JPH1017615A - Production of mercapto polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily isolate a mercapto polymer in powdery form without causing it to gel by reacting a water-insoluble halogenated polymer with an alkali metal hydrosulfide under specified conditions. SOLUTION: A water-insoluble halogenated polymer (e.g. a chlorinated PE) is reacted with an alkali metal hydrosulfide (e.g. NaSH) by using water pref. in an amt. of 0.1-20 times that of the polymer, an org. solvent pref. being an aliph. hydrocarbon (e.g. n-heptane) and/or an alxohol (e.g. n-butanol) pref. having a solubility parameter of 9.9cal<1/2> .cm<-3/2> or lower pref. in an amt of 0.1-20 times that of the polymer, and a phase transfer catalyst (e.g. benzyltri-n- butylammonium cloride) pref. in an amt. of 0.1-20mol% based on halogen atoms of the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a mercapto group-containing polymer by reacting an alkali metal hydrosulfide with a water-insoluble halogen-containing polymer.

[0002]

2. Description of the Related Art Conventionally, polyvinyl chloride as a halogen-containing polymer is reacted with an alkali metal hydrosulfide to obtain a chloro group (-C
l) is substituted with a mercapto group (-SH) (thiolation)
A method for producing polyvinyl mercaptan as a mercapto group-containing polymer is known. And, for example, Polymer Collection, Vol. 36, No. 8, p523-52
No. 6 (1979) discloses that, in the reaction of polyvinyl chloride with sodium hydrosulfide in water, nitrobenzene is used as a swelling agent for the polyvinyl chloride and a surfactant is used as a phase transfer catalyst to obtain the above-mentioned compound. It is described that the reaction is accelerated.

[0003]

Industrially, it is desirable that the mercapto group-containing polymer be obtained in powder form. However, in the above-mentioned conventional method using nitrobenzene, the obtained polyvinyl mercaptan, that is, the mercapto group-containing polymer is gelled. Therefore, it is difficult to isolate the polymer containing a mercapto group, and there is a problem that the polymer cannot be obtained in powder form.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to isolate a mercapto group-containing polymer in a powder form without gelling the resulting polymer. It is an object of the present invention to provide a manufacturing method capable of performing the above.

[0005]

Means for Solving the Problems In order to solve the above-mentioned conventional problems, the present inventors have intensively studied a method for producing a mercapto group-containing polymer by reacting an alkali metal hydrosulfide with a halogen-containing polymer. did. As a result, at the time of the reaction, by using water, an organic solvent, and a phase transfer catalyst under specific conditions, the obtained mercapto group-containing polymer does not gel, and the mercapto group-containing polymer is in a powder form. They have found that they can be isolated and have completed the present invention.

That is, in order to solve the above-mentioned problems, the process for producing a mercapto group-containing polymer according to the first aspect of the present invention comprises adding a water-insoluble halogen-containing polymer to water, an organic solvent, and an organic solvent. A method for producing a mercapto group-containing polymer in which an alkali metal hydrosulfide is reacted with a catalyst, wherein the organic solvent has a solubility parameter of 9.9 cal ^{1 /
It is} a compound of ² · cm ^−3/2 or less and / or an alcohol.

According to the above method, the obtained mercapto group-containing polymer does not gel, and the mercapto group-containing polymer can be isolated in powder form.

Hereinafter, the present invention will be described in detail. The method for producing a mercapto group-containing polymer according to the present invention comprises a step of reacting a water-insoluble halogen-containing polymer with water, an organic solvent, and a phase transfer catalyst to react an alkali metal hydrosulfide with a mercapto group. a method of manufacturing a containing polymer, the organic solvent, solubility parameter 9.9cal ^1/2 · cm ^-3/2
The following compounds and / or alcohols are the methods.

The halogen-containing polymer (hereinafter simply referred to as a polymer) is not particularly limited as long as it is a compound which is insoluble in water and has a halogen which can be substituted for a mercapto group. Further, the content of halogen in the halogen-containing polymer is not particularly limited.

