JP2001240661A - Functional polyester polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester polymer excellent in heat resistance, low water- absorption and optical characteristics, and further excellent in moldability. SOLUTION: This polyester polymer is obtained by condensing a diol component comprising at least one kind of tricyclo[5.2.1.02,6]decanedimethanols represented by formula (1) (wherein, two hydroxymethyl groups are bonded to the carbon atoms constituting the tricyclo[5.2.1.02,6]decane ring; and the carbon atoms constituting the ring may have other substituents), with a carboxylic acid. The number average molecular weight of the polyester polymer is e.g. 1,000-150,000, preferably about 3,000-100,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester polymer and a method for producing the same, and more particularly, to a polymer having heat resistance, low water absorption, small optical anisotropy and excellent moldability. The present invention relates to a polyester polymer and a method for producing the same. This polyester polymer is useful as an optical material, an electronic information material, a medical device material, and the like.

[0002]

2. Description of the Related Art In recent years, research and development using plastics as optical materials, electronic information materials, medical device materials and the like have been vigorously conducted. In optical materials and electronic information materials,
It is required to have low optical anisotropy in addition to transparency, low water absorption and heat resistance. In addition, medical device materials are required to have blood compatibility, mechanical strength, hydrolysis resistance, and the like.

[0003] As optical materials, polymethyl methacrylate, polycarbonate, amorphous polyolefin and the like are used. However, although polymethyl methacrylate is excellent in transparency and small in optical anisotropy, it has high hygroscopicity, so that deformation such as warpage is likely to occur, and heat resistance is not sufficient. Although polycarbonate has excellent heat resistance, it has a large optical anisotropy. Amorphous polyolefins have low optical anisotropy and are excellent in heat resistance, but have problems in moldability, adhesiveness and the like.

On the other hand, attempts have been made to apply polyester as an optical material or an electronic information material. For example, JP-A-1-138225 discloses a polyester resin using a diol or dicarboxylic acid having an aromatic ring in a side chain. JP-A-2-38428 discloses a polyester copolymer using diphenyldicarboxylic acid as a dicarboxylic acid component. JP-A-11-35665 discloses a polyester comprising a 2,2-norbornane dimethanol derivative and terephthalic acid. However, these resins are not necessarily sufficient in terms of heat resistance, low water absorption, and optical characteristics.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel polyester polymer having excellent heat resistance, low water absorption, excellent optical properties and excellent moldability, and a process for producing the same. is there.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a polyester resin having a specific structure has excellent heat resistance, low water absorption, optical properties and moldability. Thus, the present invention has been completed.

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

Embedded image (Wherein the two hydroxymethyl groups are tricyclo [5.
2.1.0 ^2,6 ] decane ring. A diol component containing at least one tricyclo [5.2.1.0 ^2,6 ] decane dimethanol represented by the following formula: wherein the carbon atom constituting the ring may have another substituent); Provided is a polyester polymer obtained by condensation with a dicarboxylic acid component.

The present invention also relates to a diol component containing at least one kind of tricyclo [5.2.1.0 ^2,6 ] decanedimethanol represented by the above formula (1), a dicarboxylic acid component or a diol component thereof. Provided is a method for producing a polyester polymer, which comprises polycondensing a reactive derivative.

As the diol component, the following formulas (1a) to
(1c)

Embedded image (Wherein the carbon atoms constituting the ring may have a substituent), and tricyclo [5.2.1.0 ^2,6 ] decane-3,8-, 3,9- and At least one tricyclo [5.2. Selected from 4,8-dimethanols;
1.0 ^2,6 ] diol components including decandimethanols can be used.

[0010]

DETAILED DESCRIPTION OF THE INVENTION At least one tricyclo [5.2.1.0 ^2,6 ] decane dimethanol represented by the above formula (1) is included in the diol component constituting the polyester polymer of the present invention. Kinds are included.

The two hydroxymethyl groups shown in the formula are bonded to any carbon atom (bridgehead or non-bridgehead carbon atom) constituting the tricyclo [5.2.1.0 ^2,6 ] decane ring. May be. For example, tricyclo [5.2.
1.0 ^2,6 ] when the decane ring is divided into a norbornane ring and a cyclopentane ring, both of the hydroxymethyl groups may be bonded to a carbon atom on the norbornane ring side;
Two hydroxymethyl groups may both be bonded to a carbon atom on the cyclopentane ring side. Also, one hydroxymethyl group is bonded to a carbon atom on the norbornane ring side,
The other hydroxymethyl group may be bonded to the carbon atom on the cyclopentane ring side. These regioisomers can be used alone or in combination of two or more. The tricyclo [5.2.1.0 ^2,6 ] decane dimethanol represented by the formula (1) may have an endo-form and an exo-form. In the present invention, one or a mixture of these may be used. Either can be used.

