JP2002128889A - Ester of mercaptofatty acid and polyoxyalkylene compound and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide new mercaptofatty acid esters having improved solubility in water and a method of preparing these esters. SOLUTION: These (poly)thiol esters are expressed by: R1.(R2 O)n.(CO).(CH2)m.SH (R1 can be either one of hydrogen, a 1-20 C alkyl group, a 2-20C alkenyl group or a 6-20C phenyl group which may optionally have a substitution group; R2 is a 1-4C alkylene group; m is an integer of 1 to 10; and n is an integer of 1 to 30), and HS.(CH2)l.(CO).O.(R2O)n.(CO).(CH2)mSH (R2 is a 1-4C alkylene group; l and m are independently integers of 1 to 10; and n is an integer of 3 to at most 30). These esters are easily dissolved in water and readily copolymerized with other polymerizable monomers to yield block copolymers having adequate hydrophilicity. The block copolymers provided have excellent properties used as coating resins, especially as antifouling coating resins. These compounds can be used also for vulcanization agents, antioxidants, polymerization regulators, cross-linking agents, materials of medicines and agricultural chemicals and various other uses.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ester of a mercapto fatty acid and a polyoxyalkylene compound and a method for producing the ester. More specifically, the present invention relates to a novel ester of a fatty acid having a thiol group at a terminal and a polyoxyalkylene compound (hereinafter, referred to as "mercapto fatty acid ester") and a method for producing the mercapto fatty acid ester.

[0002] Such mercapto fatty acid esters are useful compounds having a wide range of uses.

[0003]

BACKGROUND OF THE INVENTION Conventionally known (poly) thiol ester compounds include, for example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate) and trimethylolpropane tris (3-mer). Mercaptopropionate) and diethylene glycol bis (3-mercaptopropionate). These known (poly) thiol ester compounds have a wide range of uses based on the action of active thiol groups. For example, it is used in various fields as a raw material of synthetic resin, a raw material such as a vulcanizing agent, an antioxidant, a polymerization regulator, a metal complex forming agent, a cross-linking agent, a drug raw material and the like.

As an example, Japanese Patent No. 2541582 discloses a series of novel (poly) thiol esters represented by diethylene glycol bis (3-mercaptopropionate) which are used as raw materials for the synthesis of sulfur-containing urethane resins. Is disclosed. However, this patent publication neither describes nor suggests a mercapto fatty acid monoester of an alkylene glycol or a mercapto fatty acid bisester of a polyalkylene glycol having a distribution of the average addition mole number of a polyoxyalkylene group.

Japanese Patent Application Laid-Open No. 54-8642 discloses hexane-
1,6-bis (2-mercaptoacetate) is disclosed. However, the above-mentioned known (poly) thiol ester compounds have a problem that their solubility in water is poor. For example, diethylene glycol bis (3-mercaptopropionate), which is included in the category of mercapto fatty acid esters of polyalkylene glycol, is not sufficiently soluble in water. Therefore, a thiol ester compound with improved water solubility is expected to open up to uses and methods of use that have been difficult with conventional (poly) thiol compounds, and the appearance of such a thiol compound has been eagerly desired.

The present inventors have conducted intensive studies to solve the problem that the conventional thiol compound has poor solubility in water. As a result, a novel mercapto fatty acid ester of a polyoxyalkylene compound was found to be soluble in water. The inventors have found that the copolymer has improved properties and excellent copolymerizability with other copolymerizable monomers, and have completed the present invention.

[0007]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a novel mercapto fatty acid ester having improved solubility in water and a method for producing the same. The purpose is to do.

[0008]

SUMMARY OF THE INVENTION The monoester of a mercapto fatty acid and a polyoxyalkylene compound according to the present invention has a general formula (1) R ¹ O. (R ² O) _n. (CO). (CH ₂ ) _m .SH ( 1) [In the formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, 6 to 20 carbon atoms, and may have a substituent. A phenyl group; R ² represents an alkylene group having 1 to 4 carbon atoms;
And the number n is from 1 to 30. ] Is represented.