The above polymer is preferably a polymer having a halogen bonded to the main chain, and specifically, for example, a polymer obtained by polymerizing a monomer containing vinyl chloride and / or vinylidene chloride; Chlorinated polyolefins such as chlorinated polyethylene; polymers obtained by polymerizing monomers containing halogenated styrene such as p-bromostyrene; and the like. The polymer described above may contain, in addition to vinyl chloride, vinylidene chloride, and halogenated styrene, a monomer that can be copolymerized with these compounds, if necessary.

The above-mentioned monomer is not particularly limited as long as it is a compound having one ethylenic double bond in the molecule. As the monomer, specifically,
For example, vinyl acetate, (meth) acrylic acid, (meth) acrylate, styrene, (meth) acrylonitrile and the like can be mentioned. Only one of these compounds may be copolymerized with vinyl chloride or the like, or two or more thereof may be copolymerized with vinyl chloride or the like. Of the compounds exemplified above, vinyl acetate is particularly preferred. Compounds having a functional group capable of reacting with a mercapto group, especially butadiene, isoprene, divinylbenzene having two or more ethylenic double bonds in the molecule, even if copolymerization with vinyl chloride or the like is possible. Are unsuitable as monomers in the present invention.

The method of polymerizing the monomer, that is, the method of producing the polymer is not particularly limited, and various conventionally known production methods can be employed. Although the molecular weight of the polymer is not particularly limited, it is 5,000 to 1,
More preferably in the range of 1,000,000.
More preferably, it is in the range of from 000 to 500,000. When the molecular weight of the polymer is smaller than 5,000, the polymer may be dissolved in the organic solvent.
When the molecular weight of the polymer is larger than 1,000,000, the polymer may not swell with the organic solvent.

Specific examples of the alkali metal hydrosulfide (hereinafter, referred to as hydrosulfide) include sodium hydrosulfide, potassium hydrosulfide and the like. Of these, sodium hydrosulfide is preferred.

[0014] The amount of the above-mentioned hydrosulfide is not particularly limited, but is based on the halogen contained in the polymer.
It is more preferably in the range of 0.01 to 1.2 times mol, and still more preferably in the range of 0.03 to 1.0 times mol.

The amount of water to be used may be appropriately set according to the type and amount of the organic solvent used, etc., so that the polymer is uniformly dispersed during the reaction, that is, the reaction system is in a uniformly dispersed state. It is desirable to set so that The amount of water used is
Specifically, it is preferably in the range of 0.1 to 20 times by weight, and preferably 0.3 to 10 times by weight based on the polymer.
More preferably, it is within the range of weight times. If the amount of water used exceeds 20 times the weight of the polymer, the concentration of hydrosulfide in the water becomes too low, and the chance of the hydrosulfide moving to the organic solvent side (organic phase) decreases. Therefore, the reaction rate in the reaction between the polymer and the hydrosulfide is undesirably reduced.

The phase transfer catalyst is not particularly limited. For example, various kinds of conventionally known cationic surfactants can be used. Specific examples of the phase transfer catalyst include quaternary ammonium salts such as tetrabutylammonium chloride, benzyltributylammonium chloride and trioctylmethylammonium chloride; phosphonium salts such as tetrabutylphosphonium chloride and benzyltributylphosphonium chloride; Is mentioned.

The amount of the phase transfer catalyst to be used is not particularly limited, and may be set according to the substitution rate at which the halogen is replaced with a mercapto group. It is more preferably in the range of from mol% to 20 mol%, and further preferably in the range of from 1 mol% to 10 mol%.

The organic solvent has a solubility parameter (δs)
9.9cal ^1/2 · cm ^-3/2 following compounds, and / or, not particularly limited as long as it is an alcohol. As the organic solvent, specifically, for example, hexane (δs
= 7.3), cyclohexane (δs = 8.2), heptane (δs = 7.4) and other aliphatic hydrocarbons; toluene (δ
aromatic hydrocarbons such as s = 8.9) and xylene (δs = 8.8); ketones such as cyclohexanone (δs = 9.9) and methyl isobutyl ketone (δs = 8.4); ethyl acetate (δs) = 9.1), esters such as methyl acetate (δs = 9.6); and alcohols such as n-butanol and ethanol. These organic solvents may be used alone or as a mixture of two or more. Among these, the solubility parameter 9.0cal ^1/2 · cm ^-3/2 following compounds, and even more preferably aliphatic hydrocarbons. When an aliphatic hydrocarbon is used as the organic solvent, drying at the time of isolating the polymer containing a mercapto group becomes easy.
The solubility parameter is a value generally used as a factor representing the polarity of a compound.
Polymer Data Handbook Basic Edition (edited by the Society of Polymer Science, published by Baifukan, first edition January 30, 1986) 595-5
The solubility parameter δ of the organic solvent described on page 98
A value of s (cal ^1/2 · cm ^−3/2 ) can be adopted.

