JP2001114883A - Method for producing biodegradable aliphatic polyester and/or copolymer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a hardly colored biodegradable aliphatic polyester and/or a copolymer thereof, having usefulness as a medical material or a substitute of a general purpose resin, further having sufficiently drawn out characteristics originally possessed by the biodegradable aliphatic polyester and/or the copolymer thereof at a short time. SOLUTION: This method for producing the biodegradable aliphatic polyester and/or the copolymer thereof comprises using a main raw material having the total content of the organic impurities included in the main raw material within a specified amount, carrying out the polymerization reaction in the simultaneous presence of both of one or more kinds of tin compounds, and one or more kinds of acidic organic sulfone compounds as polymerization catalysts, and carrying out at least a part of the polymerization reaction by a solid phase polymerization reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a biodegradable aliphatic polyester and / or a copolymer thereof. Specifically, in addition to having usefulness as a medical material or a general-purpose resin substitute or a medical material, in addition to using a main raw material having a total content of organic impurities of a specific amount or less, in the presence or absence of a reducing agent, A biodegradable aliphatic compound that performs a polymerization reaction in the presence of at least one or more tin compounds and one or more acidic organic sulfone compounds at the same time as a polymerization catalyst, and performs at least a part of the polymerization reaction by a solid-state polymerization reaction The present invention relates to a method for producing a polyester and / or a copolymer thereof.

[0002]

2. Description of the Related Art Plastics are widely used in every field of daily life because they are light and easy to process and can be obtained at low cost. They have greatly contributed to technological progress in various industrial fields. I have. However, in addition to increasing the amount of plastic waste that becomes unnecessary after use, it is hardly decomposed in the natural environment, so that there is a problem that it remains semi-permanently even if it is buried. BACKGROUND ART In recent years, environmental problems such as spoiled landscapes and destruction of the living environment of terrestrial and marine life due to discarded plastics have occurred worldwide. To address such problems, a plastic recycling system such as a separate waste collection system, a returnable system, or a deposit system has been considered, but the realization of such a system has not fully penetrated to the end user. Is the current situation.

On the other hand, biodegradable plastics having a biodegradable function that is degraded by enzymes of microorganisms that are ubiquitous in nature have recently attracted attention and have the potential to solve the aforementioned environmental problems. At present, many environmentally friendly products using this biodegradable plastic have been proposed. For example, in the field of packaging containers, it has been applied to beverages, hard containers such as shampoo bottles, soft packaging materials such as snacks, and liquid containers made of composite materials combined with paper. Furthermore, in other fields, it is widely applied to tableware, stationery, and miscellaneous goods, and many of them are commercialized. Some municipalities use biodegradable plastic garbage bags to collect household garbage.

[0004] Biodegradable plastics having biodegradability include resin compositions obtained by mixing natural substances such as polysaccharides and saccharides such as cellulose and starch with other plastics, resins synthesized by microorganisms, There is a synthetic resin. Biodegradable plastics other than those utilizing (poly) saccharides such as starch, chitin, chitosan or bacterial cellulose are mainly composed of aliphatic polyesters. As aliphatic polyesters produced by microorganisms, those having a hydroxyalkanoate unit are known, and 3-hydroxybutyrate / 3-hydroxyvalerate is commercially available under the trade name "Biopol" (manufactured by Monsanto). Chemically synthesized polycaprolactone,
In addition to polybutylene succinate, there is polylactic acid made from lactic acid.

[0005] These polyesters are degraded in a natural environment without causing any harm, and are not only biodegradable to be eventually converted into water and carbon dioxide by microorganisms, but also mechanically and mechanically. It has excellent physical and chemical performance, and is a plastic that has recently received special attention in various fields such as medical materials and general-purpose resin substitutes.

A method for producing such a biodegradable plastic is, for example, in the case of polylactic acid, a method in which ring-opening polymerization is carried out via lactide, which is a cyclic dimer of lactic acid (Japanese Patent Application Laid-open No. Sho 56 (1988)).
No. 45920) and a method of direct dehydration polycondensation (JP-A-59-96123, JP-A-61-02852).
No. 1) is known.

