JP4977099B2 - Radical polymerizable group-containing cyclic polysulfide, process for producing the same, and polymer thereof - Google Patents

Description

  The present invention relates to a cyclic polysulfide containing a radical polymerizable group, a method for producing the same, and a polymer obtained by polymerizing or copolymerizing the cyclic polysulfide.

Polymer gels are used in various fields. Recently, soft contact lenses, drug release alone, artificial muscles and robot hands (actuators), drug delivery systems (DDS), separation and purification materials, cell culture substrates It is used for functional materials such as shape memory materials.
Conventionally, polymer gels are classified according to the difference in structure of their three-dimensional cross-linked parts, and there are only two types: chemical gels and physical gels. In the former, the cross-linking points are constituted by covalent bonds, whereas in the latter, the cross-linking points are constituted by relatively weak bonds such as hydrogen bonds, and in any gel, the cross-linking points are always fixed. .
Thus, in recent years, a topological gel in which a crosslinking point is formed of a cyclic compound as a third gel has attracted attention. This topological gel exhibits different properties from conventional gels due to the cross-linking point sliding along the molecular chain (pulley effect). That is, the topological gel can move the most burdensome part at the time of stretching due to the pulley effect, so that it can be stretched while dispersing the force, and has high extensibility and superior to the conventional gel. Since it also has water absorption, application to the biotechnology field is expected.
As such a topological gel, a radical copolymer of a crown ether derivative having one vinyl group and a vinyl monomer (see Non-Patent Document 1 to Non-Patent Document 3), a polymer having a dibenzocrown ether skeleton in the main chain, There are known polymers made of a polymer having a macrocyclic structure in the main chain, such as a cross-linked product composed of only moving cross-linking points (Non-patent Document 4) by reaction with a dumbbell-shaped ammonium salt.

A. Zada, Y. Avny, A. Zilkha, Eur. Polym. J., 35, 1159 (1999). A. Zada, Y. Avny, A. Zilkha, Eur. Polym. J., 36, 351 (2000). A. Zada, Y. Avny, A. Zilkha, Eur. Polym. J., 36, 359, (2000). Toshikazu TAKATA Polymer.Journal, vol. 38, No 1 (2006)

  An object of the present invention is to provide a radically polymerizable group-containing cyclic polysulfide capable of obtaining a polymer having a macrocyclic structure, a production method thereof, and a polymer obtained by polymerizing the radically polymerizable group-containing cyclic polysulfide. There is.

  The radical polymerizable group-containing cyclic polysulfide of the present invention is represented by the following formula (1).

In [the formula (1), R ^1, -CH ^₂ -O-R ₂ (where, R ² is. Represents an alkyl group or a substituted or unsubstituted phenyl group having 1 to 6 carbon atoms) groups represented by , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. k is an integer of 1-100 . ]

  The method for producing a radically polymerizable group-containing cyclic polysulfide according to the present invention includes a step of reacting a cyclic polysulfide represented by the following formula (2) with 3-chloromethylstyrene.

[In the formula (2), R ¹ represents —CH ₂ —O—R ² (where R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. k is an integer of 1-100 . ]

  In the method for producing a radically polymerizable group-containing cyclic polysulfide according to the present invention, 2,4-thiazolidione is reacted with a thiirane compound represented by the following formula (3) to be represented by the above formula (2). It is preferable to have a step of synthesizing a cyclic polysulfide.

[In the formula (3), R ¹ represents —CH ₂ —O—R ² (where R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. ]

The polymer of the present invention has a number average molecular weight of 300 to 50,000 represented by the following formula (4).

[In the formula (4), R ¹ is a group represented by —CH ₂ —O—R ² (wherein R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. k is an integer of 1-100 . ]

The polymer of the present invention is obtained by polymerizing the above-mentioned radical polymerizable group-containing cyclic polysulfide and a monomer copolymerizable therewith , and has a number average molecular weight of 300 to 50,000 .

  According to the radically polymerizable group-containing cyclic polysulfide of the present invention, a polymer having a cyclic polysulfide skeleton can be obtained by polymerization, and such a polymer can be used as a polymer constituting a topological gel. It is.

