JPH0586078A - Phosphorus-containing polythiol and its production - Google Patents

Abstract

PURPOSE:To provide a new compound having high refractive index and balanced optical properties such as specific gravity, transparency and weather resistance and useful as a material for lens. CONSTITUTION:The compound of formula I (A<1> is alkylene, etc.; X<1> is O or S; A<2> is alkylene, etc.; A<3> is alkyl, aralkyl, etc.), e.g. p- methoxyphenyldithiophosphonic ac id 0,S-di-2-mercaptoethyl ester. The compound of formula I can be produced by reacting a thiol compound of formula II with a compound of formula III and optionally reacting the reactional product with a thiol compound of formula IV (X<5> is O or S).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphorus-containing polythiol, which has a wide range of applications such as raw materials for synthetic resins, vulcanizing agents, cross-linking agents, epoxy resin curing agents, antioxidants, pharmaceutical and agricultural chemical intermediates And a novel phosphorus-containing polythiol having

[0002]

2. Description of the Related Art A polythiol compound having a plurality of mercapto groups in one molecule is a useful compound used for resin modification and crosslinking. In recent years, particularly in the field of optical materials, introduction of a sulfur atom into a resin has been studied as one means for increasing the refractive index of the resin, and these polythiol compounds have been used as useful resin raw materials.

[0003]

The resin obtained from the above polythiol compound as a raw material has a considerably higher refractive index than conventional lens materials. However, it is not a material that is well balanced in terms of characteristics such as specific gravity, transparency, and weather resistance, and is not always satisfactory as a lens material.

[0004]

As a result of intensive studies to overcome the above problems, the present inventors have succeeded in synthesizing a novel polythiol compound having a phosphorus atom, and have a resin using the polythiol compound as a raw material. Has been found to be a material capable of achieving the above object, and has come to propose the present invention.

That is, the present invention provides the following formula (1)

[0006]

[Chemical 11]

[0007] [where, A ^{1 is, - (R 1 -X 2)} m -R 2 -
{However, R ¹ and R ² are the same or different alkylene groups, or

[0008]

[Chemical formula 12]

(Wherein k is an integer of 0 to 2), X ² is an oxygen atom or a sulfur atom, and m is an integer of 0 or more. } And A ² is -R ^3- (X ³ -R
⁴ ) _n- {wherein R ³ and R ⁴ are the same or different alkylene groups, or

[0010]

[Chemical 13]

(Wherein k is an integer of 0 to 2), X ³ is an oxygen atom or a sulfur atom, and n is an integer of 0 or more. A}, A ^{3 _{is, - (X 4) p -R}} 5
{However, R ⁵ is an alkyl group or

[0012]

[Chemical 14]

(However, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰
Are the same or different hydrogen atoms, alkyl groups,
An aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group,
q is an integer of 0 or more. ), X ⁴ is an oxygen atom or a sulfur atom, and p is 0 or 1. } And X ¹ is an oxygen atom or a sulfur atom. ] It is phosphorus containing polythiol shown by these.

X ¹ , X ² , X ³ and X ⁴ in the general formula (1) may be oxygen atoms or sulfur atoms.
From the viewpoint of high refractive index, sulfur atom is particularly preferable.

The alkylene group represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (1) is not particularly limited,
Since the refractive index decreases as the carbon number increases,
It is preferable to select within the range of 6, especially within the range of 2 to 4.

Further, the alkyl group represented by R ⁵ in the above general formula (1) is not particularly limited, but in general, a linear or branched one having 1 to 4 carbon atoms is preferable. .. Typical examples of the alkyl groups that are generally and preferably used include methyl group, ethyl group, n-propyl group, is
o-propyl group, n-butyl group, iso-butyl group, t
A butyl group and the like.

R ⁶ , R ⁷ , R ⁸ in the general formula (1)
R ⁹ and R ¹⁰ are the same or different hydrogen atoms,
It is an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group.

Although the above alkyl group is not particularly limited,
Generally, linear or branched ones having 1 to 4 carbon atoms are suitable. Typical examples of the alkyl groups that are generally suitably used include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a t-butyl group. ..