Further, another polymerization method is disclosed in
No. 255488 discloses a low-molecular-weight homopolymer or copolymer of L- and / or D-lactic acid, which is a powder or a particle and has a crystallinity of 10% or more as measured by X-ray diffraction, in an inert gas atmosphere. Alternatively, a technique is disclosed in which the molecular weight is increased by heating under a vacuum at a temperature higher than the glass transition temperature of the polymer and lower than the melting temperature of the polymer.

In any of the production methods, like any other plastic, the properties of the obtained plastic are as follows: a) molecular weight and molecular weight distribution; b) types and contents of impurities not involved in the polymerization reaction; c) polymerization. Types and contents of impurities involved in the reaction; d) defects in the chemical structure of the main chain caused by the incorporation of impurities involved in the polymerization reaction into the main chain skeleton; e) side reactions caused by the impurities; and Even so, it is greatly influenced by factors such as unexpected side reactions that occur during production, and also affects quality. Among these groups of factors, a) to e) are factors relating to impurities contained in the raw material. In other words, the characteristics of the plastic greatly depend on the purity of the raw material in the production method.

[0009] Therefore, in order to bring out sufficient properties of plastics, and to maintain and improve the quality of products, the raw materials used in the production of plastics must be refined. However, the biodegradable aliphatic polyester and / or its copolymer described in the present invention and the polyester, polyamide, polycarbonate, polyether and polyimide other than the present invention have been generally used in the production method of a condensation polymer. With respect to the purity of the raw materials used, or the impurities contained therein, or after clearly showing the relationship between the impurities contained and the properties of the obtained polymer, there are almost no examples showing the production method, and in the present invention, None of the biodegradable aliphatic polyesters discussed are at all. Further, the effect of the impurities was not clarified.

Various compounds have been proposed as polymerization catalysts for use in synthesizing polyesters. However, there is no clear example showing that two or more specific compounds are simultaneously used in a polymerization reaction.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a biodegradable aliphatic polyester and / or a copolymer thereof, which is useful as a medical material or a substitute for a general-purpose resin. An object of the present invention is to provide a method for efficiently producing a biodegradable aliphatic polyester and / or a copolymer thereof with less coloring.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have used a main raw material having a total content of organic impurities of a specific amount or less, and By conducting a polymerization reaction in the presence or absence of at least one or more tin compounds and one or more acidic organic sulfone compounds simultaneously as a polymerization catalyst, a high molecular weight biodegradable fat can be obtained in a short time. An aliphatic polyester and / or a copolymer thereof was obtained, and further, the optical properties of the biodegradable aliphatic polyester and / or the copolymer were improved and found to be extremely excellent, thereby completing the present invention.

That is, the present invention provides: 1) using a main raw material having a total content of organic impurities having 1 to 10 carbon atoms contained in the main raw material of not more than 0.2 mol% with respect to the main raw material. At least one tin compound selected from tin, tin oxide, and tin chloride in the presence or absence of a reducing agent, and at least one acidic compound having a reciprocal value of an acid dissociation constant of 3.66 or less. A method for producing a biodegradable aliphatic polyester and / or a copolymer thereof, wherein a polymerization reaction is carried out in the presence of both an organic sulfone compound and a polymerization catalyst at the same time, and at least a part of the polymerization reaction is carried out by a solid-state polymerization reaction 2) The total content of organic impurities having 1 to 10 carbon atoms contained in the main raw material is 0.2 mol% or less in total with respect to the main raw material, and the number of carbon atoms contained in the main raw material is 1 From 10 organic impurities Wherein the contents of pyruvic acid, 2-hydroxy-n-butyric acid, and ethyl lactate are 0.06 mol% or less, 0.02 mol% or less, and 0.02 mol% or less, respectively, based on the main raw material. Using the main raw material that is
In the presence or absence of a reducing agent, at least one or more tin compounds selected from tin, tin oxide, and tin chloride, and one or more acidic organic compounds having a reciprocal value of an acid dissociation constant of 3.66 or less. A method for producing a biodegradable aliphatic polyester and / or a copolymer thereof, wherein a polymerization reaction is carried out in the presence of both a sulfone compound and a polymerization catalyst at the same time, and at least a part of the polymerization reaction is carried out by a solid-state polymerization reaction. And 3) the biodegradable aliphatic polyester and / or a copolymer thereof has the formula (1)