When an organic solvent is used, the polymer swells with the organic solvent. That is, the polymer is swollen by the organic solvent and is in a state of being dispersed in water. For this reason, the hydrosulfide easily penetrates into the polymer.

The amount of the organic solvent to be used is not particularly limited, but may be 0.1 to 20 times the weight of the polymer.
It is more preferably within the range of 0.3 times by weight, more preferably within the range of 0.3 times by weight to 10 times by weight.
If the amount of the organic solvent used is less than 0.1 times the weight of the polymer, the polymer may not be able to swell uniformly. On the other hand, if the amount of the organic solvent used is more than 20 times by weight of the polymer, the concentration of the reaction system is reduced, and the reaction rate in the reaction between the polymer and hydrosulfide is not preferred.

The entire amount of the organic solvent may be absorbed by the polymer, or a part of the organic solvent may not be absorbed by the polymer. As the organic solvent, and the solubility parameter 10.0cal ^1/2 · cm ^-3/2 or more, and not the alcohol compounds, for example, the use of nitrobenzene, polymers, as well as swelling, fused together Alternatively, they are fused. As a result, the resulting mercapto group-containing polymer gels. Therefore, for example, a solubility parameter of 10.0 cal ^1/2 · cm such as nitrobenzene
Organic solvents that are not less than ^−3/2 and are not alcohols are not suitable as organic solvents in the present invention.

The method of reacting the polymer with the hydrosulfide is as follows:
There is no particular limitation, and the same operation as a normal two-phase reaction operation can be performed. The method of mixing water, the organic solvent, the polymer, the hydrosulfide and the phase transfer catalyst is not particularly limited. As a mixing method,
Specifically, a method of mixing all at once; water, an organic solvent,
A method of mixing a polymer and a phase transfer catalyst and then mixing a hydrosulfide with the mixture; a method of mixing water, an organic solvent, a hydrosulfide and a phase transfer catalyst, and then mixing a polymer with the mixture; , A method of mixing a polymer swollen with an organic solvent to the mixture after mixing the hydrosulfide and the phase transfer catalyst; mixing water, an organic solvent, a hydrosulfide and the polymer with the mixture, A method of mixing a transfer catalyst; Further, the method of adding the hydrosulfide or the phase transfer catalyst to water or the like is not particularly limited, and may be added as a solid or as an aqueous solution. Further, the aqueous solution of hydrosulfide may be sequentially added to the reaction system.

By reacting the polymer with the hydrosulfide by the above-mentioned reaction operation, the halogen group (-
X) is substituted (thiolated) with a mercapto group (-SH), thereby producing the mercapto group-containing polymer according to the present invention and by-producing an alkali metal halide.

The reaction conditions in the above reaction are not particularly limited. The reaction temperature is preferably in the range of 30 ° C. to 120 ° C., and more preferably in the range of 50 ° C. to 100 ° C., although it depends on the organic solvent used. When the reaction temperature is lower than 30 ° C., the reaction rate in the reaction between the polymer and the hydrosulfide is undesirably reduced. On the other hand, if the reaction temperature is higher than 120 ° C., the crosslinking reaction proceeds, and the mercapto group-containing polymer has a crosslinked structure, becomes insoluble in an organic solvent, and gelates, which is not preferable.

The reaction time may be, for example, a polymer, hydrosulfide,
When the type and combination of the phase transfer catalyst and the organic solvent, the amount of use, and the addition of hydrosulfide as an aqueous solution, the time required for the sequential addition, the reaction temperature, etc., may be set as appropriate, but from 2 hours to Preferably, it is within a range of 10 hours. The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure. In the above reaction, conventionally known antioxidants can be used as necessary.

