JPH09302094A - Thioesterified resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thioesterified resin by reacting a multi-functional acid halide, in the presence of a tertiary amine, with a thiol obtained by the ring opening polymerization and addition reaction of a dithiocarbonated multifunctional compound with an active hydrogen compound. SOLUTION: A multifunctional compound having at least one five-membered ring dithiocarbonate group represented by formula I (wherein R<1> to R<3> are each a lower alkyl), such as bisphenol-A bifunctional dithiocarbonate, is dissolved in an aprotic solvent, such as tetrahydrofuran, and an active hydrogen compound, such as benzylamine, is added thereto in an amount of about 1-2.5 equivalents for each equivalent of the dithiocarbonate group, the resultant mixture being submitted to reaction for about 24 hours at room temperature. Then, about 1-4 equivalents of a tertiary amine, such as triethylamine and subsequently about 0.5-1.5 equivalents of a multifunctional acid halide, such as terephthalic acid dichloride, are added to the resultant mixture to submit it to reaction for about 24 hours at room temperature. Thereafter, the product is taken out to obtain a thioesterified resin having structural units of formula II (wherein R<4> is an active hydrogen compound residue; B is a residue other than the carboxyl group of a multifunctional carboxylic acid).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thioester-containing resin useful as an optical material having a high refractive index or a substitute material for polysulfide rubber used for hoses, shock absorbers, belts, packings and the like.

[0002]

BACKGROUND OF THE INVENTION A 5-membered ring dithiocarbonate derivative is used as a photosensitive resin or a polymer cross-linking agent because of its high reactivity. When it has an aromatic ring, sulfur and aromatic ring are introduced. Since it can increase the refractive index, it is also used as an optical material. On the other hand, polysulfides are known as polysulfide synthetic rubbers having a wide range of properties such as liquid-soft rubber-hard rubber. As polysulfide rubber, oil resistance, aging resistance,
Taking advantage of its excellent ozone resistance and corona resistance,
It is used for fuel tanks, fuel hoses, adhesives, sealants, etc. The properties of such a polysulfide are adjusted by changing the type of the monomer or the degree of polymerization, but one type of resin cannot satisfy all the performances. For example, if the processability is insufficient. The deficiency was compensated by blending an epoxy resin or a polysulfide having a different polymerization degree. In addition, since the bond is a disulfide bond, it is difficult to obtain a film exhibiting toughness because the film exhibits high flexibility but poor hardness.

[0003]

An object of the present invention is to provide a novel thioester-containing resin exhibiting toughness.

[0004]

The present invention provides a compound represented by the general formula (I):

[0005]

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Wherein R ¹ , R ² and R ³ are the same or different and each represent hydrogen or lower alkyl, or R ¹ and R ² are saturated together with two adjacent carbon atoms. Represents a hydrocarbon ring, R ⁴ represents an active hydrogen compound residue, and B represents a residue excluding two carboxyl groups of a polyfunctional carboxylic acid). Regarding

The present invention also has the general formula (II)

[0008]

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(Wherein R ¹ , R ² and R ³ have the same meanings as defined above), a polyfunctional compound having at least one 5-membered dithiocarbonate group and an active hydrogen compound are developed. The present invention relates to a thioester-containing resin represented by the above general formula (I) obtained by reacting a thiol produced by a cyclopolyaddition reaction with a polyfunctional acid halide compound in the presence of a tertiary amine, and a method for producing the same.

[0010]

[Chemical 6]

(Wherein R ¹ , R ² , R ³ , R ⁴ and B
Represents the same meaning as described above) In the definition of each group of the general formula (I) and the general formula (II),
The lower alkyl has a straight or branched carbon number of 1 to
12 of, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-
Butyl, pentyl, isoamyl, hexyl, heptyl,
Examples include octyl, nonyl, decyl, undecyl and dodecyl. The saturated hydrocarbon ring has 5 to 12 carbon atoms.
Examples thereof include monocyclic hydrocarbon rings such as cyclopentane, cyclohexane, cycloheptane, cyclodecane, and cycloundecane, and polycyclic hydrocarbon rings such as norbornane, bornane, menthane, norpinane, and pinane.