The aryl group is not particularly limited in carbon number, but is preferably an aryl group having 6 to 14 carbon atoms such as phenyl group, naphthyl group, phenanthryl group, anthryl group, tolyl group or xylyl group. The aralkyl group is not particularly limited in carbon number, but is a benzyl group, a phenethyl group, a phenylpropyl group,
An aralkyl group having 7 to 10 carbon atoms such as a phenylbutyl group is desirable. The alkoxy group is not particularly limited, but a linear or branched one having 1 to 4 carbon atoms is generally preferable. Typical examples of the alkoxy groups which are generally and preferably used are given below: methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso.
Examples include -butoxy group and t-butoxy group.

Further, the alkylthio group is not particularly limited, but a linear or branched one having 1 to 4 carbon atoms is generally preferred. Typical examples of the alkylthio group which are generally and preferably used include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group,
Examples thereof include n-butylthio group, iso-butylthio group, t-butylthio group and the like.

The aryloxy group is not particularly limited, but it is generally preferable that the aryloxy group has 6 to 10 carbon atoms, and specific examples thereof include a phenoxy group and a naphthyloxy group.

Further, the arylthio group is not particularly limited, but it is generally preferable that the arylthio group has 6 to 10 carbon atoms, and specific examples thereof include a phenylthio group and a naphthylthio group.

In the above general formula (1), m and n may be integers of 0 or more, but if they are too large, the weather resistance may decrease, so that they are preferably in the range of 0 to 2. ..

Further, q in the general formula (1) may be an integer of 0 or more, but 0 is preferable because the refractive index decreases as the carbon number increases.

When k, m, n, p and q are 0,-(CH ₂ ) _k -,-(R ¹ -X ² ) _m -,-(X ³ -R
_{^{4) n -, - (X}} 4) p - and - (CH _{2) q} - represents a respective bond.

Specific examples of the compound of the present invention are as follows.

P-methoxyphenyldithiophosphonic acid O, S-di-2-mercaptoethyl, phenyltrithiophosphonic acid di-2-mercaptoethyl, dithiophosphoric acid O
-Phenyl O ', S-di-2-mercaptoethyl, phenyldi-p-mercaptophenyl tetrathiophosphate, Op-methoxyphenyl O', S-di-p dithiophosphate
-Mercaptophenyl, p-methylthiophenyldi-2-mercaptoethyl tetrathiophosphate, p-methylthiophenyldithiophosphonic acid O, S-di-2-mercaptoethyl, trithiophosphate O-p-methylthiophenyl S, S'-di -P-mercaptophenyl, biphenyldithiophosphonic acid O, S-di-p-mercaptophenyl,
Di-2-mercaptoethyl p-phenoxyphenyltrithiophosphonate, O, S-di-2-mercaptoethyl p-phenylthiophenyldithiophosphonate, di-p-mercaptophenyl benzyltrithiophosphonate, S-trithiophosphate Benzyl O, S'-di-p-mercaptophenyl, methyldi-2-mercaptoethyl tetrathiophosphate, di-p-mercaptomethylbenzyl phenyltrithiophosphonate, O-phenyl S, S 'trithiophosphate
-Di-2- (p-2-mercaptoethylphenyl) ethyl, phenyl dithiothiophosphate di-2- (2-mercaptoethylthio) ethyl, p-2-methoxyphenyldithiophosphonate O-2-mercaptoethyl Sp-mercapto Phenyl, dithiophosphoric acid Op-methoxyphenyl O '
-P-mercaptophenyl S-2-mercaptoethyl,
O-2-mercaptoethyl trithiophosphate S-p-methoxyphenyl S'-p-mercaptomethylbenzyl, p
-Methylthiophenyl trithiophosphonate 2-mercaptoethyl p-mercaptomethylbenzyl, dithiophosphoric acid O-2-mercaptoethyl O'-p-methylthiophenyl S-2- (p-2-mercaptoethylphenyl) ethyl, biphenyltrithio 2-mercaptoethyl 2- (p-2-mercaptoethylphenyl) ethyl phosphonate,
2-mercaptoethyl 2- (2-mercaptoethylthio) ethyl p-phenoxyphenyltrithiophosphonate,
p-phenylthiophenyldithiophosphonic acid Op-mercaptophenyl Sp-mercaptomethylbenzyl,
Benzyltrithiophosphonate p-mercaptophenyl 2
-(P-2-mercaptoethylphenyl) ethyl, benzyl tetrathiophosphate 2-mercaptophenyl 2- (2
-Mercaptoethylthio) ethyl, methyl tetrathiophosphate p-mercaptomethylbenzyl 2- (p-2-mercaptoethylphenyl) ethyl, phenyltrithiophosphonate 2- (2-mercaptoethylthio) ethyl p-mercaptomethylbenzyl, Trithiophosphoric acid O, S-di-
2-mercaptoethyl S'-phenyl, di-2-mercaptoethyl p-benzylphenyl trithiophosphonate,
Methyldithiophosphonic acid O, S-di-2-mercaptoethyl, trithiophosphoric acid O, S-di-2-mercaptoethyl S'-tolyl and the like can be mentioned.