Further, the mercapto group-containing polymer having the above constitution is insoluble in water. Therefore, after completion of the reaction, the polymer containing a mercapto group can be isolated in a powder form by performing solid-liquid separation by filtration or the like. In addition, the mercapto group-containing polymer can be easily purified by dissolving the mercapto group-containing polymer in an appropriate solvent and then pouring it into a large amount of water to precipitate.

As described above, the method for producing a mercapto group-containing polymer according to the present invention comprises the step of reacting a polymer with a hydrosulfide using water, an organic solvent, and a phase transfer catalyst. a method of manufacturing a polymer, the organic solvent, solubility parameter 9.9cal ^1/2 · cm ^-3/2 following compounds, and / or a method which is an alcohol. According to the above method, the obtained mercapto group-containing polymer does not gel, and the mercapto group-containing polymer can be isolated in powder form. According to the above method, the obtained mercapto group-containing polymer does not gel, and the mercapto group-containing polymer can be isolated in powder form.

The polymer containing a mercapto group is soluble in an organic solvent and can be used in a wide range of applications such as a crosslinking agent for polymers such as epoxy resins and polyene resins, a modifying agent for polymers, an adhesive and a fiber treatment agent. Can be offered.

[0029]

The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

Example 1 A 300 equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet pipe, and a dropping funnel was used.
Chlorinated polyethylene as a polymer (manufactured by Daiso Corporation, trade name: H-135, molecular weight: 150,000, chlorine content: 35% by weight, no crystallinity, hereinafter referred to as CPE) 50 in a four-neck ml flask 0.0g (chlorine content 0.494
Molar), n-heptane (solubility parameter of the organic solvent: 7.4cal ^1/2 · cm ^-3/2) were charged and 50 g.

On the other hand, 100 g of water and sodium hydrosulfide as hydrosulfide (manufactured by Kishida Chemical Co., Ltd.,
9.5 g (purity 70%) (0.119 mol, 24 mol% based on the chloro group in CPE), and benzyltri-n-butylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter, BTBAC) as a phase transfer catalyst Written as
After charging 3.7 g (0.012 mol, 2.4 mol% based on the chloro group in the CPE), 30 g of the inside of the dropping funnel was charged.
Replaced with nitrogen gas for minutes.

Next, the contents of the flask were heated until the internal temperature reached 80 ° C. while stirring under a stream of nitrogen gas.
After reaching 80 ° C., the solution in the dropping funnel was dropped over 10 minutes. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 5 hours while stirring under a nitrogen gas atmosphere. During the reaction, the CPE swollen by n-heptane was uniformly dispersed in water.
After the completion of the reaction, the reaction solution was cooled to room temperature, and the produced polymer and water were separated by filtration.

After the above polymer was washed with a mixed solution of 50 g of n-heptane and 50 g of water, the polymer and the mixed solution (washing solution) were separated by filtration. 6
It was dried under reduced pressure at 0 ° C. As a result, 49.6 g of a light yellow powdery polymer was obtained. The presence or absence of a mercapto group was confirmed by measuring the infrared absorption spectrum of the obtained polymer. As a result of the measurement, as shown in FIG. 1, in the infrared absorption spectrum, 2550 cm ^{−1 to} 2600 cm
Absorption characteristics derived from the mercapto group are observed around ^-1 ,
It was confirmed that the chloro group of the CPE was substituted with a mercapto group. This confirmed that the polymer had a mercapto group, that is, the polymer was a mercapto group-containing polymer according to the present invention.

The mercapto group-containing polymer was subjected to elemental analysis to calculate the content of each element. As a result, it was found that 1 g of the mercapto group-containing polymer contained 0.35 mmol of mercapto groups and 9.55 mmol of unsubstituted chloro groups.