In the formula (1), the carbon atom constituting the ring (the carbon atom at the bridgehead or non-bridgehead) may have another substituent in addition to the two hydroxymethyl groups. Examples of such a substituent include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, and decyl groups (eg, C _1-10 alkyl groups, preferably C _1-4 alkyl groups); Cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl and naphthyl groups; alkoxy groups such as methoxy, ethoxy and isopropoxy groups (for example, C
_1-4 alkoxy group); methoxycarbonyl, ethoxycarbonyl, alkoxycarbonyl groups such as isopropoxycarbonyl group (e.g., C _1-4 alkoxy - carbonyl group); a hydroxyl group; an acetyl, propionyl, butyryl, acyl groups such as benzoyl group A carboxyl group; a nitro group; a substituted or unsubstituted amino group; a halogen atom;

The tricyclo [5.2.
1.0 ^2,6 ] decandimethanols, the above-mentioned formula (1
a) Tricyclo [5.2.1.
0 ^2,6 ] decane-3,8-dimethanols, tricyclo [5.2.1.0 ^2,6 ] decane-3,9-dimethanols and tricyclo [5.2.1.0 ^2,6 ] Decane-4,
8-dimethanols are preferred. Equations (1a) to (1
In c), the substituents that the carbon atoms constituting the ring may have are the same as described above.

The tricyclo [5.2.
1.0 ^2,6 ] decane dimethanol can be obtained by a known or conventional method.

In the present invention, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol represented by the formula (1) is
Only one kind of compound may be selected and used, or a plurality of compounds may be used in combination. As the diol component constituting the polyester polymer of the present invention, another diol component is used in combination with the tricyclo [5.2.1.0 ^2,6 ] decanedimethanol represented by the above formula (1). You can also. Examples of such a diol component include diols used as raw materials for general polyesters, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane. Aliphatic diols such as diols and neopentyl glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,1-cyclohexanedimethanol, 2-methyl-1,1 -Cyclohexanediol, hydrogenated bisphenol A, 2,2-
Norbornane dimethanol, 3-methyl-2,2-norbornane dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 2,6-norbornane dimethanol, perhydro-1,4: 5,8
-Dimethanonaphthalene-2,3-dimethanol, adamantane dimethanol, 1,3-dimethyl-5,7-adamantane dimethanol, 1,3-adamantanediol, 1,3-dimethyl-5,7-adamantanediol, etc. Alicyclic diols; hydroquinone, catechol, resorcinol, naphthalene diol, xylylene diol,
Aromatic diols such as bisphenol A, an ethylene oxide adduct of bisphenol A, bisphenol S, and an ethylene oxide adduct of bisphenol S; and ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, and dipropylene glycol. The above diol components can be used alone or in combination of two or more.

The proportion of tricyclo [5.2.1.0 ^2,6 ] decanedimetal represented by the above formula (1) in all diol components constituting the polyester polymer of the present invention can be arbitrarily changed. However, usually 1 to 100 mol%, preferably 5 to 100 mol%, more preferably 10 to 1 mol%
It is about 00 mol%.

The dicarboxylic acid component constituting the polyester polymer of the present invention is not particularly limited as long as it is generally used as a raw material for polyester.
Terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,
4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-diphenoxyethane-4 ', 4 "-dicarboxylic acid, anthracenedicarboxylic acid, Aromatic dicarboxylic acids such as 2,5-pyridinedicarboxylic acid and diphenylketone dicarboxylic acid; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid; 1,4-cyclohexanedicarboxylic acid 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,
2,3-norbornanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, 2,6-norbornanedicarboxylic acid, perpidro-1,4: 5,8-dimethanonaphthalene-2,3-dicarboxylic acid, adamantanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 1,3-dimethyl-5,7-adamantanedicarboxylic acid; These dicarboxylic acid components can be used alone or in combination of two or more.

The polyester polymer of the present invention is preferably a polyester polymer which does not contain a component having a polymerizable double bond as a dicarboxylic acid component. Particularly, a dicarboxylic acid component having no polymerizable double bond and a diol Saturated polyester consisting of components (thermoplastic polyester)
It is preferred that

The number average molecular weight of the polyester polymer of the present invention is, for example, about 1,000 to 150,000, preferably about 3,000 to 100,000. The reduced viscosity of the polyester polymer of the present invention, in terms of mechanical properties when formed into a molded product, has a concentration of 1 in a phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 4/6).
The measured value under the conditions of 2 g / dl and a temperature of 35 ° C.
It is preferably about 5 or more.

The polyester polymer of the present invention comprises: a diol component containing at least one component selected from tricyclo [5.2.1.0 ^2,6 ] decanedimetal represented by the formula (1); It can be produced by polycondensing a dicarboxylic acid component or a reactive derivative thereof.

As the reactive derivative of the dicarboxylic acid component, for example, dicarboxylic acid esters, dicarboxylic acid anhydrides, dicarboxylic acid halides (dicarboxylic acid chlorides and the like) and the like can be used. Dicarboxylic esters, dicarboxylic anhydrides, and dicarboxylic acid halides can be derived from the corresponding dicarboxylic acids by conventional methods.

As an embodiment of the production of the polyester polymer of the present invention, a general polyester production method can be applied. For example, when a free dicarboxylic acid or dicarboxylic anhydride is used as a raw material, the diol component and the dicarboxylic acid or dicarboxylic anhydride are placed in a reactor and heated, and water generated by the reaction is distilled out of the system. The polyester polymer can be produced by removing the mixture. This reaction does not necessarily require a catalyst, but the use of a catalyst can accelerate the reaction. As the catalyst, for example, alkali metal, alkaline earth metal, zinc,
Examples include acetates, carbonates, hydroxides, and alkoxides of metals such as titanium, cobalt, and manganese. The reaction temperature is about 120 to 300 ° C, preferably 160 to 300 ° C.
It is about ° C. The reaction pressure is usually normal pressure, but the esterification reaction may be performed under reduced pressure in order to promote the removal of water and excess diol components. The molar ratio of the diol component to the dicarboxylic acid or dicarboxylic anhydride may be about 1, but an excess of the diol component may be used to obtain a high molecular weight polyester.

When a dicarboxylic acid ester is used as a raw material, a polyester polymer can be produced by charging a diol component, a dicarboxylic acid ester, and a catalyst into a reactor and distilling off alcohol produced by the reaction outside the system. . As the dicarboxylic acid ester, methyl ester, ethyl ester, propyl ester, butyl ester and the like of dicarboxylic acid can be used, but methyl ester is particularly preferable in view of easiness of reaction and cost. Examples of the catalyst include alkali metals, alkaline earth metals, zinc, lead, titanium, cobalt, manganese, tin, antimony, germanium and other metal carboxylate, carbonate, hydroxide, alkoxide, oxide and the like. Is mentioned. The reaction temperature is about 120 to 300 ° C., preferably 16
It is about 0 to 300 ° C. The reaction pressure may be normal pressure, but the esterification reaction may be performed under reduced pressure in order to promote the removal of alcohol. The molar ratio of the diol component to the dicarboxylic acid ester may be about 1, but an excess amount of the diol component may be used to obtain a high molecular weight polyester.

As a method for obtaining a polyester polymer by using a dicarboxylic acid halide such as a dicarboxylic acid chloride as a raw material, (i) reacting a diol component with a dicarboxylic acid halide at a high temperature without a solvent to form a halogen (Ii) a method in which a diol component and a dicarboxylic acid halide are reacted in a solvent at a low temperature to distill off the generated hydrogen halide or neutralize with a basic substance. . The reaction temperature can be appropriately selected from the range of about 0 to 280 ° C.

The solvent used in the method (ii) is not particularly limited as long as it is inert to the reaction.
Halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, monochlorobenzene and trichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; tetrahydrofuran, dioxane;
Ethers such as dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile;
Examples include amides such as dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxides such as dimethylsulfoxide; imidazolines such as 1,3-dimethyl-2-imidazoline; and hexanemethylphosphoramide. it can. Examples of the basic substance include tertiary amines such as triethylamine, tributylamine, and N, N-dimethylaniline; and basic nitrogen-containing compounds such as pyridine, α-picoline, β-picoline, γ-picoline, and quinoline. Heterocyclic compounds; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkali metal salts such as sodium acetate, sodium carbonate, sodium hydrogen carbonate, potassium acetate, potassium carbonate and the like. In addition, the said N-methyl-2-
Solvents such as pyrrolidone also function as basic substances.

The polyester polymer produced by the polymerization can be isolated by a conventional method such as filtration, concentration, precipitation, crystallization, and solidification by cooling.

[0027]

The polyester polymer of the present invention has a bulky alicyclic structure and is excellent in heat resistance, low water absorption, optical properties and moldability. Therefore, optical disks, lenses,
It is useful as various optical and electronic information materials such as optical connectors, medical infusion kits, medical instrument materials such as catheters, syringes, and vacuum blood collection tubes.

[0028]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 In a 50 ml flask, 2.09 g of 1,4-cyclohexanedicarboxylic acid chloride and 10 ml of dried monochlorobenzene were charged under dry nitrogen, and tricyclo [5.2. A mixed solution of 1.96 g of [1.0 ^2,6 ] decanedimethanol and 5 ml of dry pyridine was added dropwise over 5 minutes. After the completion of dropping, the mixed solution is heated to 80 ° C.
For 2 hours. After the polymerization is completed, the reaction mixture is mixed with 500
The resulting polymer was precipitated by dropping little by little into ml of methanol. After filtering and washing this polymer,
After vacuum drying, 3.32 g of a white polyester polymer was obtained.
Obtained. The number average molecular weight and molecular weight distribution (Mw / Mn) of the obtained polymer were measured by GPC.
They were 2,800 and 3.25. The Tg (glass transition temperature) of this polymer and the 5% thermogravimetric loss temperature in nitrogen were measured by DSC (differential scanning calorimetry) and TG-DTA.
(Thermal balance), as a result, 87.9 ° C and 41
5.2 ° C.

 ──────────────────────────────────────────────────続 き Continued from the front page F term (reference) 4J029 AA03 AB01 AB04 AD01 AE04 AE05 AE06 BD10 CA01 CA04 CA05 CA06 CB04A CB05A CB06A CB10A CC06A CC09 CD03 CD07 CE04 CF07 CF08 CF15 DA13 DB07 JA081 JA091 J111 J03 J01JF121F JF161 JF181 JF321 JF541 JF571

Claims (6)

[Claims] [Claim 1] The following formula (1) (Wherein the two hydroxymethyl groups are tricyclo [5.
2.1.0 ^2,6 ] decane ring. A diol component containing at least one tricyclo [5.2.1.0 ^2,6 ] decane dimethanol represented by the following formula: wherein the carbon atom constituting the ring may have another substituent); A polyester polymer obtained by condensation with a dicarboxylic acid component. 2. The following formulas (1a) to (1c): (Wherein the carbon atoms constituting the ring may have a substituent), and tricyclo [5.2.1.0 ^2,6 ] decane-3,8-, 3,9- and At least one tricyclo [5.2. Selected from 4,8-dimethanols;
1.0 ^2,6 ] obtained by condensation of a diol component containing decane dimethanols with a dicarboxylic acid component.
The polyester polymer as described in the above. 3. A compound having a number average molecular weight of 1,000 to 150,0.
The polyester polymer according to claim 1, wherein the number is 00. 4. The number average molecular weight is from 3,000 to 100,0.
The polyester polymer according to claim 1, wherein the number is 00. 5. The following formula (1) (Wherein the two hydroxymethyl groups are tricyclo [5.
2.1.0 ^2,6 ] decane ring. A diol component containing at least one tricyclo [5.2.1.0 ^2,6 ] decane dimethanol represented by the following formula: wherein the carbon atom constituting the ring may have another substituent); A method for producing a polyester polymer, comprising polycondensing a dicarboxylic acid component or a reactive derivative thereof. 6. The following formulas (1a) to (1c): (Wherein the carbon atoms constituting the ring may have a substituent), and tricyclo [5.2.1.0 ^2,6 ] decane-3,8-, 3,9- and At least one tricyclo [5.2. Selected from 4,8-dimethanols;
1.0 ^2,6 ] The process for producing a polyester polymer according to claim 5, wherein a diol component containing decane dimethanols is polycondensed with a dicarboxylic acid component or a reactive derivative thereof.