The phosphorus-containing polythiol represented by the general formula (1) may be obtained by any method, but generally it can be produced by the method described below.

The following equation (2)

[0030]

[Chemical 15]

[0031] [where, A ^{1 is, - (R 1 -X 2)} m -R 2 -
{However, R ¹ and R ² are the same or different alkylene groups, or

[0032]

[Chemical 16]

(Wherein k is an integer of 0 to 2), X ² is an oxygen atom or a sulfur atom, and m is an integer of 0 or more. } And X ¹ is an oxygen atom or a sulfur atom. ] The thiol compound shown by the following formula (3)

[0034]

[Chemical 17]

[Wherein A ³ is-(X ⁴ ) _p -R ⁵ {wherein R ⁵ is an alkyl group or

[0036]

[Chemical 18]

(However, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰
Are the same or different hydrogen atoms, alkyl groups,
An aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group,
q is an integer of 0 or more. ), X ⁴ is an oxygen atom or a sulfur atom, and p is 0 or 1. }. ] With a compound represented by
Furthermore, the following formula

[0038]

[Chemical 19]

[However, A ² is -R ^3- (X ³ -R ⁴ ) _n-
{However, R ³ and R ⁴ are the same or different alkylene groups, or

[0040]

[Chemical 20]

(Wherein k is an integer of 0 to 2), X ³ is an oxygen atom or a sulfur atom, and n is an integer of 0 or more. } And X ⁵ is an oxygen atom or a sulfur atom. ] It is the method of making the thiol compound shown by these react.

The compounds represented by the above general formulas (2), (3) and (4), which are raw materials, may be obtained by any method. Specific examples of the reaction for obtaining the compound represented by the general formula (1) are as follows.

The charged molar ratio of each compound may be appropriately selected as necessary, but in the method of reacting only the compound represented by the general formula (2) and the compound represented by the general formula (3), the general formula ( In the method of using 1 mol of the compound represented by the general formula (3) for 4 mol of the compound represented by 2) and further reacting the compound represented by the general formula (4),
Generally, 1 mol of the compound represented by the general formula (3) and 2 mol of the compound represented by the general formula (4) are generally used with respect to 2 mol of the compound represented by the general formula (2).

In the above reaction, known solvents can be used as long as they do not react with the raw materials, but it is usually preferable not to use a solvent from the viewpoint of improving the yield.

The temperature in the above reaction varies depending on the kind of the raw material, but it is generally 20 to 120 ° C., more preferably 60 to 100 ° C. The reaction time also varies depending on the type of raw material, but usually 10 minutes to
It is sufficient to select from the range of 24 hours, preferably 30 minutes to 12 hours. In addition, stirring is preferably performed during the reaction.

The method for isolating and purifying the desired product, that is, the compound represented by the general formula (1) from the reaction system is not particularly limited, and known methods can be employed.

The compound represented by the general formula (1) of the present invention gives a resin having a high refractive index, a small specific gravity and excellent transparency and impact resistance by polyaddition with polyisocyanate.

Specific examples of the polyisocyanate include xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate.

The polymerization method for obtaining the high refractive index resin by polyaddition of the phosphorus-containing polythiol of the present invention and polyisocyanate is not particularly limited, and a known cast polymerization method can be adopted.

Further, a radical-polymerizable monomer is synthesized by reacting the compound represented by the general formula (1) of the present invention with a compound having a radical-polymerizable group by utilizing the mercapto group. You can The homopolymer of the radical-polymerizable monomer or the copolymer of the radical-polymerizable monomer and the copolymerizable monomer is a resin having a high refractive index, a small specific gravity and excellent transparency. The compound having a radically polymerizable group is not particularly limited, but acrylic acid halide, methacrylic acid halide and

[0051]

[Chemical 21]

(However, r is 1 or 2, and Z is a halogen atom.) And the like are preferably used.

The compound represented by the general formula (1) can also be polyadded with a compound having two or more unsaturated bonds in one molecule. The mixing ratio of the compound having two or more unsaturated bonds in one molecule and the phosphorus-containing polythiol represented by the general formula (1) is such that unsaturated bonds / SH
The molar ratio is preferably 0.5 to 3.0, and more preferably 1.0 to 2.0.

[0054]

[Effect] The resin obtained by addition-polymerizing the phosphorus-containing polythiol of the present invention and polyisocyanate is a material having a high refractive index and a well-balanced optical characteristics such as specific gravity, transparency, and weather resistance. It can be preferably used as an optical material, especially as a lens material.

Further, a radical-polymerizable monomer can be obtained by utilizing the mercapto group of the phosphorus-containing polythiol compound of the present invention to react with a compound having a radical-polymerizable group. This radical-polymerizable monomer has a high refractive index by radical polymerization and gives a resin having excellent optical properties such as specific gravity, transparency and weather resistance.

[0056]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Various properties of the phosphorus-containing polythiol obtained in the examples were measured by the following test methods.

(1) IR spectrum (IR) A DIGILAB FTS-7 type Fourier transform infrared spectrophotometer manufactured by BIO-RAD was used to measure by the KBr method or the liquid film method.

(2) ¹ H-nuclear magnetic resonance spectrum ( ¹ H-
NMR spectrum) PXM-60SI type (60 MHz) manufactured by JEOL Ltd.
Was used to dilute the sample in CDCl ₃ and tetramethylsilane was measured as an internal standard.

(3) Elemental analysis Carbon and hydrogen were analyzed using CHN coder MT-2 type manufactured by Yanagimoto Seisakusho Co., Ltd., and sulfur and phosphorus were measured by a flask combustion method.

(4) Refractive Index Using an Abbe refractometer manufactured by Atago Co., Ltd., the refractive index at 20 ° C. was measured. Bromonaphthalene or methylene iodide was used as the contact liquid.

(5) Weather resistance A sample was placed in a long-life xenon fade meter (FAC-25AX-HC type) manufactured by Suga Test Instruments Co., Ltd., and polystyrene was placed for comparison, and exposed to xenon light for 100 hours, and then polystyrene. A sample having a lower degree of coloring was evaluated as ◯, an equivalent sample was evaluated as Δ, and a higher sample was evaluated as x.

Example 1 In a three-necked flask equipped with a thermometer, a stirrer and a reflux tube.

[0064]

[Chemical formula 22]

20.0 g (0.050 mol) and 2-mercaptoethanol 42.6 g (0.55 mol) were added at room temperature. While stirring the reaction solution well, set the reaction temperature to 1
The temperature was gradually raised to 00 ° C, and the mixture was stirred at 100 ° C for 2 hours.

Then, the reaction mixture was poured into water and extracted with toluene, and then the organic layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 28.2 g of a colorless transparent oily substance.

In the IR spectrum of this product, 31
Absorption based on C—H bond at 50 to 2850 cm ⁻¹ , 25
Absorption based on S—H bond at 50 cm ⁻¹ , and 688
Absorption based on the P = S bond was observed at cm ^-1 (Fig. 1).

Further, ¹ H-NMR (CDCl ₃
In a solvent, tetramethylsilane standard, ppm), δ
Signal from methoxyphenyl group (b) at 6.8 to 8.2 ppm, signal from oxymethylene group at 4.3 ppm (c), signal from methoxy group at 3.9 ppm (a), 2.5 to 3 A thiomethylene group-derived signal (d) was observed at 0.3 ppm, and a mercapto group-derived signal (e) was observed at 1.5 to 1.8 ppm (FIG. 2).