The chlorine substitution rate in CPE by sodium hydrosulfide was determined as follows. That is, after the completion of the reaction, the combined solution of the filtrate obtained by filtration of the reaction solution and the filtrate obtained by filtration of the washing solution contains an aqueous phase and n-
It had separated into two phases, a heptane phase. The amount of chlorine contained in the aqueous phase was quantified using an ion chromatograph, and the amount of chlorine contained in BTBAC was subtracted from the amount to calculate the chlorine substitution rate of CPE. Thus, it was found that the chlorine substitution rate in the CPE was 3.5 mol%. In addition, the chlorine substitution rate indicates that the theoretical yield of the mercapto group-containing polymer is 49.8 g, so that the yield of the mercapto group-containing polymer obtained by the above reaction is 99.6%. all right.

Example 2 The same reaction and operation as in Example 1 were carried out except that the organic solvent was changed to cyclohexanone (solubility parameter: 9.9 cal ^1/2 · cm ^{−3 / 2} ). Was. During the reaction, CPE swollen by cyclohexanone was uniformly dispersed in water. After the completion of the reaction, the reaction solution was cooled to room temperature, and the produced polymer and water were separated by filtration.

The above polymer was converted to cyclohexanone 50
After washing with a mixed solution of g and 50 g of water, the polymer and the mixed solution (washing solution) were separated by filtration. The polymer was dried at 60 ° C. under reduced pressure. As a result, 49.3 g of a light yellow powdery polymer was obtained. The light yellow powdery polymer was soluble in tetrahydrofuran (THF).

The presence or absence of a mercapto group was confirmed by measuring the infrared absorption spectrum of the obtained polymer.
As a result of the measurement, as shown in FIG. 2, in the infrared absorption spectrum, absorption characteristics derived from a mercapto group were observed around 2550 cm ^{−1 to} 2600 cm ⁻¹ , whereby
It was confirmed that the polymer was a mercapto group-containing polymer according to the present invention.

The mercapto group-containing polymer was subjected to elemental analysis to calculate the content of each element. As a result, it was found that 1 g of the mercapto group-containing polymer contained 0.40 mmol of mercapto groups and 9.50 mmol of unsubstituted chloro groups.

Further, the same operation as in Example 1 was performed to determine the chlorine replacement ratio in CPE by sodium hydrosulfide. Thereby, the chlorine substitution rate in the CPE was 4.0.
Mole%. In addition, the chlorine substitution rate indicates that the theoretical yield of the mercapto group-containing polymer is 49.8 g, so that the yield of the mercapto group-containing polymer obtained by the above reaction is 99.0%. all right.

Example 3 The same reaction and operation as in Example 1 were performed, except that the organic solvent was changed to n-butanol. During the reaction, CPE swollen by n-butanol was uniformly dispersed in water. After the completion of the reaction, the reaction solution was cooled to room temperature, and the produced polymer and water were separated by filtration.

The above polymer was added to 50 g of n-butanol.
After washing with a mixed solution of water and 50 g of water, the polymer and the mixed solution (washing solution) were separated by filtration. 6
It was dried under reduced pressure at 0 ° C. As a result, 49.5 g of a light yellow powdery polymer was obtained. The light yellow powdery polymer was soluble in tetrahydrofuran (THF).

The presence or absence of a mercapto group was confirmed by measuring the infrared absorption spectrum of the obtained polymer.
As a result of the measurement, as shown in FIG. 3, in the infrared absorption spectrum, absorption characteristics derived from a mercapto group were observed around 2550 cm ^{−1 to} 2600 cm ⁻¹ , whereby
It was confirmed that the polymer was a mercapto group-containing polymer according to the present invention.

Further, the mercapto group-containing polymer was subjected to elemental analysis to calculate the content of each element. As a result, it was found that 1 g of the mercapto group-containing polymer contained 0.36 mmol of mercapto groups and 9.54 mmol of unsubstituted chloro groups.

Further, the same operation as in Example 1 was performed to determine the chlorine replacement ratio in CPE by sodium hydrosulfide. Thereby, the chlorine substitution rate in the CPE was 3.6.
Mole%. In addition, the chlorine substitution rate indicates that the theoretical yield of the mercapto group-containing polymer is 49.8 g, so that the yield of the mercapto group-containing polymer obtained by the above reaction is 99.4%. all right.