In the monoester, m of the mercapto fatty acid constituting the general formula (1) is preferably 1 to 3. Further, n of the polyoxyalkylene group constituting the general formula (1) is preferably a number of 3 to 10. Furthermore, a method for producing a monoester of a mercapto fatty acid represented by the general formula (1) and a polyoxyalkylene compound is described by a general formula (2) R ¹ O · (R ² O) _n · H (2) R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group having 6 to 20 carbon atoms and optionally having a substituent, ² represents an alkylene group having 1 to 4 carbon atoms, and n represents 1 to
The number 30 is shown. A polyoxyalkylene compound represented by] the general formula _{(3) HOOC · (CH 2} ) m · SH (3) wherein the mercapto fatty acid m is represented by the number of 1 to 10] It is characterized by reacting.

The bisester of a mercapto fatty acid and a polyoxyalkylene compound according to the present invention is represented by the following general formula (4): HSCH (CH ₂ ) _l （(CO) ・ O ・ (R ² O) _n・ (CO) ・(CH ₂ ) _m · SH (4) [wherein, R ² represents an alkylene group having 1 to 4 carbon atoms, l and m each independently represent a number of 1 to 10, and n is more than 3 and 30
The following numbers are shown. ] Is represented.

In the bisester, it is preferable that l and m of the mercapto fatty acid constituting the general formula (4) are each independently 1 to 3, and the polyoxyalkylene group constituting the general formula (4) N is preferably a number exceeding 3 and not more than 10. Further, a method for producing a bisester of a mercapto fatty acid represented by the general formula (4) and a polyoxyalkylene compound is described by the general formula (2a) R ¹ O · (R ² O) _n · H (2a) [formula ( In 2a), R ¹ represents a hydrogen atom, R ² represents an alkylene group having 1 to 4 carbon atoms, and n represents a number exceeding 3 and 30 or less. A polyoxyalkylene compound represented by the general formula (3):
(3a) HOOC · (CH ₂ ) _m · SH (3) HOOC · (CH ₂ ) _l · SH (3a) [In the formula (3), m represents a number of 1 to 10, and in the formula (3a), l shows the number of 1-10. And a mercapto fatty acid represented by the following formula:

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the monoester and bisester of a mercapto fatty acid with a polyoxyalkylene compound according to the present invention, the method for producing the same and the use thereof will be described in detail. These monoesters and bisesters are represented by the following general formulas (1) and (4), respectively.

R ¹ O · (R ² O) _n · (CO) · (CH ₂ ) _m · SH (1) wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An alkenyl group having 2 to 20 carbon atoms, a phenyl group having 6 to 20 carbon atoms and optionally having a substituent, R ² represents an alkylene group having 1 to 4 carbon atoms, and m represents 1 to 1
The number of 0 is shown, and n shows the number of 1-30. ] _{HS · (CH 2) l ·} (CO) · O · (R 2 O) n · (CO) · (CH 2) m · SH (4) wherein, R ² is alkylene of 1 to 4 carbon atoms 1 and m independently represent a number from 1 to 10, and n is greater than 3 and 30
The following numbers are shown. The novel monoester or bisester represented by the above general formula (1) or (4) according to the present invention (hereinafter collectively referred to as “present ester”, “present compound”, etc.) Compared to the known thiol esters of
It has the following structural features: This compound has one or two reactive thiol groups in the molecule. Furthermore, the hydrophilicity of the entire compound can be adjusted by expansion and contraction of the hydrophilic polyoxyalkylene group portion. Especially n is 3
By introducing a larger polyoxyalkylene group, the hydrophilicity of the compound can be increased. In addition, a compound having a large molecular weight can be obtained by combining this group with a polymethylene group derived from a mercapto fatty acid. Further, by adjusting the kind and ratio of the polar group to be introduced as a substituent, the characteristics of the present compound become more flexible. As a result, the present ester having a highly reactive thiol group and good affinity for water is an antioxidant, a polymerization regulator,
In addition to being usable as a metal complex-forming agent, it is useful as a raw material for synthetic resins, a raw material for vulcanizing agents, a raw material for synthesis of other compounds such as a raw material for drugs, or as an active substance that can be used in a wide variety of ways.

In the monoesters and bisesters represented by the above general formulas (1) and (4) according to the present invention, R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms. It represents an alkenyl group or a phenyl group having 6 to 20 carbon atoms and which may have a substituent. Among alkyl groups having 1 to 20 carbon atoms, in addition to methyl and ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,
It may have a branch in addition to a straight chain. Some of the hydrogen atoms in the alkyl group may be a hydroxyl group, a hydroxylalkyl group, an alkoxyl group, a polyoxyalkylene group, an amino group, an N-substituted amino group, an amide group, an N-substituted amide group, an epoxy group, It may be further substituted by a functional group such as a sulfanyl group and a halogen group. By introducing these functional groups, the properties of the mercapto fatty acid ester can be further changed. In particular, an alkyl group having 1 to 10 carbon atoms is preferable in terms of ease of synthesis or availability.