[0069]

[Chemical formula 23]

Further, elemental analysis values (values in parentheses are calculated values) are C: 38.89% by weight (38.80), H:
5.11 wt% (5.03), S: 37.60 wt%
(37.67) and P: 9.03% by weight (9.10), which were in good agreement with the calculated values.

Examples 2-33 The phosphorus-containing polythiols shown in Table 1 were synthesized by using the various raw materials in the same manner as described in detail in Example 1. Table 1 also shows the properties of the obtained phosphorus-containing polythiol and the results of elemental analysis.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

[0080]

[Table 9]

[0081]

[Table 10]

[0082]

[Table 11]

Application Example 1 5.00 g (0.015 mo) of the compound obtained in Example 1
l) and m-xylylene diisocyanate 2.76 g
(0.015 mol) and 0.05 g of di-n-butyltin dilaurate (7.9 × 10 ⁻⁵ mol) were well stirred,
Gradually heating and polyaddition were performed over 24 hours. This product has a refractive index (n _D ) of 1.662 and an Abbe number (ν) of 3
1, the specific gravity was 1.34, the weather resistance was ◯, and it was colorless and transparent.

Application Examples 2 to 33 In the same manner as in Application Example 1, polymers were obtained using the phosphorus-containing polythiols obtained in Examples 2 to 33 and various monomers. The physical properties of the obtained polymer are shown in Table 2.

[0085]

[Table 12]

[0086]

[Table 13]

[0087]

[Table 14]

[0088]

[Table 15]

[0089]

[Table 16]

[0090]

[Table 17]

[0091]

[Table 18]

[0092]

[Table 19]

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the phosphorus-containing polythiol of the present invention obtained in Example 1.

FIG. 2 is a ¹ H-nuclear magnetic resonance spectrum of the phosphorus-containing polythiol of the present invention obtained in Example 1.

Claims (2)

[Claims] 1. The following formula: [However, A ¹ is-(R ¹ -X ² ) _m -R ^2- {however, R ¹
And R ² are the same or different alkylene groups,
Or [Chemical 2] (However, k is an integer of 0 to 2), X ² is an oxygen atom or a sulfur atom, and m is an integer of 0 or more. A}, A ^{2 is, -R 3 - (X 3 -R} 4) n - { However, R ³ and R ⁴
Are the same or different alkylene groups, or (However, k is an integer of 0 to 2.), X ³ is an oxygen atom or a sulfur atom, and n is an integer of 0 or more. }, A ³ is-(X ⁴ ) _p -R ⁵ {wherein R ⁵ is an alkyl group or (However, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each the same or different hydrogen atom, alkyl group, aryl group,
It is an aralkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group, and q is an integer of 0 or more. ), X ⁴ is an oxygen atom or a sulfur atom, and p is 0 or 1. } And X ¹ is an oxygen atom or a sulfur atom. ] The phosphorus-containing polythiol shown by these. 2. The following formula: [However, A ¹ is-(R ¹ -X ² ) _m -R ^2- {however, R ¹
And R ² are the same or different alkylene groups,
Or (However, k is an integer of 0 to 2), X ² is an oxygen atom or a sulfur atom, and m is an integer of 0 or more. } And X ¹ is an oxygen atom or a sulfur atom. ] And a thiol compound represented by the following formula: [However, A ^{3 _{is, - (X 4) p -R}} 5 { However, R ⁵
Is an alkyl group or (However, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each the same or different hydrogen atom, alkyl group, aryl group,
It is an aralkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group, and q is an integer of 0 or more. ), X ⁴ is an oxygen atom or a sulfur atom, and p is 0 or 1. }. ] The compound represented by the formula: [However, A ^{2 is, -R 3 - (X 3 -R} 4) n - { However, R ³
And R ⁴ are the same or different alkylene groups,
Or (However, k is an integer of 0 to 2.), X ³ is an oxygen atom or a sulfur atom, and n is an integer of 0 or more. } And X ⁵ is an oxygen atom or a sulfur atom. ] The thiol compound shown by these is made to react, The manufacturing method of phosphorus-containing polythiol of Claim 1 characterized by the above-mentioned.