JPH04323209A - Polymer of new thioacetal compound and its production - Google Patents

Abstract

PURPOSE:To obtain the subject new polymer useful as a main component for optical polymer having high refractive index by carrying out radical polymerization or anionic polymerization of a specific unsaturated carboxylic acid ester having thioacetal group. CONSTITUTION:The objective polymer of a thioacetal compound containing the recurring structure unit of formula IV (n is positive integer) can be produced by the radical polymerization of one or more sulfur-containing unsaturated ester compounds selected from the compounds of formula I [[R<1>, R<2> and R<4> are H, 1-3C (substituted) univalent aliphatic hydrocarbon group or 1-3C alkyl (thio) ether; R<1> and R<2>, R<1> and R<4>, R<2> and R<4> or R<1>, R<2> and R<4> may together form a ring; R<3> is 1-4C bivalent hydrocarbon group or bivalent group of formula II (R<a> and R<b> are 1-4C hydrocarbon group; k and l are 0 or 1) or formula III; m is integer of 0-3; R<5> is H or methyl] in a solvent (e.g. o-xylene).

Description

Description: FIELD OF INDUSTRIAL APPLICATION The present invention relates to a novel thioacetal compound polymer that has not been described in any literature and a method for producing the same. [0002] The thioacetal compound polymer of the present invention is a novel polymer that has not been described in any literature. [0003] An object of the present invention is to provide a novel thioacetal polymer that has not been described in the literature and a method for producing the same. An object of the present invention is to provide a polymer and a method for producing the polymer. [Means for Solving the Problem] The present invention provides novel polymers having the following general formula (a): [0006] [In the formula, R1, R2 and R4 are the same] R1 and R2 or R1 and R4, R2 and R
4 , or R1 , R2 and R4 may each be combined to form a ring, and R3 has 1 to 1 carbon atoms.
4 divalent hydrocarbon group or the following formula (a-1) or (a-2): --(Ra)k --S--(Rb)l --
(a-1)─(Ra)k─O─(Rb)l
─ (a-2) (wherein Ra and R
b may be the same or different, and 2 having 1 to 4 carbon atoms;
is a divalent hydrocarbon group, k and l are 0 or 1), m is an integer of 0 to 3, R5 is a hydrogen atom or a methyl group, and n is a positive integer] is a positive integer. [0007] The present invention also provides a method for producing the novel thioacetal compound polymer using the following formula (b):
[0008] [In the formula, R1 , R2 , R3 , R4
, R5 and m are as defined in formula (a) above. A method for producing a polymer is provided. [0010] The novel thioacetal compound polymer of the present invention and the method for producing the same will be explained in detail below. The thioacetal compound polymer of the present invention contains at least one type of repeating structural unit represented by the above general formula (a). In the general formula (a) representing this repeating structural unit, R1, R2
and R4 may be the same or different and represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a monovalent alkyl (thio)ether group having 1 to 3 carbon atoms. be. Substituted or unsubstituted 1 having 1 to 3 carbon atoms
Typical examples of aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, etc. Typical examples of alkyl (thio)ether groups having 1 to 3 carbon atoms include methylthio group, Ethylthio group, propylthio group,
Isopropyl group, methylthiomethyl group, ethylthiomethyl group, methylthioethyl group, methylthiomethylthiomethyl group, methyldithio group, ethyldithio group, methyldithiomethyl group, methoxy group, ethoxy group, propoxy group, methoxyethyl group, ethoxymethyl group, etc. Can be mentioned. Also, these R1 and R2, R1 and R4, R2 and R
4 , or R1 , R2 and R4 may each be bonded to form a ring, for example, dithiolane, dithiane, trithian, trithioadamantane or the like. Further, R3 is a divalent hydrocarbon group having 1 to 4 carbon atoms or the following formula (a-1) or (a-2):
(Ra)k ─S─(Rb)l─
(a-1)─(Ra)k─O─(Rb)l─
It is a divalent group represented by (a-2), and m is an integer of 0 to 3. Typical examples of this divalent hydrocarbon group include methylene group,
Examples include ethylene group, propylene group, ethylmethylene group, methylethylene group, dimethylmethylene group, and the like. In addition, in formula (a-1) or (a-2), Ra and Rb may be the same or different, and have 1 to 4 carbon atoms.