[0014]

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And one or more formulas (2)

[0016]

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(In the formulas (1) and (2), R1 and R2 represent hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert.
-Represents a monovalent selected from -butyl group, which may be the same or different from each other, a is an integer of 0 to 6, and may be the same or different from each other, and x And y represent a copolymerization ratio. ), Wherein the copolymerization ratio x / y is from 100/0 to 50/50 m
ol% / mol%, and its weight average molecular weight is 1
The production method according to the above 1) or 2), which is 0000 or more.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a biodegradable aliphatic polyester and / or a copolymer thereof will be abbreviated as “polyester of the present invention”. The “main raw material” used in the production of the polyester of the present invention is 2-hydroxypropanoic acid and its derivatives. The derivatives are: 1) acid fluoride, acid chloride, and acid bromide of 2-hydroxypropanoic acid, 2) mixed anhydride of 2-hydroxypropanoic acid with other carboxylic acids, sulfonic acids, and phosphoric acids 3) Target anhydrides of 2-hydroxypropanoic acid 4) Oligomers which are linear multimers obtained by polymerizing 2-hydroxypropanoic acid, and 5) 1,4-dioxa-3,6-dimethylcyclohexane which is a cyclic dimer -2,5-dione. 1)
(3) to (3) have an L-form and a D-form, but their use is not particularly limited. Preferably, the L-form is used.

Raw materials other than the main raw materials used in the production of the biodegradable aliphatic polyester copolymer are hereinafter referred to as "auxiliary raw materials". The auxiliary raw materials can be roughly classified into hydroxycarboxylic acids and derivatives thereof.