Embodiments of the present invention will be described below.
The radical polymerizable group-containing cyclic polysulfide of the present invention (hereinafter referred to as “polymerizable cyclic polysulfide”) has a structure represented by the above formula (1).
In the formula (1) showing a polymerizable cyclic polysulfide, R ¹ is a group represented by —CH ₂ —O—R ² , a phenyl group, a naphthyl group, a butyl group, a methyl group or an ethyl group.
Here, in the group represented by —CH ₂ —O—R ² , R ² is an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group. Specific examples thereof include, for example, methoxymethyl Group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, n-pentoxymethyl group, isopentoxymethyl group, n-hexoxymethyl group, isohexoxymethyl Group, substituted or unsubstituted phenoxymethyl group, and the like. Among these, a phenoxymethyl group, a methyl group, and a phenyl group are preferable.
K is an integer of 1 or more, preferably an integer of 1 to 100.

  The polymerizable cyclic polysulfide of the present invention has a polystyrene-equivalent number average molecular weight (hereinafter simply referred to as “number average molecular weight”) Mn measured by size exclusion chromatography (SEC), for example, 100 to 50,000, The same molecular weight distribution (hereinafter simply referred to as “molecular weight distribution”) Mw / Mn is 1.0 to 4.0.

The polymerizable cyclic polysulfide of the present invention can be obtained, for example, as follows.
First, by reacting 2,4-thiazolidione and a thiirane compound represented by the above formula (3) (hereinafter referred to as “specific thiirane compound”) in an appropriate solvent in the presence of a catalyst, A cyclic polysulfide represented by the above formula (2) (hereinafter referred to as “specific cyclic polysulfide”) is synthesized.
In the reaction between 2,4-thiazolidione and a specific thiirane compound, 2,4-thiazolidione is cleaved and a CC bond in the sulfide group of one or more specific thiirane compounds is inserted and inserted (insertion reaction). Furthermore, the compound obtained thereby is cleaved and recombined (exchange reaction), whereby a specific cyclic polysulfide is synthesized.

Preferable specific examples of the specific thiirane compound include phenoxypropylene sulfide (in the formula (3), R ² is a phenyl group), n-butoxypropylene sulfide (in the formula (3), R ² is an n-butoxymethyl group) ) And the like.
The ratio of 2,4-thiazolidione to a specific thiirane compound depends on the molecular weight of the target specific cyclic polysulfide, but the specific thiirane compound is 1.0 to 300 mol per 1 mol of 2,4-thiazolidione. Preferably there is.

As the solvent, for example, N-methylpyrrolidone, dichlorobenzene and the like can be used.
The concentration of 2,4-thiazolidinedione in the solvent is preferably 0.1 mol / L or more, more preferably 1.0 mol / L or more.
When the concentration of 2,4-thiazolidinedione is too small, the reaction may not proceed sufficiently.

As the catalyst, a quaternary onium salt can be used, and specific examples thereof include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, Examples include cetyltrimethylammonium bromide, tetrapropylammonium bromide, and benzyltriethylammonium chloride. Of these, tetrabutylammonium chloride is preferred.
These quaternary salts are used in combination with salts such as 18-crown-6-ether, potassium chloride, potassium bromide, potassium iodide, cesium chloride, potassium phenoxide, sodium phenoxide, potassium benzoate and the like. You can also.
Moreover, the usage-amount of a catalyst is 0.01-0.5 mol with respect to 1 mol of 2, 4- thiazolidinedione.

The reaction temperature is preferably 20 to 100 ° C. If the reaction temperature is too low, it may be difficult to proceed the reaction.
The reaction time is, for example, 1 to 24 hours.

The specific cyclic polysulfide thus obtained and 3-chloromethylstyrene are reacted in an appropriate solvent in the presence of a catalyst to obtain the polymerizable cyclic polysulfide of the present invention.
The ratio of the specific cyclic polysulfide and 3-chloromethylstyrene is, for example, 1.0 to 10.0 mol of 3-chloromethylstyrene with respect to 1 mol of the specific cyclic polysulfide.
As the solvent, for example, acetonitrile, methylene chloride, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide and the like can be used.
Moreover, the density | concentration of the specific cyclic polysulfide in a solvent is 0.1-10.0 mol / L, for example.
As the catalyst, di-μ-hydroxobis [N, N, N ′, N′-tetramethylethylenediamine copper (II)] dichloride can be used.
Moreover, the usage-amount of a catalyst is 0.01-1.0 mol with respect to 1 mol of specific cyclic polysulfides.