is a divalent hydrocarbon group, and k and l are 0 or 1. Representative examples of the divalent hydrocarbon group for Ra or Rb include a methylene group, an ethylene group, a propylene group, a butylene group, and the like. R5 is a hydrogen atom or a methyl group. In the polymer of the present invention, as a representative example of the repeating structural unit represented by the above formula (a), the following formula:
[0015] Examples include those represented by the formula (5) and (6) (wherein n is as defined in the above formula (a)). The polymer of the present invention may be composed only of at least one type of repeating structural unit selected from the repeating structural units represented by the above formula (a), or may contain other structural units. Good too. The content of at least one repeating structural unit selected from the repeating structural units represented by formula (a) in the polymer of the present invention is typically 50% or more. Typical polymers of the present invention include:
Examples include those having a weight average molecular weight of 10 x 103 to 5 x 105. The polymer of the present invention can be produced, for example, by a method including the step of polymerizing at least one sulfur-containing unsaturated ester compound selected from the compounds represented by formula (b) above. . In the general formula (b) representing the sulfur-containing unsaturated ester compound used in this method, R1
, R2, R3, R4, R5 and m are as defined for general formula (a) above. Representative examples of the sulfur-containing unsaturated ester compound represented by the general formula (b) include those represented by the following formula. [0022] [0022] [0023] The sulfur-containing unsaturated ester compound represented by the above general formula (b), which is the starting material for the polymer of the present invention, can be produced by, for example, , the following general formula (c): [Formula 10] [0025] [In the formula, R1, R2 and R4 are as defined in the above formula (a), and R6 is the following formula (
c-1): -R3 -OM
(c-1) an oxygen-containing thioacetal compound (wherein R3 is as defined in formula (a) above, and M is a hydrogen atom or an alkali metal) and the following general formula (d): X-CO-C(R5)=CH2
(d) [In the formula (a), R5 is as defined in the above formula (a), and X is a halogen atom]. In the general formula (c) representing the oxygen-containing thioacetal compound used in this method, R
1 , R2 and R4 are as defined for general formula (a) above. Moreover, R6 is the formula (c-1
), and in this formula (c-1), R3 is as defined in the above formula (a). In the formula (c-1), M is a hydrogen atom or an alkali metal. Representative examples of this alkali metal include sodium, potassium, and lithium. Specific examples of the oxygen-containing thioacetal compound represented by the general formula (c) include 2-hydroxymethyl-1,3-dithiolane, 2-hydroxymethyl-2-
Methyl-1,3-dithiolane, 2-hydroxyethyl-
2-methyl-1,3-dithiolane, 2-hydroxymethyl-1,3-dithiane, 2-hydroxymethyl-2-methyl-1,3-dithiane, 2-hydroxyethyl-1,
3-dithiane, 2-hydroxyethyl-2-methyl-1
, 3-dithiane and the like. In the general formula (d) representing another raw material, the acid halide compound, R5 is as defined in the formula (a) above, and X is a halogen atom. Typical examples of the halogen atom for X include chlorine, bromine, and iodine. Specific examples of the acid halide compounds include acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, acrylic acid iodide, and methacrylic acid iodide. In this method, the molar ratio of the oxygen-containing thioacetal compound/acid halide compound is in the range of 0.1 to 10. The reaction is carried out in the presence of a solvent. Typical examples of solvents used include aprotic organic solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, benzene, toluene, and dimethoxyethane. [0033] The reaction temperature is appropriately selected depending on the raw materials, solvent, and other conditions used, but is usually -20 to 30°C.
A typical range is ℃. The reaction pressure is preferably normal pressure. Further, the reaction atmosphere is preferably a nitrogen atmosphere. When using a compound in which M in the general formula (c) is a hydrogen atom as the raw material oxygen-containing thioacetal compound, adding a basic compound such as triethylamine to the reaction mixture facilitates the reaction. It is advantageous in that it progresses to As a result of the above reaction, the sulfur-containing unsaturated ester compound represented by the general formula (b), which is the starting material for the polymer of the present invention, can be obtained from the reaction mixture obtained. Recovery of the sulfur-containing unsaturated ester compound represented by the general formula (b) from the reaction mixture can be carried out according to various methods, and is not particularly limited. For example, methanol is added to the reaction mixture to convert unreacted acid halide compounds contained in the reaction mixture into volatile ester compounds and remove them. Next, the reaction mixture was washed with water, and the organic layer was dried by adding magnesium sulfate.
Concentrate under reduced pressure to obtain the crude product. Furthermore, by purifying this crude product, the sulfur-containing unsaturated ester compound represented by the general formula (b), which is the target compound, can be easily obtained. Examples of the purification method include silica gel column chromatography using a hexane-ethyl acetate eluent. This sulfur-containing unsaturated ester compound is
In its infrared absorption spectrum, the wave number is 1720 cm.