Alkenyl groups having 2 to 20 carbon atoms include vinyl, isopropenyl, 1-propenyl, allyl, 1-
Butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, hexenyl group, heptenyl group,
Octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, eicosenyl group, etc. It may be. These alkenyl groups may be further substituted by unsubstituted alkenyl groups or functional groups similar to the above-mentioned alkyl groups. Among them, an alkenyl group having 2 to 10 carbon atoms is preferable from the viewpoint of easy synthesis or availability.

The phenyl group having 6 to 20 carbon atoms and which may have a substituent has not only the phenyl group itself but also a substituent such as the above-mentioned linear or branched alkyl group or alkenyl group. Includes phenyl groups. These substituents also include C1-C14 alkyl and alkenyl groups having oxygen, nitrogen, sulfur, phosphorus atoms and the like. Further, these substituents may be on one carbon atom of the benzene ring or on different carbon atoms of the benzene ring. Among them, a phenyl group having no substituent or a phenyl group substituted by an alkyl or alkenyl group having 1 to 10 carbon atoms is preferable from the viewpoint of ease of synthesis or availability. Specifically, a phenyl group, a benzyl group, a phenethyl group, a tolyl group, a xyl group,
Examples include a mesityl group, a cumenyl group, a styryl group, a cinnamyl group, and the like, but are not limited thereto.

R ² represents an alkylene group having 1 to 4 carbon atoms, and specific examples include methylene, ethylene, trimethylene, propylene, tetramethylene, ethylethylene and the like. In the mercapto fatty acid ester represented by the general formula (1) or (4), l and m of the portion derived from the mercapto fatty acid skeleton are each independently a number of 1 to 10, and such a mercapto fatty acid ester is derived. Specific examples of possible mercapto fatty acids include mercaptoacetic acid (l or m = 1) to mercaptopropionic acid (2 on the left), mercaptobutyric acid (3 on the left), mercaptovaleric acid (4 on the left), and mercaptohexanoic acid (5 on the left). ), Mercaptoheptanoic acid (6 on the left), mercaptooctanoic acid (7 on the left), mercaptononanoic acid (8 on the left), mercaptocapric acid (9 on the left), and mercaptoundecanoic acid (10 on the left). Of these, l or m = 1
~ 3 mercaptoacetic acid, mercaptopropionic acid, and mercaptobutyric acid are preferably used.

N representing the chain length of the polyoxyalkylene group derived from the polyoxyalkylene compound also means the average number of moles of the polyoxyalkylene group, as described later. n is a number of 1 to 30 in the case of a monoester, and more than 3 and 30 or less in the case of a bisester. In particular,
In the mercapto fatty acid monoester represented by the general formula (1), n is 3 to 10, or in the mercapto fatty acid bisester represented by the general formula (4), n is a number exceeding 3 and not more than 10. Bisesters are preferably used. Even if the molecule has an oxyethylene group that is a hydrophilic moiety, mono- or di-oxyethylene glycol or mono- or di-oxyethylene glycol ester is not sufficiently hydrophilic, and mercapto fatty acid ester is The present inventors have found that a polyoxyalkylene group in which the average number of moles added, such as a polyoxyethylene group, that is, n is larger than 3, is more effective for exhibiting hydrophilicity. Therefore, by adjusting the length of the polyoxyalkylene group as required or necessary, the properties of the mercapto fatty acid ester, particularly the hydrophilicity, can be changed.

Production Method The monoester (represented by the formula (1)) according to the present invention comprises a polyoxyalkylene compound represented by the following formula (2), a mercapto fatty acid represented by the following formula (3), The bisester (shown by the formula (4)) according to the present invention has the following formula (2)
a) a polyoxyalkylene compound represented by the formula (3) or (3)
The mercapto fatty acid represented by a) can be produced by esterification in the presence of, for example, an acid or alkali catalyst.

