefin or unsaturated carboxylic acid graft polyolefin and paraffinic hydrocarbon having a carbon number of more than 8 is in a liquid state, so that chlorination is uniformly performed. As a result, a chlorinated polyolefin with a structure in which chlorine is randomly distributed on the polymer chain is produced, and has excellent solubility in organic solvents. In addition, the melting point of the raw material polymer is lowered by the plasticizing action of the paraffinic hydrocarbon, and the chlorination reaction can be carried out at a relatively low temperature, thereby preventing coloring of the product. Since paraffinic hydrocarbons having carbon atoms of 8 or more are used, the reaction can be carried out at normal pressure, the operation is simple, and the equipment is inexpensive.

Since paraffin can also react with chlorine, chlorinated paraffin can be produced at the same time.

〔Example〕

Hereinafter, the present invention will be specifically explained based on Examples.
The present invention is not limited thereby.

Example 1 Isotactic polypropylene (
Weight average molecular weight = 180,000) 60g and normal paraffin (CI4H30: 48%, C, , H, □: 48%)
240g was charged and heated using an oil bath. 1
After completely melting the mixture of polypropylene and normal paraffin at 50°C, the temperature is lowered to bring the internal temperature to 12°C.
The temperature was 0°C.

The mixture was a clear liquid. Take out the contents 120
Viscosity measured with a B-type viscometer at °C is 1500 cp
It was +. Chlorination was started by blowing gaseous chlorine from the bottom of the flask while stirring.

Chlorination was carried out while maintaining the temperature at 120°C, and the contents were appropriately extracted during the reaction, and chlorine was blown into the reactor to complete the reaction while measuring the chlorine content. The chlorine content of the reactant was 34%. The reaction product was poured into a large amount of isopropyl alcohol to precipitate chlorinated polypropylene and taken out, and the supernatant liquid was distilled under reduced pressure to remove isopropyl alcohol to obtain chlorinated paraffin. The chlorine content of the chlorinated polypropylene was measured to be 28%. The chlorine content of the chlorinated paraffin was 36%.

Example 2 (Graft reaction of unsaturated carboxylic acid) Isotactic polypropylene (weight average molecular weight, 6
1,000) Place 300 g in a 1 liter flask with a stirrer and heat to 180°C using an oil bath. While stirring, add 12 g of maleic anhydride and 1.2 g of di-t-butyl peroxide as an organic peroxide. was added over 2 hours, and then reacted for 2 hours. The resulting product contained 3% of maleic 5-6 acid anhydride.

(Chlorination reaction) 150 g of isotactic polypropylene graft-modified with the unsaturated carboxylic acid obtained above and 150 g of normal paraffin (same as in Example 1) were mixed and melted, and a chlorination reaction was carried out in the same manner as in Example 1. I did it. The chlorinated polypropylene obtained after separation of the chlorinated paraffins had a chlorine content of 22%.

Example 3 Ethylene-vinyl acetate copolymer (vinyl acetate content 19%)
, melt flow rate 150g/10min) 100g and normal paraffin (same as Example 1) 20
A chlorination reaction was carried out in the same manner as in Example 1 using 0 g. Chlorinated ethylene obtained after separating chlorinated paraffin
The vinyl acetate copolymer had a chlorine content of 18%.

Example 4 Isotactic polypropylene (weight average molecular weight 26
100g) and paraffin wax (C2oH5o
1 (melting point: 44° C.) were mixed and melted, and a chlorination reaction was carried out in the same manner as in Example 1. The chlorinated polypropylene obtained after separation of the chlorinated paraffins had a chlorine content of 21%.

Example 5 Isotactic polypropylene (weight average molecular weight, 6
240 g of paraffin) and 60 g of normal paraffin (same as in Example 1) were mixed and melted, and a chlorination reaction was carried out in the same manner as in Example 1, except that the temperature was 135°C. The chlorinated polypropylene obtained after separation of the chlorinated paraffins had a chlorine content of 21%.