Comparative Example 1 Nitrobenzene (solubility parameter: 10.0 cal ^1/2 · cm ^{−3 / 2} ) was used as an organic solvent.
The same reactions and operations as in Example 1 were carried out, except for replacing the above. During the reaction, the CPEs swollen by nitrobenzene fused to each other, were not uniformly dispersed in water, and had massive aggregates in some places. After the completion of the reaction, the reaction solution was cooled to room temperature, and the produced polymer and water were separated by filtration.

The above polymer was mixed with 50 g of nitrobenzene.
After washing with a mixed solution of water and 50 g of water, the polymer and the mixed solution (washing solution) were separated by filtration. 6
It was dried under reduced pressure at 0 ° C. As a result, 48.5 g of a yellow powdery polymer was obtained. The yellow powdery polymer is
When added to tetrahydrofuran (THF), the polymer swelled to a gel and did not dissolve.

The presence or absence of a mercapto group was confirmed by measuring the infrared absorption spectrum of the obtained polymer.
As a result of the measurement, as shown in FIG. 4, in the infrared absorption spectrum, absorption characteristics derived from a mercapto group were observed around 2550 cm ^{−1 to} 2600 cm ⁻¹ , whereby
It was confirmed that the polymer had a mercapto group.

The polymer was subjected to elemental analysis to calculate the content of each element. As a result, it was found that 1 g of the polymer contained 0.68 mmol of sulfur and 9.02 mmol of unsubstituted chloro groups. From the above results, part of the chloro group in the CPE was replaced by sulfur, but part of the sulfur introduced into the CPE by the substitution was not present in the form of a mercapto group, and was not present in the CPE. It turned out that the reaction was spent.

Further, the same operation as in Example 1 was performed to determine the percentage of chlorine substitution in CPE by sodium hydrosulfide. Thereby, the chlorine substitution rate in the CPE was 6.8.
Mole%. The chlorine substitution rate indicates that the theoretical yield of the mercapto group-containing polymer is 49.8 g. Therefore, the polymer obtained by the above reaction, that is, the yield of the comparative mercapto group-containing polymer is 9%.
It was found to be 7.4%.

[0051]

As described above, the method for producing a mercapto group-containing polymer according to claim 1 of the present invention comprises the steps of: adding water, an organic solvent, and a phase transfer catalyst to a water-insoluble halogen-containing polymer. using a method of manufacturing a mercapto group-containing polymer is reacted with an alkali metal hydrosulfide, the organic solvent is the solubility parameter 9.9cal ^1/2 · cm ^-3/2 following compounds, and / or , Alcohols.

Therefore, the resulting polymer containing a mercapto group does not gel and can be isolated in powder form. Thereby, there is an effect that a simple method for producing a mercapto group-containing polymer can be provided.

The above-mentioned mercapto group-containing polymer is soluble in organic solvents and can be used in a wide range of applications such as, for example, crosslinking agents for polymers such as epoxy resins and polyene resins, modifiers for polymers, adhesives and fiber treatment agents. Can be provided.

[Brief description of the drawings]

FIG. 1 is a chart of an infrared absorption spectrum of a mercapto group-containing polymer obtained in one example of the present invention.

FIG. 2 is a chart of an infrared absorption spectrum of a polymer containing a mercapto group obtained in another example of the present invention.

FIG. 3 is a chart of an infrared absorption spectrum of a mercapto group-containing polymer obtained in still another example of the present invention.

FIG. 4 is a chart of an infrared absorption spectrum of a polymer obtained in a comparative example of the present invention.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yuichi Kita 992, Nishioki, Okihama-shi, Aboshi-ku, Himeji-shi, Hyogo

Claims (1)

[Claims] 1. A water-insoluble halogen-containing polymer, comprising:
A method for producing a mercapto group-containing polymer in which an alkali solvent is reacted with an alkali metal hydrosulfide using an organic solvent and a phase transfer catalyst, wherein the organic solvent has a solubility parameter of 9.9 cal ^1/2 ·
A method for producing a mercapto group-containing polymer, which is a compound having a size of cm ^−3/2 or less and / or an alcohol.