R ¹ O · (R ² O) _n · (CO) · (CH ₂ ) _m · SH (1) [In the formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms, a phenyl group having 6 to 20 carbon atoms and optionally having a substituent, R ² represents an alkylene group having 1 to 4 carbon atoms, and m represents 1 to
10 represents the number, and n represents the number of 1 to 30. ] HS · (CH ₂₎ in _{l · (CO) · O ·} (R 2 O) n · (CO) · (CH 2) m · SH (4) [Equation (4), R ² is 1 to the number of carbon atoms 4 represents an alkylene group,
And m independently represent a number of 1 to 10, and n represents a number exceeding 3 and 30 or less. R ¹ O · (R ² O) _n · H (2) wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An alkenyl group having 2 to 20 carbon atoms, a phenyl group having 6 to 20 carbon atoms and optionally having a substituent, R ² represents an alkylene group having 1 to 4 carbon atoms, and n represents 1-3
Indicates the number of 0. R ¹ O · (R ² O) _n · H (2a) wherein R ¹ is a hydrogen atom, R ² is an alkylene group having 1 to 4 carbon atoms, and n is a number exceeding 3 and not more than 30. Show. HOOC · (CH ₂ ) _m · SH (3) HOOC · (CH ₂ ) _l · SH (3a) [in the formula (3), m represents a number of 1 to 10, and in the formula (3a), l represents The number of 1-10 is shown. The mercapto fatty acid (3) is reacted with 0.98 to 1.5 mol, preferably 1.0 to 1.1 mol, per 1 mol of the polyoxyalkylene compound (2). Mercapto fatty acid (3), (3
a) is reacted in an amount of 1.96 to 3 mol, preferably 2 to 2.2 mol.

As mercapto fatty acids, commercially available products such as mercaptoacetic acid and mercaptopropionic acid may be used, or they may be synthesized by introducing a thiol group into the corresponding fatty acid. In addition to the free acid of the mercapto fatty acid, an acid anhydride thereof, or an acid halide thereof such as chloride and bromide can be preferably used in the esterification reaction.

Similarly, the polyoxyalkylene compound (2)
Alternatively, as the polyoxyalkylene compound (2a), a commercially available commercially available product may be used, or polyoxyethylene glycol may be synthesized by reacting alcohol or glycol with ethylene oxide. At this time, since the addition mole number of the alkylene oxide such as ethylene oxide is generally not uniform, a mixture of various polyoxyalkylene glycols (2) or (2a) having different addition mole numbers of the alkylene oxide is generated. For example, when synthesizing tetraethylene glycol, the number of moles of ethylene oxide added (n) is
Usually, a distribution of n = 1 to 10 is shown, in which the component having the highest content is tetraethylene glycol (C4) in which n = 4.
Becomes Further, when synthesizing hexaethylene glycol, the number of moles added (n) usually shows a distribution of C2 to C16, and the component having a high content is C6.

When it is necessary to use a mercapto fatty acid ester formed from a single polyoxyethylene glycol, the desired component may be separated from the polyoxyethylene glycol mixture and used. Economics are reduced. However, when it is used for ordinary applications, it is usually used as a mixture of polyoxyalkylene glycols having various moles of alkylene oxide added. Therefore, as long as the average number of moles added (n) is within the above range, the ester may be produced using a polyoxyalkylene glycol having a distribution of components. In this case, even if, for example, an ester of di- or triethylene glycol is contained in addition to ethylene glycol, a mixture having a distribution of components can be produced as long as it does not adversely affect the performance, so that productivity is high.

Examples of the acid catalyst include mineral acids such as sulfuric acid and hydrochloric acid, alkanesulfonic acids such as methanesulfonic acid and ethanesulfonic acid; aromatic sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid; Alkylene sulfonic acids such as sulfonic acid and tetraethylene sulfonic acid; arylenedisulfonic acid; and the like. Sulfuric acid, p-toluenesulfonic acid and the like are preferable from the viewpoint of easy availability. The amount of the catalyst used is not particularly limited, but is usually 0.001 to 10% by weight, preferably 0.01 to 3% by weight, based on the raw material mixture for the reaction.