Example 6 Isotactic polypropylene (weight average molecular weight: 1
80,000 g) and 240 g of normal paraffin (same as in Example 1) were mixed and melted, and a chlorination reaction was carried out in the same manner as in Example 1, except that the temperature was 150°C. During the reaction, the color gradually started to change and eventually turned black. The chlorinated polypropylene obtained after separating the chlorinated paraffin had a 7 8 chlorine content of 28% and was black in color.

Comparative Example 1 Isotactic polypropylene (weight average molecular weight: 1
80,000) and 240 g of normal paraffin (same as in Example 1) were mixed and melted, and when the temperature was lowered to 110°C, crystals began to precipitate, but the temperature remained at 110°C.
The chlorination reaction was started by performing the same operation as in Example 1 while maintaining the temperature at °C. As the viscosity gradually increased, the reaction solution began to become colored and could no longer be stirred, so the reaction was stopped. The chlorinated polypropylene obtained after separating the chlorinated paraffin had a chlorine content of 11% and was brown in color.

Comparative Example 2 Isotactic polypropylene (weight average molecular weight: 1
Example 1
Chlorination was carried out in the same manner as above. After the reaction was completed, it was filtered to obtain chlorinated polypropylene. Chlorine content rate 3
%Met.

Comparative Example 3 Isotactic polypropylene (weight average molecular weight: 1
80,000) to obtain powder with an average particle size of 120μ. In a 10 liter flask equipped with a stirrer, chlorine blower, and waste gas outlet, add 300 g of ground isotactic polypropylene.

Add 6 liters of water and 1 g of surface lubricant, and while stirring, blow gaseous chlorine from the bottom of the flask at a temperature of 90°C while irradiating with ultraviolet rays. During the reaction, remove the contents as appropriate and chlorinate while measuring the chlorine content. I did it. After the reaction, the product was filtered, washed repeatedly with an aqueous alkali solution and then with water, and dried. When the chlorine content was measured, it was 4
It was 5%.

Comparative Example 4 600 g of isotactic polypropylene (weight average molecular weight: 180,000) and 20 liters of carbon tetrachloride were placed in a 30-liter glass-lined reaction tank equipped with a stirrer, a chlorine blower, a waste gas outlet, and a condenser. was charged, and polypropylene was heated and dissolved at a temperature of 110°C under a pressure of 90°C. Gaseous chlorine was blown into the flask from the bottom at 110° C. while irradiating ultraviolet rays, and the chlorination reaction was carried out while appropriately extracting the contents and measuring the chlorine content. After the reaction was completed, carbon tetrachloride was removed by distillation under reduced pressure. The chlorine content of the obtained chlorinated product was 28%.

The chlorinated polyolefins produced in Examples 1 to 6 and Comparative Examples 1 to 4 were dissolved in toluene to a concentration of 20% by weight, and the solubility in toluene and storage stability of toluene solutions (-
The fluidity after being left at 5°C for one day and night was tested. Table 1 shows the results.
Shown below.

Table 1 As seen from Table 1, the chlorinated polyolefin of the present invention has excellent solubility.

Example 7 Atactic polypropylene (weight average molecular weight 2500
G) Chlorination was carried out in the same manner as in Example 1 using 30 g and 270 g of normal paraffin (same as in Example 1) to obtain chlorinated polypropylene with a chlorine content of 68%.

1 2 Example 8 30 g of polyethylene (weight average molecular weight 6000) and 270 g of normal paraffin (same as Example 1)
Chlorination was carried out in the same manner as in Example 1 using the same method as in Example 1 to obtain chlorinated polyethylene with a chlorine content of 68%.

Comparative Example 5 Polyethylene (weight average molecular weight: 6000) was chlorinated in the same manner as in Comparative Example 3, and the chlorine content was 69.
% of chlorinated polyethylene was obtained.