Since it exhibits a characteristic absorption derived from the α,β-unsaturated ester bond in the vicinity of −1, it can be identified based on this. The polymer of the present invention can be produced by reacting a reaction mixture containing at least one selected from the sulfur-containing unsaturated ester compounds represented by the above formula (b) as a main component. However, the format of the reaction is not particularly limited. For example, any polymerization method such as radical polymerization or anionic polymerization can be used. [0040] When the polymer of the present invention is produced by radical polymerization, the radical polymerization initiator used in radical polymerization is not particularly limited and may be any one commonly used in radical polymerization. For example, peroxides such as benzoyl peroxide, di-t-butyl peroxide, hydrogen peroxide, and t-butyl hydroperoxide; azo compounds such as azobisisobutyronitrile, azobisisopropyl, and azobis-2-propylonitrile; Examples include. These may be used alone or in combination of two or more. [0041] The amount of this radical polymerization initiator used is
Usually, the amount is about 0.001 to 10 mol%, preferably about 0.01 to 1 mol% of the monomers used. [0042] The polymerization temperature is typically in the range of 30 to 100°C. Although the polymerization reaction does not require the use of a solvent, it is preferable to use a solvent because a high molecular weight polymer can be obtained. The solvent used is benzene,
Examples include organic solvents such as toluene and xylene. These may be used alone or in combination of two or more. Furthermore, the reaction atmosphere is preferably a nitrogen atmosphere. After the polymerization reaction is completed as described above, a solution is prepared by dissolving the reaction mixture in a solvent such as THF, and this solution is stirred into a solvent such as methanol in which the polymer of the present invention is poorly soluble. Add it dropwise to re-precipitate. Next, the reprecipitated polymer is filtered and dried under reduced pressure to obtain a purified product. [Examples] The present invention will be specifically explained below with reference to Examples, but these Examples are not intended to limit the scope of the present invention in any way. (Production Example 1) 2-Hydroxymethyl-2-
8.20 g of methyl-1,3-dithiolane and 11.5 ml of triethylamine were mixed with 10 g of diisopropyl ether.
0 ml and stirred. After cooling to 0°C, 6.09 ml of acrylic acid chloride was mixed with 1 ml of diisopropyl ether.
A solution obtained by dissolving the solution in 0 ml was added dropwise to react. After stirring for 2 hours, 1.5 ml of methanol was added to stop the reaction. 150 ml of water was added to the resulting reaction mixture, and the organic layer was separated. The remaining aqueous layer was extracted with 100 ml of diisopropyl ether. The diisopropyl ether extracts were combined, dried over magnesium sulfate, and concentrated. The obtained concentrated liquid was purified by silica gel column chromatography to obtain an oily reaction product 3.
．． 22g was obtained. The Rf value and refractive index (n
The measurement results of D25), IR measurement, 1H-NMR, UV measurement, mass spectrometry, and elemental analysis were as follows. Rf value: 0.25 (Silica gel: Merck 5735,
Eluent: hexane/ethyl acetate = 9/1 mixture) Refractive index (nD 25): 1.5385 IR (neat): 2925, 1720, 1500, 1
190 cm-1 1H-NMR (CDCl3 internal standard): δ 1.
75 (s, 3H) 3.30 (s, 4H) 4.22 (s, 2H) 5.7 to 6.6 (m, 3H) UV (diisopropyl ether): λmax 236
nm, ε462 MS: M+ 204 Elemental analysis: Measured value: C; 49.68, H
;6.23,S;28.90
Calculated value: C; 49.51, H; 6.46, S; 29.3
From the above results, it was confirmed that the reaction product was 2-methyl-2-propenoyloxymethyl-1,3-dithiolane represented by the following formula: embedded image. (Production Example 2) 2-hydroxyethyl-2-methyl-1,
7.50 g of 3-dithiolane and 11 g of triethylamine
．． 5 ml was added to 100 ml of diisopropyl ether and stirred. After cooling to 0° C., a solution of 6.09 ml of acrylic acid chloride dissolved in 50 ml of diisopropyl ether was added dropwise to react. After stirring for 2 hours, 1.5 ml of methanol was added to stop the reaction. 150 ml of water was added to the resulting reaction mixture, and the organic layer was separated. Add 10 diisopropyl ether to the remaining aqueous layer.
Extraction treatment was performed using 0 ml. The diisopropyl ether extracts were combined, dried over magnesium sulfate, and concentrated. The obtained concentrated liquid was purified by silica gel column chromatography to obtain 1.76 g of an oily reaction product. Rf value of this reaction product, refractive index (nD 25),
The measurement results of IR measurement, 1H-NMR, UV measurement, mass spectrometry, and elemental analysis were as follows. Rf value: 0.53 (Silica gel: Merck 5735,
Eluent: hexane/ethyl acetate = 9/1 mixture) Refractive index (nD 25): 1.5298 IR (neat): 2925, 1720, 1505, 1
190 cm-1 1H-NMR (CDCl3 internal standard): δ 1.