Such an esterification reaction may be performed in the absence of a solvent, or may be performed in the presence of a solvent. When using a solvent, the mercapto fatty acid (3) and the polyoxyalkylene compound (2) to be used,
The type is not particularly limited as long as it does not react with (2a). For example, aliphatic hydrocarbons such as heptane and decalin; alicyclic hydrocarbons such as cyclohexane and cycloheptane; aromatic hydrocarbons such as xylene and toluene; halogenated hydrocarbons such as chloroform and monochlorobenzene; No. In the present invention, among these solvents, non-polar solvents that do not particularly react with the raw materials are more preferable, and for the purpose, hydrocarbons such as toluene, benzene and hexane; and halogenated solvents such as chloroform and monochlorobenzene And hydrocarbons.

In the esterification reaction in the presence of an acid catalyst, the reaction temperature is usually adjusted to 60 to 60 ° C. while stirring the starting materials under normal pressure.
The reaction is carried out while maintaining the temperature at 200 ° C., preferably 90 to 140 ° C., to remove by-product water out of the reaction system. The reaction time depends on conditions such as the reaction temperature, but is usually about several hours. In order to remove by-product water out of the system, a method using a solvent azeotropic with water (for example, benzene, toluene, or the like) or a method using a dehydrating agent such as molecular sieves is preferable.

If the produced ester can be washed with water, it may be neutralized with an aqueous solution of an alkaline substance such as sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia and the like, and washed with water. If washing with water is not possible, the crude product can be neutralized by adding an amine in an amount equivalent to the acid value, and washed with the used solvent. Then, after distilling off the solvent, the desired product can be separated by filtration.

Applications The mercapto fatty acid esters (1) and (4) according to the present invention are used as raw materials for synthetic resins such as sulfur-containing polyurethane resins, curing agents for epoxy resins, polymerization regulators, resin modification, crosslinking or oxidation. It is used for prevention. In addition, the ester is a useful compound having a wide range of uses as a vulcanizing agent, a crosslinking agent, an antioxidant, a metal complex forming agent, a lubricant additive, a biochemical drug, and the like.

Since the mercapto fatty acid esters (1) and (4) according to the present invention have excellent solubility in water or an aqueous medium, they can be uniformly added to water or a medium mainly composed of water or an emulsion paint. It can be a dissolved composition.
When the mercapto fatty acid ester according to the present invention (1), (4) is added to water or a medium mainly containing water, or to an emulsion paint, the amount of addition is 0.5 to the total amount of the obtained composition. 50% by weight, preferably 1 to 10% by weight is desirable. By adding a hydroxide of an alkali metal or an alkaline earth metal or a water-soluble amine to such a composition, the composition becomes weakly alkaline, for example, a pH of 7.5 to 7.5.
9 can also be used.

[0030]

The mercapto fatty acid monoester (1) and the mercapto fatty acid bisester (4) according to the present invention are useful new compounds having various uses. That is, the above mercapto fatty acid esters having high solubility in water can be used more widely than before.

For example, the above esters can be suitably used by adding them to water or a medium mainly composed of water, for example, an emulsion paint.

[0032]

EXAMPLES Hereinafter, the mercapto fatty acid ester according to the present invention and the method for producing the same will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0033]

Example 1 Synthesis of polyethylene glycol bis (3-mercaptopropionate) (compound 1) In a four-necked flask equipped with a thermometer and a water separator, 531.6 g (5.01 mol) of 3-mercaptopropionic acid and polyethylene glycol were placed. (Average molecular weight 196.9, n = 4.1) 492.3 g (2.5
0 mol), p-toluenesulfonic acid 19.1 g and toluene 7
97.4 g was charged and reacted at 100 to 125 ° C. for 5 hours to remove water generated outside the system. The amount of generated water was 90.0 g. The reaction system was cooled to room temperature, washed with 330 g of a 10% aqueous sodium carbonate solution, and then twice with 265 g of water. Next, toluene was distilled off under reduced pressure, followed by filtration to obtain 815 g (2.19 mol) of polyethylene glycol bis (3-mercaptopropionate) (n = 4.1) as a pale yellow transparent liquid. The analysis results of the synthesized ester were as follows.

[0034]

[0035]

Example 2 Synthesis of 1-methoxy polyethylene glycol (3-mercaptopropionate) (compound 2) In a four-necked flask equipped with a thermometer and a water separator, 21.4 g (0.20 mol) of 3-mercaptopropionic acid was added. 1-methoxypolyoxyethylene-68-ol (average molecular weight 1033.3, n =
22.7) 208.7 g (0.20 mol), p-toluenesulfonic acid 4.3
g and 161 g of toluene were charged and reacted at 100 to 125 ° C. for 5 hours, and water generated during the reaction was removed from the system. The amount of generated water was 3.9 g. The toluene is distilled off under reduced pressure,
After the reaction system was cooled to room temperature and neutralized with 4.96 g of t-C12-C14 amine, the target product was a pale yellow paste, 1-methoxypolyethylene glycol (3-mercaptopropionate)
(N = 22.7), 234.8 g were obtained.