Comparative Example 6 Polyethylene (weight average molecular weight: 6000) was chlorinated in the same manner as in Comparative Example 4, and after the reaction was completed, steam distillation was performed to take out the powder.

The chlorine content was 68%.

The chlorinated polyethylene produced in Examples 7 and 8 and Comparative Example 5.6 was dissolved in toluene to a concentration of 40% by weight,
Solubility in toluene and viscosity of toluene solution (25℃, B
Mold accuracy 81) and storage stability (fluidity after being left at -10°C for 1 day and night) were tested.

The results are shown in Table 2.

Table 2 As can be seen from Table 2, the chlorinated polyethylene of the present invention has a low viscosity in toluene solution and excellent solubility. Also,
Good storage stability.

〔Effect of the invention〕

Since the method of the present invention is carried out with the configuration described above, it has the great effect of being able to simultaneously produce chlorinated polyolefin and chlorinated paraffin, and is significantly superior to conventional methods as it dramatically improves productivity. . In addition, since the reaction can be carried out at normal pressure, the operation during chlorination is simple and the reaction equipment is inexpensive.

3 4 The chlorinated polyolefin produced by the method of the present invention has excellent solubility in organic solvents because the reaction is carried out uniformly.

Procedural amendment (self-effect 1, indication of case 1999 Patent Application No. 336901 2, name of invention Process for producing chlorinated polyolefin 3, person making the amendment Relationship to the case Patent applicant address Marunouchi, Chiyoda-ku, Tokyo) -Chome 4-5 name
Name (234) Sanyo Kokusaku Pulp Co., Ltd. 4, Agent Address: 16, Kanda Kita Jomonocho, Chiyoda-ku, Tokyo, 101 Ei Building, 3rd Floor, 5, Column 6 for detailed description of the invention in the specification to be amended, Contents of the amendment As shown in the attached document, the following matters in the specification of this application are corrected.

Record 1. On page 4, line 8 of the specification The text "Special Publication Publication 1973-" was corrected to "Special Publication Publication 1974-".

2. On the second line from the bottom of page 4 of the specification. 1 Normally 10 microns" Corrected: "Normally several tens of microns."

3. Line 1 of page 4 of the specification It says "polyfin" Corrected to "polyolefin."

4. On page 4, line 4 of the specification It says "reaction is ga" “Reaction,” I corrected.

5. Accompanied by the same page agent j It says "aromatic organic solution number" Corrected to "aromatic organic solvent."

It says "solvent like" Corrected to "Solvent like this."

7. Line 1 of page 4 of the specification It says "C2oH1゜" Corrected as “C24H,o”.

8. On page 4, line 7 of the specification It says "surface lubricant" Corrected to "surfactant".

6. On page 13, line 18 of the specification

Claims (5)

[Claims] (1) Mixing a polyolefin or a polyolefin graft-modified with an unsaturated carboxylic acid and a paraffinic hydrocarbon having a carbon number of more than 8, and chlorinating the mixture to a chlorine content of 5 to 75% at a temperature where the mixture is liquid. A method for producing a chlorinated polyolefin, characterized by: (2) The method for producing a chlorinated polyolefin according to claim 1, wherein the paraffinic hydrocarbon is a normal paraffin having 10 to 35 carbon atoms. (3) The method for producing a chlorinated polyolefin according to claim 1, wherein the chlorination temperature is 50 to 140°C. (4) The method for producing a chlorinated polyolefin according to claim 1, wherein the ratio of the polyolefin or the polyolefin graft-modified with an unsaturated carboxylic acid to the paraffinic hydrocarbon having more than 8 carbon atoms is 95/5 to 1/99. (5) The method for producing a chlorinated polyolefin according to claim 1, wherein the mixture of a polyolefin or a polyolefin graft-modified with an unsaturated carboxylic acid and a paraffinic hydrocarbon having more than 8 carbon atoms has a viscosity of 3000 cps or less.