78 (s, 3H) 2.30 (t, 2H) 3.32 (s, 4H) 4.34 (t, 2H) 5.78 (dd, 1H) 6.17 (d, 1H) 6.32 ( d, 1H) UV (diisopropyl ether): λmax 241
nm, ε286 MS: M+ 218 Elemental analysis: Measured value: C; 46.91, H
;5.73,S;32.70
Calculated value: C; 47.03, H; 5.92, S; 31.3
From the above results, it was confirmed that the reaction product was 2-methyl-2-propenoyloxyethyl-1,3-dithiolane represented by the following formula: . (Example 1) 5 m of o-xylene was added to the reaction vessel.
2-methyl-2- obtained in Production Example 1
Propenoyloxymethyl-1,3-dithiolane 1.0
0g was added and dissolved. Next, 0.8 mg of azobisisobutyronitrile was added, and after bubbling with nitrogen for 30 minutes, the mixture was stirred for 14 hours to react while maintaining the temperature at 50°C. After concentrating the obtained reaction mixture, 5 m of toluene was added.
A reaction mixture solution was obtained. This reaction mixture solution was added little by little to 200 ml of methanol with vigorous stirring to precipitate the polymer produced by the reaction. The polymer precipitated in methanol was collected by filtration and drying under reduced pressure to obtain 0.97 g of a colorless and transparent polymer. The weight average molecular weight, IR spectrum and NMR spectrum of the obtained polymer were measured and subjected to elemental analysis. 2-methyl-2- which is a monomer of the polymer
The refractive index (nD
) is 1.57 to 1.58. The results are shown below. Weight average molecular weight: 19 x 104 IR spectrum (film, cm-1): 2850.1
735,1445, 1370,1255,1155 Elemental analysis: Measured value: C; 46.88, H; 5.74, S
;31.10, Calculated value: C;47
．． 03, H; 5.92, S; 31.39, 005
3] (Example 2) 1 ml of o-xylene was charged into a reaction vessel, and 1.00 g of 2-methyl-2-propenoyloxyethyl-1,3-dithiolane obtained in Production Example 2 was added and dissolved. . Next, azobisisobutyronitrile 0
．． After adding 8 mg and bubbling nitrogen for 30 minutes, the mixture was stirred and reacted for 16 hours while maintaining the temperature at 50°C. The obtained reaction mixture was concentrated and then dissolved in 15 ml of THF to obtain a reaction mixture solution. This reaction mixture solution was added little by little to 200 ml of methanol with vigorous stirring to precipitate the polymer produced by the reaction. The polymer precipitated in methanol was collected by filtration and drying under reduced pressure to obtain 0.65 g of a colorless and transparent polymer. The weight average molecular weight, IR spectrum and NMR spectrum of the obtained polymer were measured and subjected to elemental analysis. 2-methyl-2- which is a monomer of the polymer
The refractive index (nD
) is 1.56-1.57). The results are shown below. Weight average molecular weight: 15.5 x 104 IR spectrum (film, cm-1): 2850.1
730,1440, 1365,1260,1160 Elemental analysis: Measured value: C; 49.51, H; 6.28, S
;29.30, Calculated value: C;49
．． 51, H; 6.46, S; 29.37, 005
5] [Effects of the Invention] The polymer of the present invention is a novel polymer that has not been described in any literature. This new polymer is suitable as a main component of high refractive index polymers for optical applications. Moreover, the production method of the present invention is useful as a method for producing this polymer.

Claims (2)

[Claims] [Claim 1] The following general formula (a): [Formula 1] [In the formula, R1, R2 and R4 may be the same or different, and represent a hydrogen atom, a substituted or unsubstituted monovalent group having 1 to 3 carbon atoms] is an aliphatic hydrocarbon group or a monovalent alkyl (thio)ether group having 1 to 3 carbon atoms, and R1 and R
2 or R1 and R4, R2 and R4, or R1, R2 and R4 may be bonded to each other to form a ring, and R3 is a divalent hydrocarbon group having 1 to 4 carbon atoms or the following formula (a -1) or (a-2): ─(Ra )k ─S─(Rb )l ─
(a-1)─(Ra)k─O─(Rb)l
─ (a-2) (wherein Ra and R
b may be the same or different, and 2 having 1 to 4 carbon atoms;
is a divalent hydrocarbon group, k and l are 0 or 1), m is an integer of 0 to 3, R5 is a hydrogen atom or a methyl group, and n is a positive integer] is a positive integer. [Claim 2] A compound represented by the following formula (b): [In the formula, R1, R2, R3, R4, R5 and m are as defined in the above formula (a)] The method for producing a polymer of a thioacetal compound according to claim 1, comprising the step of polymerizing at least one sulfur-containing unsaturated ester compound.