Specific examples of the former hydroxycarboxylic acid include: a) 2-hydroxy compounds, 2-hydroxyethane acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, Hydroxyheptanoic acid, 2-hydroxyoctanoic acid, a) 2-hydroxy-2-substituted substrate, 2-hydroxy-2-methylpropanoic acid, 2-hydroxy-2-methylbutanoic acid, 2-hydroxy-2-methylpentane Acid, 2-hydroxy-2-methylhexanoic acid, 2-hydroxy-2-methylheptanoic acid, 2-hydroxy-2-
Methyloctanoic acid, 2-hydroxy-2-ethylbutanoic acid, 2-hydroxy-2-ethylpentanoic acid, 2-hydroxy-2-ethylhexanoic acid, 2-hydroxy-2-
Ethylheptanoic acid, 2-hydroxy-2-ethyloctanoic acid, 2-hydroxy-2-propylpentanoic acid, 2-
Hydroxy-2-propylhexanoic acid, 2-hydroxy-2-propylheptanoic acid, 2-hydroxy-2-propyloctanoic acid, 2-hydroxy-2-butylhexanoic acid, 2-hydroxy-2-butylheptanoic acid, 2- Hydroxy-2-butyloctanoic acid, 2-hydroxy-2-
Isopropyl ethanoic acid, 2-hydroxy-2-isopropylpropanoic acid, 2-hydroxy-2-isopropylbutanoic acid, 2-hydroxy-2-isopropylpentanoic acid, 2-hydroxy-2-isopropylhexanoic acid,
-Hydroxy-2-isopropylheptanoic acid, 2-hydroxy-2-isopropyloctanoic acid, 2-hydroxy-2-isobutylethaneic acid, 2-hydroxy-2-isobutylpropanoic acid, 2-hydroxy-2-isobutylbutanoic acid, 2 -Hydroxy-2-isobutylpentanoic acid,
2-hydroxy-2-isobutylhexanoic acid, 2-hydroxy-2-isobutylheptanoic acid, 2-hydroxy-
2-isobutyloctanoic acid, 2-hydroxy-2-te
rt-butyl ethane acid, 2-hydroxy-2-tert
-Butylpropanoic acid, 2-hydroxy-2-tert-
Butylbutanoic acid, 2-hydroxy-2-tert-butylpentanoic acid, 2-hydroxy-2-tert-butylhexanoic acid, 2-hydroxy-2-tert-butylheptanoic acid, 2-hydroxy-2-tert-butyloctanoic acid C) 3-hydroxy compounds, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 3-hydroxypentanoic acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, d) 3- Hydroxy-3-substituted substrates, 3-hydroxy-3-methylbutanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-3-methylheptanoic acid, 3- Hydroxy-3-methyloctanoic acid, 3-hydroxy-3-
Ethylpentanoic acid, 3-hydroxy-3-ethylhexanoic acid, 3-hydroxy-3-ethylheptanoic acid, 3-hydroxy-3-ethyloctanoic acid, 3-hydroxy-3
-Propylhexanoic acid, 3-hydroxy-3-propylheptanoic acid, 3-hydroxy-3-propyloctanoic acid, 3-hydroxy-3-butylheptanoic acid, 3-hydroxy-3-butyloctanoic acid, 3-hydroxy-3 −
Isopropylpropanoic acid, 3-hydroxy-3-isopropylbutanoic acid, 3-hydroxy-3-isopropylpentanoic acid, 3-hydroxy-3-isopropylhexanoic acid, 3-hydroxy-3-isopropylheptanoic acid, 3
-Hydroxy-3-isopropyloctanoic acid, 3-hydroxy-3-isobutylpropanoic acid, 3-hydroxy-
3-isobutylbutanoic acid, 3-hydroxy-3-isobutylpentanoic acid, 3-hydroxy-3-isobutylhexanoic acid, 3-hydroxy-3-isobutylheptanoic acid,
3-hydroxy-3-isobutyloctanoic acid, 3-hydroxy-3-tert-butylpropanoic acid, 3-hydroxy-3-tert-butylbutanoic acid, 3-hydroxy-3-tert-butylpentanoic acid, 3-hydroxy-
3-tert-butylhexanoic acid, 3-hydroxy-3
-Tert-butylheptanoic acid, 3-hydroxy-3-
tert-butyloctanoic acid, e) 4-hydroxy compound, 4-hydroxybutanoic acid, 4-hydroxypentanoic acid, 4-hydroxyhexanoic acid, 4-hydroxyheptanoic acid, 4-hydroxyoctanoic acid, f) 4-hydroxy -4-substituted substrates, 4-hydroxy-4-methylpentanoic acid, 4-hydroxy-4-methylhexanoic acid, 4-hydroxy-4-methylheptanoic acid, 4-hydroxy-4-methyloctanoic acid, 4- Hydroxy-4-ethylhexanoic acid, 4-hydroxy-4-