Elemental analysis: Sulfur (S)% Measured value 2.61% Calculated value 2.75% Refractive index n _D ° C 1.4669 (38 ° C) Melting point (° C) 32 (end of melt) Purity 95.0% (determined from the measured value of SH%) IR 2890, 1740, 1110 cm ^-1

[0037]

Example 3 Synthesis of Polyethylene Glycol Bis (3-mercaptopropionate) (Compound 3) As in Example 1, 3-mercaptopropionic acid and polyethylene glycol (average molecular weight 596.0, n = 13.1)
The reaction was carried out in the same manner as in Example 1 to obtain a transparent viscous liquid, polyethylene glycol bis (3-mercaptopropionate) (n = 13.1).

[0038] Elemental analysis: sulfur (S)% measured 7.57% Calculated 7.97% refractive index n _D ℃ 1.4828 (25 ℃) purity 95.0% (determined from SH% of the measured value) IR 2870,1740,1120 cm ^{- 1} Polymer using CS-20 (Compound 1)

[0039]

Example 4 Production of Copolymer A Xylene was placed in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket.
400 parts by weight were charged, and heated and stirred under a temperature condition of 85 ° C. while blowing nitrogen. While maintaining the same temperature, i-butyl methacrylate 237 was introduced into the reaction vessel from the dropping device.
Parts by weight, 98 parts by weight of methyl methacrylate, 39 parts by weight of ethyl acrylate, 20 parts by weight of compound 1 and 4 parts by weight of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. Then, after stirring at the same temperature for 4 hours, 2,2 '
-1 part by weight of azobisisobutyronitrile was added, and the mixture was further stirred for 4 hours. Next, 1 part by weight of 2,2'-azobisisobutyronitrile was added, and the mixture was further stirred at the same temperature for 8 hours to obtain a colorless and transparent copolymer A solution.

Heating residue of the obtained polymer solution (105 ° C.)
Residue after drying in a hot air dryer for 3 hours) is 49.7wt
%, The viscosity at 25 ° C. was 113 cps, the number average molecular weight (Mn) measured by GPC was 3483, and the weight average molecular weight (Mw) was 6310. GPC measurement conditions are as follows. Equipment: Tosoh HLC-8120GPC Column: Tosoh, Super H2000 + H4000, 6mm ID15c
m Eluent: THF Detector: RI column constant temperature: 40 ℃

[0041]

Example 5 Production of Copolymer B Copolymer was prepared in the same manner as in Example 4 except that the composition of the mixture of the dropping components was changed as shown in Table 1 in the production of copolymer A in Example 4. The copolymer B was obtained, and the physical properties of the copolymer (solution) were measured in the same manner as described above.

Table 1 shows the results.

[0043]

[Table 1]

The copolymer thus produced is a block copolymer containing a polyoxyalkylene unit in a vinyl polymerizable polymer. Such a block (co) polymer can be produced by radical polymerization of a vinyl polymerizable monomer in the presence of the mercapto fatty acid and the polyoxyalkylene compound of the present invention. Various monomers can be used as the vinyl polymerizable monomer for the above purpose. Examples thereof include derivatives such as (meth) acrylic acid and esters thereof; styrene and styrene derivatives; vinyl esters such as vinyl acetate and vinyl propionate. And vinyl polymerizable compounds such as α, β-unsaturated carboxylic acids such as maleic acid, itaconic acid, crotonic acid, and citraconic acid, and derivatives thereof.

The block copolymer thus obtained is composed of a block component made of a vinyl (co) polymer and a polyoxyalkylene block component. When an ester of a mercapto fatty acid, which is a monofunctional mercapto compound, and a polyoxyalkylene compound is used among the compounds of the present invention, the block (co)
The polymer has an AB block structure as a main component, and when an ester of a bifunctional mercapto fatty acid and a polyoxyalkylene compound is used, the block (co) polymer is an ABBA type. It is guessed that this block structure is a main component.