Examples of the polyfunctional carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and other bifunctional carboxylic acids, trimellitic acid, Examples include trifunctional carboxylic acids such as tricarballylic acid. Examples of the polyfunctional compound having one or more 5-membered ring dithiocarbonate groups include 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2. -Epoxydecane, 1,2-epoxydodecane, 1,2-epoxyhexadecane, 1,2
-Epoxy-5-hexene, 4- (2,3-epoxyhexyloxy) phenyl-4- (decyloxy) benzoate, 7,8-epoxy-2-methyloctadecane, 2,
Monofunctional dithiocarbonate compounds obtained by dithiocarbonating monofunctional epoxy compounds such as 3-epoxynorbornene, 2,3-epoxypropylbenzene and N- (2,3-epoxypropyl) phthalimide with carbon disulfide, bisphenol A, Obtained by reacting polychlorophenol such as bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, catechol, resorcin, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, hydroquinone and epichlorohydrin Multifunctional dithiocarbonate compound obtained by dithiocarbonating polyhydric glycidyl ether with carbon disulfide, glycerin, neopentyl glycol, diethyl propane diol, butyl ethyl propane di Glycidyl group such as polyfunctional dithiocarbonate compound and glycidyl (meth) acrylate obtained by dithiocarbonating polyhydric glycidyl ether obtained by reacting polyhydric alcohol such as alcohol with epichlorohydrin Polymer compounds such as copolymers of dithiocarbonate group-containing acrylic monomers obtained by dithiocarbonating an acrylic monomer with carbon disulfide and other copolymerizable monomers, and the like, among others, a polyfunctional dithiocarbonate compound or Polymer compounds are preferred.

The active hydrogen compound may be any compound as long as it undergoes a nucleophilic addition reaction to the thiocarbonyl group of the 5-membered ring dithiocarbonate group, but an amino compound is preferred. The amino compound is a compound having a primary or secondary amino group, for example, ammonia, methylamine, ethylamine, propylamine, butylamine, isobutylamine, sec-butylamine, hexylamine, octylamine, 1,2-dimethylpropylamine. , 2-ethylhexylamine, allylamine, 3
-Aliphatic primary or secondary amines such as methoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, dipropylamine, dibutylamine, diisobutylamine, dioctylamine, bis (2-ethylhexyl) amine, pyrrolidine, Piperazine,
Alicyclic secondary amines such as piperidine, morpholine and thiomorpholine, benzylamine, dibenzylamine, β
-Aromatic amines such as phenethylamine, basic nitrogen-containing heterocyclic compounds such as pyrrole and imidazole, 2-hydroxymethylaminoethanol, 3-aminopropanol,
Hydroxyamines such as 2-aminopropanol, monoethanolamine and diethanolamine, ethylaminoethylamine, 1,2-diaminopropane, 1,3-diaminopropane, methylaminopropylamine, 2- (2
-Hydroxyethylamino) propylamine, bis (3
-Aminopropyl) ether, 1,3-bis (3-aminopropoxy) -2,2-dimethylpropane, 1,4-
Preferable examples include difunctional amines such as diaminobutane and 1,6-hexamethylenediamine, and trifunctional amines such as dicyandiamide. The amino compound is 5
When reacting with a polyfunctional compound having one or more membered ring dithiocarbonate groups, the dithiocarbonate group may be reacted with 0.
It is preferable to add 5 to 3 equivalents, preferably 1 to 2.5 equivalents.

Examples of the tertiary amine include trimethylamine, triethylamine, tributylamine, trioctylamine and the like. Among them, triethylamine is particularly preferable. The compounding amount in the reaction system is 0.5 to 5 equivalents, preferably 1 to the thiol group produced.
~ 4 equivalents. As the polyfunctional acid halide compound,
Malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, maleic acid dichloride, fumaric acid dichloride, phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, malonic acid dibromide, succinic acid dibromide, glutaric acid dibromide , Adipic acid dibromide, maleic acid dibromide, fumaric acid dibromide,
Bifunctional acid halide compounds such as phthalic acid dibromide, isophthalic acid dibromide and terephthalic acid dibromide, trifunctional compounds such as trimellitic acid trichloride, tricarballylic acid trichloride, trimellitic acid tribromide and tricarballylic acid tribromide Acid acid halide compounds and the like. The amount of the thiol to be reacted is 0.1 to 3 equivalents, preferably 0.5 to 1.5 equivalents, relative to the thiol produced.

In the present invention, the solvent may or may not be used, but when it is used, an aprotic solvent is preferable, for example, tetrahydrofuran (THF), dioxane, dioxolane, trioxane, diethyl cellosolve, dibutyl cellosolve, diethyl carbyl. Tol, ether solvent such as dibutyl carbitol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvent such as diethyl ketone, acetonitrile, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and the like, preferably THF, acetone, Ethyl acetate or the like is used. The amount of the aprotic solvent used is not particularly limited, but is 0.1% based on the total solid content.
-100 parts by weight are preferred.

The reaction temperature, reaction time and reaction pressure are not particularly limited, but the reaction temperature is 0-10.
It is preferable that the reaction temperature is 0 ° C., the reaction time is 2 to 60 hours, and the pressure is normal pressure or slight pressurization. When the solvent is used after the completion of the reaction, the solvent can be removed by heating, removal under reduced pressure or the like. It can also be purified by washing, drying and the like.

Next, physical properties of the thioester-containing resin of the present invention will be described with reference to test examples.

Test Example 1 Tensile Test The polysulfide resin obtained in Example 1 described later was punched out in a dumbbell shape with a film thickness of 300 μm, and a tensile test was carried out at a pulling speed of 10 mm / min, a chuck distance of 60 mm, and 25 ° C. The results are shown in Table 1.

[0019]

[Table 1]

As is clear from Table 1, the thioester-containing resin of the present invention has excellent tensile strength.
Hereinafter, the present invention will be described in more detail with reference to Examples.

[0021]

【Example】

Example 1 100.0 g (0.11 mol) of bisphenol A type bifunctional glycidyl ether (obtained by reacting bisphenol A and epichlorohydrin; commercial product) and 5.0 g (0.06 mol) of lithium bromide were added. It was dissolved in 1 L of THF at room temperature, and 126.6 g (1.
66 mol) was added, and the mixture was reacted at 45 ° C. for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 600 ml of chloroform, 400 ml of acetone and 1 L of water were added to the residue to separate the layers. The extracted organic layer is saturated saline solution 8
It was washed with 00 ml and dried over 60 g of anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel chromatography to give 43.0 g (0.04 mol) of bisphenol A type bifunctional dithiocarbonate.
I got In a 50 ml reaction vessel equipped with a stirrer and a nitrogen introducing tube, 1 mmol of the bisphenol A type bifunctional dithiocarbonate compound obtained above was dissolved in 5 ml of THF at room temperature, and 2 equivalents of benzylamine (vs. dithiocarbonate) Group) was added, and the mixture was reacted under a nitrogen atmosphere at room temperature for 24 hours. Next, triethylamine (3 equivalents (with respect to thiol)) was added without isolation, and terephthalic acid dichloride (1 mmol) was added thereto.
A time reaction was performed. After the reaction, 100 ml of methanol
Then, the desired thioester-containing resin (A) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.47-1.70 (br,
5H), 3.43-3.70 (m, 3H), 4.08-4.75 (m, 6H), 5.88-6.10
(m, 1H), 6.60-8.00 (m, 20H) ¹³ C-NMR (CDCl ₃ ) δ (ppm): 31.0, 42.1, 49.7, 67.8, 7
7.5, 112.4, 128.0, 136.8, 143.5, 156.0, 189.9 IR ν (cm ^-1 ): 3370, 2920, 1640, 1500, 1160, 880 Resin yield obtained, number average molecular weight (Mn), molecular weight distribution (Mw) / Mn) is shown in Table 2.

[0023]

[Table 2]

[0024]

According to the present invention, a thioester-containing resin having excellent tensile strength is provided.

Claims (6)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ , R ² and R ³ are the same or different,
Hydrogen or lower alkyl, or R ¹ and R ² together with two adjacent carbon atoms each represent a saturated hydrocarbon ring; R ⁴ represents an active hydrogen compound residue;
Represents a residue excluding two carboxyl groups of a polyfunctional carboxylic acid), and a thioester-containing resin having a structural unit represented by 2. The thioester-containing resin according to claim 1, wherein the active hydrogen compound is a compound having a primary or secondary amino group. 3. A compound represented by the general formula (II): (In the formula, R ¹ , R ² and R ³ have the same meanings as described above)
The thiol produced by the ring-opening polyaddition reaction of a polyfunctional compound having one or more 5-membered dithiocarbonate groups represented by and an active hydrogen compound is reacted with a polyfunctional acid halide compound in the presence of a tertiary amine. Claim 1 obtained by
The thioester-containing resin described. 4. The thioester-containing resin according to claim 3, wherein the active hydrogen compound is a compound having a primary or secondary amino group. 5. A compound of the general formula (II) (In the formula, R ¹ , R ² and R ³ have the same meanings as described above)
The thiol produced by the ring-opening polyaddition reaction of a polyfunctional compound having one or more 5-membered dithiocarbonate groups represented by and an active hydrogen compound is reacted with a polyfunctional acid halide compound in the presence of a tertiary amine. The method for producing a thioester-containing resin according to claim 1, wherein 6. The method for producing a thioester-containing resin according to claim 5, wherein the active hydrogen compound is a compound having a primary or secondary amino group.