  According to the radical polymerizable group-containing cyclic polysulfide of the present invention, a polymer having a cyclic polysulfide skeleton can be obtained by polymerization.

The polymer of the present invention is obtained by radical polymerization of the above polymerizable cyclic polysulfide alone, or the above polymerizable cyclic polysulfide and a monomer copolymerizable therewith (hereinafter referred to as “copolymerizable monomer”). A polymer obtained by radical polymerization and obtained by polymerizing a polymerizable cyclic polysulfide alone has a structure represented by the above formula (4), and is composed of the polymerizable cyclic polysulfide and the polymer. A polymer obtained by copolymerizing a polymerizable monomer has a structure represented by the following formula (5).
The polymer of the present invention has a number average molecular weight Mn of, for example, 300 to 50,000, and a molecular weight distribution Mw / Mn of 1.0 to 4.0.

[In the formula (5), R ¹ is a group represented by —CH ₂ —O—R ² (wherein R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group, and X represents a structural unit derived from a copolymerizable monomer. k is an integer of 1 or more. ]

Specific examples of the copolymerizable monomer include acrylates such as styrene, methyl methacrylate, methyl acrylate, and hydroxymethyl acrylate.
Moreover, it is preferable that the ratio of a copolymerizable monomer is 80 mol% or less of all the monomers.

The polymerization reaction is performed in an appropriate solvent in the presence of a radical polymerization catalyst.
As the solvent, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, tetrahydrofuran or the like can be used.
Moreover, the density | concentration of the monomer in a solvent is 0.1-0.5 mol / L, for example.
As the radical polymerization catalyst, α, α′-azobisisobutyronitrile, dibenzoyl peroxide and the like can be used.
Moreover, the usage-amount of a radical polymerization catalyst is 0.01-0.5 mol with respect to 1 mol of monomers.
As polymerization reaction conditions, for example, the reaction temperature is 25 to 80 ° C., and the reaction time is 2 to 24 hours.

  Since the polymer of the present invention has a cyclic polysulfide skeleton in the main chain, it can be used as a polymer constituting a topological gel. In addition, optical materials, artificial muscles, robot hands (actuators), drug delivery systems (DDS), separation and purification materials, cell culture substrates, shape memory materials, and the like.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

In the following examples, the following materials and solvents were used.
(1) Tetrabutylammonium chloride (hereinafter referred to as “TBAC”), tetraphenylphosphonium chloride (hereinafter referred to as “TPPC”), di-μ-hydroxobis [N, N, N ′, N′-tetramethyl Ethylenediamine copper (II)] dichloride (hereinafter referred to as “Cu (TMEDA) Cl ₂ ”), cesium carbonate, tetrahydrofuran (hereinafter referred to as “THF”), chloroform, methanol and hydroquinone are commercially available products. Using.
(2) As acetonitrile, the one obtained by distilling under reduced pressure by adding diphosphorus pentoxide was used. (3) As N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”), preliminarily dried using calcium hydride and then vacuum distilled in the presence of calcium hydride was used. .
(4) As 2,4-thiazolidione (hereinafter referred to as “TADO”), recrystallization was performed using ethyl acetate.
(5) As chloromethylstyrene (hereinafter referred to as “CMS”), those separated by silica gel column chromatography (developing solvent: n-hexane) were used.
(6) As styrene, what was subjected to vacuum drying in the presence of calcium hydride after preliminary drying using calcium hydride was used.

Moreover, the following were used as a measuring apparatus.
(1) Infrared spectrophotometer (IR): “FT / IR-420” manufactured by JASCO Corporation
(2) Nuclear magnetic resonance apparatus (1 H-NMR, ¹³ C-NMR):
"JOEL ECA 500", "JOEL ECA 600" manufactured by JEOL Ltd. (3) Size exclusion chromatography (SEC):
HLC-8220 manufactured by Tosoh Corporation, column: TSKgelG1000H
Standard: Polystyrene manufactured by Tosoh Corporation, Developing solvent: THF
(4) Recycle preparative high performance liquid chromatography (HPLC):
“HPLC-908 type” manufactured by Nippon Analytical Industrial Co., Ltd. Column: JAIgel 1H-A +, JAIgel 1H-F
Developing solvent: Chloroform (5) Elemental analysis:
"PE 2400 Series CHNS / O Analyzer" manufactured by PerkinElmer Japan Co., Ltd.

<Example 1>
In a glove box with a humidity of 10% or less, an ampoule tube was charged with 0.04 g (0.3 mmol) of 2,4-thiazolidione, 0.25 g (1.5 mmol) of phenoxypropylene sulfide, and 0.004 g (5 mol%) of TBAC as a catalyst. NMP was further added so that the monomer concentration was 1M. Next, a two-way cock was attached, and after freezing and degassing were repeated three times, the tube was sealed and reacted at 60 ° C. for 24 hours. After completion of the reaction, the mother liquor was poured into methanol, the methanol insoluble matter was recovered and dissolved in a small amount of chloroform, and precipitation purification treatment was performed using methanol. The obtained methanol insoluble matter was dried under reduced pressure for 24 hours to obtain a colorless solid.
From the results of NMR analysis and IR analysis, it was confirmed that the obtained product was a cyclic polysulfide represented by the following formula (A). Hereinafter, this is referred to as CPS (A).
Moreover, from the result of SEC, the number average molecular weight Mn of CPS (A) was 1300, and molecular weight distribution Mw / Mn was 1.3.

The results of NMR analysis and IR analysis of the obtained product are shown below, and the ¹ H-NMR spectrum is shown in FIG.
○ ¹ H-NMR (600 Mz, DMSO-d6, TMS) δ (ppm):
3.02 (br, 10.0 H, H ^c ), 3.28 (br, 5.0 H, H ^b ), 3.78 (s, 2.0 H, H ^a ), 4.13 (br, 10 ^{.0H, H e), 6.28~7.25 (} br, 15.0H, H d, H f, H g)
○ IR (KRS, film, cm ^-1 ):
3048 (νC-H aromatic), 2927 (νC-H aliphatic), 1751 (νC = O amid), 1683 (νC = O thioester), 1599, 1584 (νC = C aromatic), 1301, 1031 (νC—O—) C ether), 753 (C-S-C sulfide)

In a sample bottle, 1.07 g (0.7 mmol) of cyclic polysulfide (A) and 30 mL of acetonitrile were added to make the system uniform. In a glove box, 0.35 g (1.5 equivalents) of cesium carbonate, 0.16 g (50 mol%) of Cu (TMEDA) Cl ₂ and 0.55 g (5 equivalents) of CMS were added to the system, which was then sealed, and at room temperature. Stir for 24 hours. After completion of the reaction, the mother liquor was diluted with chloroform and washed with water. Next, the organic layer was concentrated and subjected to precipitation purification using methanol as a poor solvent. Methanol-insoluble material was diluted with chloroform, passed through an alumina column, and concentrated. This was separated by silica gel column chromatography to obtain a colorless and transparent solid. Yield was 1.0 g (95%).
From the results of NMR analysis and IR analysis, it was confirmed that the obtained product was a polymerizable cyclic polysulfide represented by the following formula (B). Hereinafter, this is referred to as PCPS (B). Moreover, from the result of SEC, the number average molecular weight Mn of PCPS (B) was 1400, and molecular weight distribution Mw / Mn was 1.3.

The results of NMR analysis and IR analysis of the obtained product are shown below, the ¹ H-NMR spectrum diagram is shown in FIG. 2, and the IR spectrum diagram is shown in FIG.
○ ¹ H-NMR (600 Mz, DMSO-d6, TMS) δ (ppm):
3.02 (br, 10.7 H, H ^c ), 3.25 (br, 4.5 H, H ^b ), 3.79 (br, 2.0 H, H ^a ), 3.86 (br, 1. ^{8H, H h), 4.13 (} br, 10.3H, H e), 5.20 (br, 1.0H, H m), 5.73 (br, 1.0H, H l), 6. ^{65 (br, 1.1H, H k} ), 6.85~7.34 (br, 17.1H, H d, H f, H g, H i, H j)
○ IR (KRS, film, cm ^-1 ):
3048 (νC-H aromatic), 2927 (νC-H aliphatic), 1750 (νC = O aide), 1684 (νC = O thioester), 1635 (νC = C vinyl), 1599, 1584 (νC = C aromatic), 1301, 1031 (νC—O—C ether), 754 (C—S—C sulfide)

<Example 2>
In a sample bottle, 1.4 g (1 mmol) of PCPS (B) was weighed, and 0.5 mL of DMF (monomer concentration was 2 M) was added to make uniform. This solution was transferred to an ampule tube containing a rotor, and 8.1 mg (5 mol%) of α, α′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) was added. After attaching a two-way cock, repeating freezing and degassing three times, the tube was sealed and reacted at 60 ° C. for 24 hours. After completion of the reaction, the reaction mother liquor was diluted with chloroform and subjected to isolation and purification by HPLC. The yield was 1.1 g (85%).
From the result of NMR analysis, it was confirmed that the obtained product was a polymer represented by the following formula (C). Hereinafter, this is referred to as a polymer (C).
From the SEC results, the number average molecular weight Mn of the polymer (C) was 37500, and the molecular weight distribution Mw / Mn was 3.96.

The results of NMR analysis of the obtained product are shown below, and the ¹ H-NMR spectrum is shown in FIG.
○ ¹ H-NMR (600 Mz, DMSO-d6, TMS) δ (ppm):
^{0.60~1.73 (br, 1.7H, H k} , H l), 2.97 (br, 8.9H, H c), 3.14 (br, 3.5H, H b), 3 ^{.66 (br, 1.0H, H a} ), 3.80 (br, 2.8H, H h, H a), 3.97 (br, 11.1H, H e), 5.60~6. ^{40 (br, 1.2H, H i} , H j), 6.23 (br, 17.5H, H d, H g), 7.12 (br, 10.3H, H f)

<Examples 3 to 7>
According to the formulation shown in Table 1 below, PCPS (B) and styrene were copolymerized by the following operation.
PCPS (B) was weighed into a sample bottle, and DMF was added in an amount such that the monomer concentration was 2M, and the mixture was made uniform. This solution was transferred to an ampoule tube containing a rotor, and AIBN was added in an amount of 5 mol% based on styrene and monomers. After attaching a two-way cock, repeating freezing and degassing three times, the tube was sealed and reacted at 60 ° C. for 24 hours. After completion of the reaction, the reaction mother liquor was diluted with chloroform and subjected to isolation and purification by HPLC.
From the results of NMR analysis, it was confirmed that each of the obtained products was a polymer represented by the following formula (D). Hereinafter, these are referred to as a polymer (D-1) to a polymer (D-5).
Table 1 below shows the number average molecular weight Mn and the molecular weight distribution Mw / Mn of the polymer (D-1) to the polymer (D-5) by SEC.

The results of NMR analysis of the polymer (D-3) obtained in Example 5 are shown below, and the ¹ H-NMR spectrum is shown in FIG.
○ ¹ H-NMR (600 Mz, DMSO-d6, TMS) δ (ppm):
^{1.00~2.00 (br, 24.5H, H k} , H l, H m,, H n), 3.00 (br, 7.9H, H c), 3.16 (br, 2. ^{7H, H b), 3.71 (} br, 1.0H, H a), 3.80 (br, 2.8H, H h, H a), 4.03 (br, 7.3H, H e) , 6.00~7.20 (br, 59.6H, H d, H f, H g,, H i, H j, H m,, H n, H o, H p, H q)

<Reference Example 1>
In a glove box with a humidity of 10% or less, 12.7 g (100 mmol) of TADO, 28.9 g (1.5 equivalents) of CsCO ₃ , 0.52 g (5 mol%) of Cu (TMEDA) Cl ₂ in an eggplant flask, and 10 ml of acetonitrile as a solvent. And stirred at room temperature for 15 minutes. To this system, 15.3 g (100 mmol) of chloromethylstyrene was dropped, and after sealing, the mixture was stirred at room temperature for 24 hours. The reaction mother liquor was concentrated, separated by silica gel column chromatography, and recrystallized twice using ethyl acetate to obtain pale yellow needle crystals. The yield was 5.12 g (22%).
From the results of NMR analysis, IR analysis, and elemental analysis, the obtained product was 3- (vinylbenzyl) thiazolidione-2,4-dione (hereinafter referred to as “VBTADO”) represented by the following formula (E). It was confirmed that.