The polymer containing such a polyoxyalkylene unit as a block component of the polymer can increase the hydrophilicity of the polymer due to the presence of the polyoxyalkylene unit. For example, when used as a coating material,
It can be used as a material that can provide "dirt (e.g., contamination of raindrop traces)" protection or can effectively control the sustained release of a drug in water. In particular, it is a suitable material as a resin for an antifouling paint used for preventing adhesion of aquatic organisms.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshio Wachi 5-1-1 Ebisshima-cho, Sakai-shi, Osaka Sakai Chemical Industry Co., Ltd. (72) Inventor Hayami Tateishi 5-1-1 Ebisshima-cho, Sakai-shi, Osaka No. Sakai Chemical Industry Co., Ltd. (72) Inventor Noriaki Kawasaki 5-1, Ebisshima-cho, Sakai City, Osaka Prefecture Sakai Chemical Industry Co., Ltd. (72) Naoya Nakamura 1 Meiji Shinkai, Otake City, Hiroshima Prefecture 7 China Paint Co., Ltd. (72) Inventor Makoto Tsuboi 7-term China Paint Co., Ltd. F-term (reference) at 1 Meiji Shinkai, Otake City, Hiroshima Prefecture 4J005 BD02 BD06

Claims (8)

[Claims] (1) R ¹ O · (R ² O) _n · (CO) · (CH ₂ ) _m · SH (1) wherein R ¹ is a hydrogen atom, carbon number An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group having 6 to 20 carbon atoms and optionally having a substituent, and R ² has 1 to 4 carbon atoms. Represents an alkylene group, m is 1 to
10 represents the number, and n represents the number of 1 to 30. And a monoester of a mercapto fatty acid and a polyoxyalkylene compound. 2. The monoester according to claim 1, wherein said m is a number from 1 to 3. 3. The monoester according to claim 1, wherein said n is a number of 3 to 10. 4. A compound of the general formula (2) R ¹ O · (R ² O) _n · H (2) wherein, in the formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 2 carbon atoms. Represents an alkenyl group having from 20 to 20 or a phenyl group having 6 to 20 carbon atoms and optionally having a substituent; R ² represents an alkylene group having 1 to 4 carbon atoms;
The number 30 is shown. And a polyoxyalkylene compound represented by the following general formula (3): HOOC · (CH ₂ ) _m · SH (3) [In the formula (3), m represents a number of 1 to 10. Wherein R ¹ O · (R ² O) _n · (CO) · (CH ₂ ) _m · SH (1) wherein the compound is reacted with a mercapto fatty acid represented by the following formula: , R ¹ , R ² , m, n are the same as in the above formula (1). The method for producing a monoester of a mercapto fatty acid and a polyoxyalkylene compound represented by the formula: 5. The general formula (4) HS ・ (CH ₂ ) _{l l} (CO) ・ O (R ² O) _{n n} (CO) ・ (CH ₂ ) _m・ SH (4) [Formula (4) Wherein R ² represents an alkylene group having 1 to 4 carbon atoms;
And m independently represent a number of 1 to 10, and n represents a number exceeding 3 and 30 or less. And a bisester of a mercapto fatty acid and a polyoxyalkylene compound. 6. The bisester according to claim 5, wherein 1 and m of the mercapto fatty acid constituting the general formula (4) are each independently a number of 1 to 3. 7. The polyoxyalkylene group constituting the general formula (4) wherein n is a number exceeding 3 and not more than 10.
Or the bisester according to claim 6. 8. general formula ^{(2a) R 1 O · (} R 2 O) n · H (2a) wherein, R ¹ represents a hydrogen atom, R ² represents an alkylene group having 1 to 4 carbon atoms, n Indicates a number exceeding 3 and not more than 30. ] And the polyoxyalkylene compound represented by the general formula (3), (3a) HOOC · (CH 2) m · SH (3) HOOC · (CH 2) l · SH (3a) [Equation (3) , M represents a number of 1 to 10, and in the formula (3a), 1 represents a number of 1 to 10. General formula (4) characterized by reacting with a mercapto fatty acid represented by the formula: HS · (CH ₂ ) _l · (CO) · O · (R ² O) _n · (CO) · (CH ₂ ) _m · SH (4) [In the above formula, R ² , l, m, and n are the same as the above formula (4). The method for producing a bisester of a mercapto fatty acid and a polyoxyalkylene compound represented by the formula: