JP2001114860A - High-molecular compound and sulfur-containing urethane-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sulfur-contg. urethane-based resin by a new synthesis method. SOLUTION: This sulfur-contg. urethane-based resin is obtained by polymerizing a hydroxyisothiocyanate compound of the chemical formula (2): HO-R1-NCS (R1 is a chain paraffin, olefin, cycloparaffin, cycloolefin, phenylene, or a sulfur- contg. modification thereof, oxygen-contg. modification thereof, nitrogen-contg. modification thereof or aromatic ring-contg. modification thereof, or a halogen- substituted modification thereof or nitro-substituted modification thereof).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sulfur-containing urethane resin.

[0002]

2. Description of the Related Art Generally, a sulfur-containing urethane resin is synthesized by reacting a diisocyanate or a diisothiocyanate with a dithiol or a diol as shown in the following reaction formulas (3) to (5). (3)-(5)
Has a repeating unit as shown in

[0003]

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[0004]

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[0005]

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(In the above reaction formulas, R ₂ , R ₃ ,
R ₄ and R ₅ each represent a group having an arbitrary carbon bond. )

[0007]

On the other hand, the present invention relates to a sulfur-containing urethane-based resin produced by a novel synthesis method and a novel sulfur-containing urethane-based polymer compound obtained by this synthesis method. To provide.

[0008]

In order to solve the above-mentioned problems, the present invention provides a compound represented by the following chemical formula (2): HO-R ₁ -NCS (2) wherein R ₁ is a chain paraffin, olefin, A hydroxy represented by paraffin, cycloolefin, phenylene, a sulfur-containing substance, an oxygen-containing substance, a nitrogen-containing substance or an aromatic ring-containing substance thereof, or a halogen-substituted or nitro-substituted substance thereof) It is characterized in that the isothiocyanate compound is polymerized under predetermined conditions.

By the above polymerization, the following chemical formula (1)

[0010]

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(Wherein R ₁ is the same as above. N
Represents an integer. ) Can be obtained.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The sulfur-containing urethane resin according to the present invention can be obtained by polymerizing a hydroxyisothiocyanate compound represented by the following chemical formula (2), HO-R ₁ -NCS (2).

In the above chemical formula (2), R ₁ is a chain paraffin, olefin, cycloparaffin, cycloolefin, phenylene, a sulfur-containing substance, an oxygen-containing substance, a nitrogen-containing substance or an aromatic-ring-containing substance thereof, or Represents either a halogen-substituted product or a nitro-substituted product.

Examples of the hydroxy isothiocyanate compound include 4-hydroxybutyl isothiocyanate, 5-hydroxypentyl isothiocyanate,
Hydroxyhexyl isothiocyanate, 7-hydroxyheptyl isothiocyanate, 8-hydroxyoctyl isothiocyanate, 3-hydroxy-2,2-dimethyl-propyl isothiocyanate, 2- (4-hydroxyphenyl) ethyl isothiocyanate, 2- (2-
(Hydroxyethoxy) ethyl isothiocyanate, 2-
(2-hydroxyethylthio) ethyl isothiocyanate, 4-hydroxyphenyl isothiocyanate and the like.

The polymerization of the hydroxyisothiocyanate compound can be carried out by applying a temperature under non-catalytic conditions. The reaction temperature is between 50 and 250
C is good, and 120 to 180C is preferable. If the reaction temperature is low, the polymerization takes time, and if the reaction temperature is high, the sulfur-containing urethane resin may be decomposed.

The polymerization of the above hydroxyisothiocyanate compound can be carried out in the presence of a polymerization catalyst. The reaction temperature in this case is preferably from room temperature to 200 ° C.
0-150 ° C is preferred. At this time, the reaction can be stopped.

Examples of the polymerization catalyst include an iron catalyst such as iron (III) acetylacetonate, dibutyltin dilaurate,
Examples include tin catalysts such as tin octylate, nickel catalysts such as nickel (II) acetylacetonate, and amine catalysts such as 1,4-diazabicyclo [2,2,2] octane.

By the above polymerization reaction, the following chemical formula (1)
A polymer having at least the structure of
A sulfur-containing urethane resin can be obtained.

[0019]

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Incidentally, R ₁ in the chemical formula (1) is the same as described above. n represents an integer.

The sulfur-containing urethane resin obtained by the present invention can be used for optical materials and the like.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments.

Example 1 5 g of a sulfur-containing urethane resin starting from 5-hydroxypentyl isothiocyanate 5 g of 5-hydroxypentyl isothiocyanate was placed in a Teflon cup and polymerized in an oil bath at about 130 ° C. for 2 days. After completion of the reaction, the mixture was cooled to obtain a sulfur-containing urethane resin. This resin is dissolved in DMF and GP
When the molecular weight was measured at C, the number average molecular weight was 11,900,
The weight average molecular weight was 26,900. IR and N
The MR data was as follows. IR (KBr) 1533 cm ^-1 (ν _{NHC = S} ) ¹³ C NMR (in DMSO) 187.94,18
9.45 ppm (C = S).

Example 2 A sulfur-containing urethane resin starting from 6-hydroxyhexyl isothiocyanate 5 g of 6-hydroxyhexyl isothiocyanate was placed in a Teflon cup and polymerized in an oil bath at about 130 ° C. for 2 days. Was. After completion of the reaction, the mixture was cooled to obtain a sulfur-containing urethane resin. When the molecular weight of the portion of this resin dissolved in DMF was measured by GPC, the number average molecular weight was 12,000 and the weight average molecular weight was 18,700. The IR and NMR data were as follows. IR (KBr) 1528 cm ^-1 (ν _{NHC = S} ) ¹³ C NMR (in DMSO) 187.89,18
9.38 ppm (C = S).

Example 3 Sulfur-containing urethane resin starting from 2- (2-hydroxyethoxy) ethyl isothiocyanate 5 g of 2- (2-hydroxyethoxy) ethyl isothiocyanate was placed in a Teflon cup at about 130 ° C. In an oil bath for 2 days. After completion of the reaction, the mixture was cooled to obtain a sulfur-containing urethane resin. This resin is DMF
And the molecular weight was measured by GPC to find that the number average molecular weight was 7,900 and the weight average molecular weight was 14,100. The IR and NMR data were as follows. IR (KBr) 1535 cm ^-1 (ν _{NHC = S} ) ¹³ C NMR (in DMSO) 188.16,18
9.69 ppm (C = S).

Example 4 A sulfur-containing urethane resin starting from 2- (2-hydroxyethylthio) ethyl isothiocyanate 5 g of 2- (2-hydroxyethylthio) ethyl isothiocyanate was placed in a cup made of Teflon, followed by Polymerization was performed in an oil bath at 130 ° C. for 2 days. After completion of the reaction, the mixture was cooled to obtain a sulfur-containing urethane resin. This resin is DM
F was dissolved in F and the molecular weight was measured by GPC to find that the number average molecular weight was 6,400 and the weight average molecular weight was 7,800. The IR and NMR data were as follows. IR (KBr) 1550 cm ^-1 (ν _{NHC = S} ) ¹³ C NMR (in DMSO) 155.96,15
7.76 ppm (C = S).

Example 5 5 g of a sulfur-containing urethane resin p-hydroxyphenyl isothiocyanate starting from p-hydroxyphenyl isothiocyanate was placed in a Teflon cup and polymerized in an oil bath at about 130 ° C. for 5 days. After completion of the reaction, the mixture was cooled to obtain a sulfur-containing urethane resin. This resin is dissolved in DMF and GP
When the molecular weight was measured at C, the number average molecular weight was 4000 and the weight average molecular weight was 4300. In addition, IR and NMR
Were as follows. IR (KBr) 1512 cm ^-1 (ν _{NHC = S} ) ¹³ C NMR (in DMSO) 180.13 ppm
(C = S).

Example 6 A sulfur-containing urethane resin starting from 2- (4-hydroxyphenyl) ethyl isothiocyanate 5 g of 2- (4-hydroxyphenyl) ethyl isothiocyanate was placed in a Teflon cup at about 130 ° C. In an oil bath for 2 days. After completion of the reaction, the mixture was cooled to obtain a sulfur-containing urethane resin. This resin is DMF
And the molecular weight was measured by GPC to find that the number average molecular weight was 4,200 and the weight average molecular weight was 4,400. Also,
IR and NMR data were as follows. IR (KBr) 1514 cm ^-1 (ν _{NHC = S} ) ¹³ C NMR (in DMSO) 156.23 ppm
(C = S).

Example 7 5 g of a sulfur-containing urethane resin starting from 6-hydroxyhexyl isothiocyanate and 5 g of 6-hydroxyhexyl isothiocyanate and 0.25 g of iron (III) acetylacetonate were placed in a 20 ml eggplant-shaped flask. Polymerization was performed in an oil bath at 60 ° C. for 7 days. After completion of the reaction, the mixture was cooled to obtain a sulfur-containing urethane resin. When this resin was dissolved in DMF and the molecular weight was measured by GPC, the number average molecular weight was 6,500 and the weight average molecular weight was 9,100. The IR and NMR data were as follows. IR (KBr) 1527 cm ^-1 (ν _{NHC = S} ) ¹³ C NMR (in DMSO) 187.80,18
9.27 ppm (C = S).

[0030]

According to the present invention, a sulfur-containing urethane-based resin can be produced by a novel synthesis method, and a novel sulfur-containing urethane-based polymer compound can be obtained.

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4J034 AA01 BA02 CA02 CB01 CC02 CC03 CC12 CC26 CD01 CD03 CD08 CD11 HA01 HA04 HA11 HB02 HB03 HB05 HB11 HC01 HC12 HC22 JA01 KA01

Claims (4)

[Claims] 1. The following chemical formula (1): (Wherein, R ₁ is a chain paraffin, olefin, cycloparaffin, cycloolefin, phenylene, a sulfur-containing material, an oxygen-containing material, a nitrogen-containing material, an aromatic-ring-containing material, a halogen-substituted product thereof, A high-molecular compound having at least one of a group-substituted product, and n represents an integer. 2. The following chemical formula (2): HO—R ₁ —NCS (2) (wherein R ₁ is a chain paraffin, olefin, cycloparaffin, cycloolefin, phenylene, a sulfur-containing substance and an oxygen-containing substance thereof) , A nitrogen-containing compound or an aromatic ring-containing compound, or a halogen-substituted or nitro-substituted product thereof).) A sulfur-containing urethane-based resin obtained by polymerizing a hydroxyisothiocyanate compound represented by the formula: 3. The polymerization according to claim 1, wherein the polymerization is carried out under non-catalytic conditions.
The sulfur-containing urethane-based resin according to claim 2, wherein the reaction is performed at 250 ° C. 4. The sulfur-containing urethane-based resin according to claim 2, wherein the polymerization is carried out at room temperature to 200 ° C. under polymerization catalyst conditions.