JP3424251B2 - Method for producing chlorinated paraffin - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a fireproofing / waterproofing agent for cloths,
The present invention relates to a method for producing chlorinated paraffin used for fireproofing / waterproofing treatment of wood, fireproofing paint, plastic, rubber, printing ink compounding agents and the like.

[0002]

2. Description of the Related Art Currently, chlorinated paraffin is industrially produced by a method of chlorinating in a solvent inert to chlorine such as carbon tetrachloride. That is, at the end of chlorination, chlorinated paraffin, which is a reaction product, is obtained in the form of being dissolved in a solvent, and then excess chlorine, hydrochloric acid as a reaction by-product, and solvent are removed, and then cooled and solidified. This is a method of crushing and classifying into a product by an appropriate method.

The chlorination of paraffin progresses smoothly with heat generation even under normal pressure without using a solvent up to a chlorine content of up to about 50% by weight, and since the product is obtained in a liquid state, it is particularly technically technical. No problem. Also However an effort to obtain those exceeding chlorine content 50 wt% in this way, increase will occur in the viscosity of the reaction product as the increase in chlorine content, the reaction itself very slowly not easy stirring with it Since it takes a long time to complete the reaction, this method is not industrially feasible.

The paraffin content of paraffin temporarily decreases as the chlorine content increases due to the chlorination reaction.
When the content of chlorine is 70% by weight, it becomes liquid even at room temperature. When the content of chlorine is 70% by weight, the softening point is about 100 ° C. Therefore by paraffin in the reaction with the solution using a solvent in the current method, to lower the viscosity of the reactants, as a result of increased contact effect of gas-liquid, the chlorination reaction is a form which proceeds easily.

[0005]

However, due to environmental problems, it is about to come to a situation where this useful carbon tetrachloride cannot be used in the near future, and halogenated solvents having the same performance as carbon tetrachloride all have the same fate. It has been decided to follow, and the appearance of an industrial manufacturing method to replace such a solvent method is awaited. It is an object of the present invention to provide a method for producing chlorinated paraffin having a quality equivalent to that of a solvent method by chlorinating paraffin in a suspension state in an aqueous solvent.

[0006]

The present invention is a method of chlorinating paraffin having a molecular weight of 280 to 450 in an aqueous solvent in a molten suspension state at 70 to 150 ° C., wherein the chlorination reaction is completed. The method is a method for producing chlorinated paraffin, characterized in that the temperature at the time is 105 to 150 ° C.

The paraffin used in the present invention is known under the names of paraffin WAX, solid paraffin, stone wax, etc., which corresponds to 120P to 135P classified by JISK2235, and is a main component. the molecular weight is approximately 280~450, C ₂₀ ~C the molecular formula
Equivalent to ₃₂ . This paraffin has a melting point of about 50 to 70 ° C., and becomes a liquid at a temperature higher than that.

In the present invention, the introduction of chlorine is started in the temperature range higher than the softening point of the raw paraffin, in the state where the paraffin is melted and suspended in water. Further, since the chlorination reaction proceeds relatively quickly with heat generation up to a chlorine content of 50% by weight as described above, the initiation of the chlorination reaction does not require a particularly high temperature and may be in a temperature range around 80 ° C. . The rate of the chlorination reaction becomes faster as the temperature rises up to 150 ° C, but the reason why the temperature reaches a peak at 150 ° C and becomes higher than that is unknown, but rather slows down. Therefore, it is important to control the temperature to 80 ° C or higher and 150 ° C or lower.

The mixing ratio of paraffin and water may be approximately 5 to 100 with respect to 1 part by weight of paraffin, and more preferably 20 to 50 with water. The reason is that the dispersion state of paraffin in water is less than 5, and when the amount of water is less than 5, the dispersion state of paraffin in water cannot be maintained as a fine particle, resulting in a slow reaction rate. Is worse.