Ethylheptanoic acid, 4-hydroxy-4-ethyloctanoic acid, 4-hydroxy-4-propylheptanoic acid, 4-
Hydroxy-4-propyloctanoic acid, 4-hydroxy-4-isopropylbutanoic acid, 4-hydroxy-4-isopropylpentanoic acid, 4-hydroxy-4-isopropylhexanoic acid, 4-hydroxy-4-isopropylheptanoic acid, 4- Hydroxy-4-isopropyloctanoic acid, 4-hydroxy-4-butyloctanoic acid, 4-hydroxy-4-isobutylbutanoic acid, 4-hydroxy-4
-Isobutylpentanoic acid, 4-hydroxy-4-isobutylhexanoic acid, 4-hydroxy-4-isobutylheptanoic acid, 4-hydroxy-4-isobutyloctanoic acid,
4-hydroxy-4-tert-butylbutanoic acid, 4-
Hydroxy-4-tert-butylpentanoic acid, 4-hydroxy-4-tert-butylhexanoic acid, 4-hydroxy-4-tert-butylheptanoic acid, 4-hydroxy-4-tert-butyloctanoic acid; 5-hydroxypentanoic acid, 5-hydroxyhexanoic acid, 5-hydroxyheptanoic acid, 5-hydroxyoctanoic acid, which is a hydroxy compound, c) 5-hydroxy-5-methylhexane, which is a 5-hydroxy-5-substituted substrate Acid, 5-hydroxy-5-methylheptanoic acid, 5-hydroxy-5-methyloctanoic acid, 5-hydroxy-5-ethylheptanoic acid, 5-hydroxy-5-ethyloctanoic acid, 5-hydroxy-5-
Propyloctanoic acid, 5-hydroxy-5-isopropylpentanoic acid, 5-hydroxy-5-isopropylhexanoic acid, 5-hydroxy-5-isopropylheptanoic acid, 5-hydroxy-5-isopropyloctanoic acid,
-Hydroxy-5-isobutylpentanoic acid, 5-hydroxy-5-isobutylhexanoic acid, 5-hydroxy-5
-Isobutylheptanoic acid, 5-hydroxy-5-isobutyloctanoic acid, 5-hydroxy-5-tert-butylpentanoic acid, 5-hydroxy-5-tert-butylhexanoic acid, 5-hydroxy-5-tert-butylheptanoic acid 6-hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 6-hydroxyoctanoic acid, and 6) -hydroxy-6-substituted substrate 6-hydroxy-6-methylheptanoic acid, 6-hydroxy-6-methyloctanoic acid, 6-hydroxy-6-ethyloctanoic acid, 6-hydroxy-6-isopropylhexanoic acid, 6
-Hydroxy-6-isopropylheptanoic acid, 6-hydroxy-6-isopropyloctanoic acid, 6-hydroxy-6-isobutylhexanoic acid, 6-hydroxy-6-isobutylheptanoic acid, 6-hydroxy-6-isobutyloctanoic acid, 6 -Hydroxy-6-tert-butylhexanoic acid, 6-hydroxy-6-tert-butylheptanoic acid, 6-hydroxy-6-tert-butyloctanoic acid, 7-hydroxyheptanoic acid which is a 7-hydroxy compound, 7-hydroxyoctanoic acid, 7) 7-hydroxy-7-methyloctanoic acid, 7-hydroxy-7-isopropylheptanoic acid, 7-hydroxy-7-isopropyloctanoic acid, 7-hydroxy-7-substituted substrate -Hydroxy-7-isobutylheptanoic acid, 7-hydroxy-7- Soviet-butyl octanoic acid,
7-hydroxy-7-tert-butylheptanoic acid, 7
-Hydroxy-7-tert-butyloctanoic acid, 8-hydroxyoctanoic acid which is an 8-hydroxy form, and 8-hydroxy-8-isopropyloctanoic acid which is an 8-hydroxy-8-substituted substrate. 8-hydroxy-
8-isobutyloctanoic acid, 8-hydroxy-8-te
rt-butyloctanoic acid. Further, in the above-described auxiliary raw materials, the auxiliary raw material has a similar carbon main chain skeleton, and has a 2,2-position, a 3,3-position, a 4,4-position, and a 5,5-position.
The disubstituted substrates at the 6,6-, 7,7-, and 8,8-positions are added. The substituents of the disubstituted group are selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group, and may be the same or different from each other.