The results of NMR analysis, IR analysis and elemental analysis are shown below.
○ ¹ H-NMR (600 Mz, DMSO-d6, TMS) δ (ppm):
4.28 (s, 2.0 H, H ^g ), 4.66 (s, 2.0 H, H ^f ), 5.26 (d, J _ac = 102 Hz, 1.0 H, H ^a ), 5.26 (D, J _bc = 180 Hz, 1.0 H, H ^b ), 6.71 (dd, J _ca = 102 Hz, J _cb = 180 Hz, 1.0 H, H ^c ), 7.24 (d, J _ed = 78 Hz 2.0H, H ^e ), 7.44 (d, J _de = 78 Hz, 2.0H, H ^d )
○ IR (film, cm ^-1 ):
3047 (νC-H aromatic), 2984, 2947 (νC-H aliphatic), 1753 (νC = O amid), 1682 (ν C = O thioester), 1626 (νC = C vinyl), 1537, 1510 (νC = C) aromatic)
Elemental analysis Measured values: C: 61.49, H: 4.46, N: 5.72
Calculated values: C: 61.78, H: 4.75, N: 6.00

A small amount of hydroquinone as a rotator and a polymerization inhibitor is put into an ampule tube, and further VBTADO 0.07 g (0.3 mmol), PPS 0.45 g (3 mmol) and NMP 3 mL (amount that makes the PPS concentration 1M), and the humidity is 10% or less. In the glove box, TBAC (0.004 g, 5 mol%) was added as a catalyst. A two-way cock was attached and the tube was sealed after repeating freezing and degassing three times. This system was reacted at 60 ° C. for 24 hours. After completion of the reaction, the reaction mother liquor was poured into methanol, methanol insolubles were dissolved in a small amount of chloroform, and precipitation purification treatment was performed using methanol. The obtained methanol-insoluble material was dried under reduced pressure for 24 hours to obtain a colorless solid. The number average molecular weight Mn by SEC was 13300, and the molecular weight distribution Mw / Mn was 1.23.
As a result of NMR analysis of the obtained product, it was confirmed that it was a PPS ring-opening polymer, and the target polymerizable cyclic polysulfide was not obtained.

<Reference Examples 2-5>
Except that the reaction conditions were changed in accordance with the following Table 2, the same operation as in Reference Example 1 was carried out. In either case, a ring-opened polymer of PPS was produced, and the target polymerizable cyclic polysulfide was not obtained. Table 2 shows the number average molecular weight Mn and molecular weight distribution Mw / Mn by SEC of the obtained product.

It is a ¹ H-NMR spectrum of specific cyclic polysulfide obtained in Example. ^{1 is} a ¹ H-NMR spectrum diagram of a polymerizable cyclic polysulfide obtained in an example. FIG. It is IR spectrum figure of the polymerizable cyclic polysulfide obtained in the Example. It is a < ¹ > H-NMR spectrum figure of the polymer obtained in the Example. It is a < ¹ > H-NMR spectrum figure of the copolymer obtained in the Example.

Claims (5)

A radically polymerizable group-containing cyclic polysulfide represented by the following formula (1).

In [the formula (1), R ^1, -CH ^₂ -O-R ₂ (where, R ² is. Represents an alkyl group or a substituted or unsubstituted phenyl group having 1 to 6 carbon atoms) groups represented by , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. k is an integer of 1-100 . ] A method for producing a radically polymerizable group-containing cyclic polysulfide, comprising a step of reacting a cyclic polysulfide represented by the following formula (2) with 3-chloromethylstyrene.

[In the formula (2), R ¹ represents —CH ₂ —O—R ² (where R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. k is an integer of 1-100 . ] The method according to claim 2, further comprising a step of synthesizing a cyclic polysulfide represented by the formula (2) by reacting 2,4-thiazolidione with a thiirane compound represented by the following formula (3). A method for producing the radical polymerizable group-containing cyclic polysulfide as described.

[In the formula (3), R ¹ represents —CH ₂ —O—R ² (where R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. ] The polymer whose number average molecular weight represented by following formula (4) is 300-50,000 .

[In the formula (4), R ¹ is a group represented by —CH ₂ —O—R ² (wherein R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). , Phenyl group, naphthyl group, butyl group, methyl group or ethyl group. k is an integer of 1-100 . ] A polymer obtained by polymerizing the radically polymerizable group-containing cyclic polysulfide according to claim 1 and a monomer copolymerizable therewith , and having a number average molecular weight of 300 to 50,000 .

Images