In order to improve the dispersion of paraffin during the chlorination reaction, it is preferable to add a dispersant to the reaction system. A surfactant or an acrylic polymer is usually used as the dispersant, and a nonionic or anionic surfactant is used as the dispersant, such as polyoxyethylene alkyl ethers, polyoxyalkylphenol esters, polyoxyethylene alkyl. Esters, sodium alkylallyl sulfonates, alcohol sulfates, and sodium alkyl sulfonates are used. The acrylic polymer is a polymer of acrylic acid or acrylic acid ester or a copolymer thereof, or an alkali metal salt of these polymers or copolymers, and has a molecular weight of 3
000 or more, preferably 10,000 or more are used. These dispersants are preferably used in combination with a surfactant and an acrylic polymer rather than used alone, and the addition amount thereof is 0.5 to 2 based on the weight of the raw material paraffin.
% Is preferred.

Since the present invention uses water as a medium for paraffin and handles a system at a temperature of 100 ° C. or higher, a pressure vessel is required, and one raw material is a corrosive gas called chlorine, which is corrosive. Since strong hydrochloric acid is produced as a by-product, appropriate consideration must be given to the reaction vessel. A glass-lined autoclave is recommended as a container made of a material that meets these conditions and has no industrial problems. In addition to a thermometer and a pressure gauge, it is preferable that the reaction vessel is equipped with a flow meter capable of confirming the amount of chlorine gas introduced. In this way, by adjusting the temperature at the end of the chlorination reaction to 105 to 150 ° C., it is possible to chlorinate paraffin up to a chlorine content of 68 to 72% by weight. Paraffins chlorinated to a specified chlorine content are washed with an aqueous solution of caustic soda, washed with water and dried to obtain products.

[0012]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In the examples, all composition% are weight%.

Example 1 2 kg of 125 paraffin manufactured by Nippon Petrochemical Co., Ltd. (melting point: 51.7 ° C. or more, less than 54.5 ° C.) was charged into a 100 liter capacity glass-lined pressure resistant reaction vessel together with 70 l of ion-exchanged water and heated to 70 ° C. did. Paraffin melted and spread as an oil film on the water surface. When stirring was started, paraffin was dispersed in water in the form of oil drops.

Then, when chlorine gas was introduced, the absorption was stopped rapidly at first, and after absorbing 1.2 kg of chlorine at a slow speed for about 1 hour, the absorption was almost stopped. When the temperature was gradually increased, the absorption of chlorine became prompt again when the temperature reached 100 ° C. 3.8 kg of chlorine gas was additionally absorbed over about 2 hours. Since the chlorine absorption rate decreased again, the temperature was adjusted to 130 ° C. and 4.75 kg of chlorine was finally introduced. The total reaction time was 4.2 hours. At the end of the reaction, the chlorinated paraffin was floating in water in an irregular shape of large lumps to small lumps. The mixture was cooled with stirring, and chlorinated paraffins of various shapes from small fingertip-sized lumps to powder were taken out. After crushing this, washing,
When it was dried and the chlorine content was measured, it was 70.1%.

Comparative Example 1 Paraffin and ion-exchanged water were charged into a reaction vessel under the same conditions as in Example 1. When this was heated to 100 ° C. and chlorine gas was introduced while stirring, 3 kg of chlorine was absorbed in about 2 hours. When the temperature was adjusted to 155 ° C. and chlorine was further introduced, 1.72 kg of chlorine was absorbed in about 3 hours. Unlike the case of Example 1, the state of the reaction product was that it sank to the bottom of the reactor and rotated like a soft dough. The mixture was cooled while being stirred, and chlorinated paraffins having various shapes from small fingertip-sized lumps to powders similar to those in Example 1 were taken out. However, it was clearly light brown, and it was speculated that some chemical changes occurred due to the high temperature. When it was crushed, it had a pale yellow color, and when it was washed and dried and the chlorine content was measured, it was 70.3%.

Comparative Example 2 Under the same conditions as in Example 1, paraffin and deionized water were charged into a reaction vessel. When this was heated to 90 ° C. and chlorine gas was introduced while stirring, 3 kg of chlorine was absorbed in about 6 hours. When more chlorine was introduced, the absorption of chlorine was virtually stopped when 1.29 kg of chlorine was absorbed in 15 hours. The reaction product was entangled with the stirrer and caused abnormal vibration. This was cooled, the lid of the reaction vessel was opened, the reaction product was taken out, pulverized, washed and dried, and the chlorine content was measured and found to be 66.9%.

Example 2 135 paraffin manufactured by Nippon Seiro Co., Ltd. (melting point: 57.2 ° C. or higher,
10 kg of less than 60.0 ° C.) in a glass-lined pressure-resistant container having a capacity of 100 l, 70 l of ion-exchanged water and a nonionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name Neugen EA1)
20) Charged together with 5 g and 18 g of acrylic acid polymer (Rohm and Haas, trade name Primal A-1), 1
Heated to 00 ° C. When stirring was started, paraffin was dispersed in water in the form of fine oil droplets.

Next, when chlorine gas was introduced, the absorption rate decreased when 12 kg of chlorine was absorbed in about 3 hours at a rapid rate. The temperature was set to 150 ° C., and 12 kg of chlorine gas was additionally absorbed over about 2 hours. The chlorine absorption rate was almost linear, and it was thought that the reaction proceeded smoothly without any particular problems. Total reaction time is 5.5 hours and total 24kg
Chlorine was absorbed. At the end of the reaction, the chlorinated paraffin was floating in water in the form of small irregular particles. Cool with stirring, mostly powder, and a small amount of spherical lumps (1
Chlorinated pure white paraffin mixed with ˜5 mm lump) was taken out from the valve at the bottom of the reaction vessel. After crushing the whole amount, washing, drying and measuring the chlorine content, 6
It was 9.8%.

Example 3 120 paraffin manufactured by Nippon Seiro Co., Ltd. (melting point: 48.9 ° C. or higher,
(Less than 51.7 ° C.) 10 kg was charged into a reaction vessel together with ion-exchanged water and a surfactant under the same conditions as in Example 2, and 80
Heated to ° C. When stirring was started, paraffin was dispersed in water in the form of fine oil droplets.

Then, when chlorine gas was introduced, the absorption rate decreased when 11 kg of chlorine was absorbed at a rapid rate in about 3 hours. The temperature was set to 105 ° C., and 13 kg of chlorine gas was additionally absorbed over about 3 hours. The chlorine absorption rate was almost linear, and it was thought that the reaction proceeded smoothly without any particular problems. The total reaction time was 6 hours, and a total of 24 kg of chlorine was absorbed. At the end of the reaction, the chlorinated paraffin was floating in water in the form of small irregular particles. Cool with stirring, mostly powder, small amount of spherical lumps (1-6
(mm diameter) mixed with chlorinated pure white paraffin was taken out from the valve at the bottom of the reaction vessel. After crushing the whole amount, washing and drying, and measuring the chlorine content, 69.
It was 4%.

[0021]

[Table 1]

The results of the above Examples and Comparative Examples are summarized in Table 1. In Comparative Example 1, it is considered that the reaction product was damaged and colored due to the high temperature of 155 ° C., and in Comparative Example 2, it was found that only a low chlorine content was obtained due to insufficient temperature.

[0023]

According to the present invention, the raw material paraffin is subjected to the chlorination reaction in a molten suspension state in an aqueous solvent, and the reaction can be smoothly proceeded to a high chlorine content. Compared with the conventional method using an organic solvent, there are advantages that it is economical and there is no environmental pollution.

Claims (3)

(57) [Claims] 1. Paraffin having a molecular weight of 280 to 450,
A method of chlorinating in an aqueous solvent in a molten suspension state at 70 to 150 ° C., wherein the temperature at the end of the chlorination reaction is 105
The method for producing chlorinated paraffin is characterized in that the temperature is set to 150 ° C. 2. The method for producing chlorinated paraffin according to claim 1, wherein the chlorinated paraffin obtained has a chlorine content of 68 to 72% by weight. 3. The method for producing chlorinated paraffin according to claim 1 or 2, wherein the chlorination reaction is performed in an aqueous solvent in the presence of a dispersant.