Specific examples of the latter hydroxycarboxylic acid derivative include 2-hydroxybutanoic acid and 2-hydroxybutanoic acid,
Hydroxypentanoic acid, 3-hydroxypropanoic acid, 3
2-hydroxybutanoic acid, 2-hydroxybutanoic acid, 2-hydroxybutanoic acid, which is a mixed anhydride of 3-hydroxypentanoic acid and 3-hydroxypentanoic acid with acid fluoride, acid chloride and acid bromide, and carboxylic acid, sulfonic acid and phosphoric acid. Hydroxypentanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, or 3-hydroxypentanoic acid and formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, toluic acid, naphthoic acid, methanesulfonic acid, p- Mixed acid anhydrides with toluenesulfonic acid and phosphoric acid; h) mixed acid anhydrides obtained from different types of hydroxycarboxylic acids of the above a) to c); and t) hydroxycarboxylic acids of the above a) to c) The target acid anhydride obtained from the same kind of acid; and e) the linear multimer of hydroxycarboxylic acid of the above items a) to c) Ligomers, and g) cyclic dimers and trimers of hydroxycarboxylic acids.

The auxiliary raw materials shown in the above (a) to (t) are used alone.
Two or more species can be used as a mixture. That is, in the case of a biodegradable aliphatic polyester, for example, hydroxycarboxylic acid, its acid chloride, its cyclic dimer,
Even if it is one kind selected from the linear trimer, or if two or more kinds are mixed, it can be obtained by mixing all of them. In the case of a biodegradable aliphatic polyester copolymer, for example, it is obtained using hydroxycarboxylic acids having different skeletons or derivatives thereof.

Among the hydroxycarboxylic acids and derivatives thereof described in the above items a) to te), when they have an asymmetric carbon, there are optical isomers of D-form and L-form, but they are not limited at all. , They can be mixed.
Preferably, the L-form is used.

In the method for producing a polyester of the present invention, the total amount of organic impurities having 1 to 10 carbon atoms contained in the main raw material is 0.2 mol% or less based on the main raw material. I do. When organic impurities exceeding 0.2 mol% are contained in the main raw material, it causes a stop of the polymerization reaction and a cause of coloring during the production. In addition, the most excellent method for producing the polyester of the present invention is that the main material contains 1 to 10 carbon atoms.
, The total content of organic impurities is 0.1
2 mol% or less and the number of carbon atoms contained in the main raw material is 1
To 10 organic impurities, the content of pyruvic acid, 2-hydroxy-n-butyric acid, and ethyl lactate is 0.06 mol% or less, respectively, based on the main raw material.
A main raw material of not more than 02 mol% and not more than 0.02 mol% is used. When the content of each organic impurity exceeds each of the above values, the resulting polyester of the present invention cannot sufficiently exhibit excellent thermal stability and optical properties, and improvement of these properties cannot be expected.

The quantitative analysis of organic impurities contained in the main raw material of the present invention can be carried out by commonly used liquid chromatography analysis or chromatographic analysis, such as purity analysis of general organic chemicals. No method or analyzer required.

The polymerization catalyst used in the process for producing a polyester of the present invention comprises at least one tin compound selected from tin, tin oxide and tin chloride, and a logarithm of the reciprocal of the acid dissociation constant of 3.66 or less. And at least one of the acidic organic sulfone compounds, and the absence of either one does not achieve the object of the present invention.

The form of the tin compound consisting of tin, tin oxide and tin chloride is not particularly limited, and may be any of powder, granule, wire, fiber, steel wool, plate and lump. But it doesn't matter. It is preferably a steel wool or fiber having a large surface area per unit weight, and most preferably a powder.

Specific examples of the acidic organic sulfone compound in which the logarithm of the reciprocal of the acid dissociation constant is 3.66 or less are as follows.
Methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, p-nitrobenzenesulfonic acid, p-xylene -2-sulfonic acid, naphthalene-1-sulfonic acid, and naphthalene-2-sulfonic acid. The logarithm of the reciprocal of the acid dissociation constant is 3.66.
If it exceeds, not only the polymerization rate is remarkably reduced but also the degree of polymerization reached is undesirably low.

The polymerization catalyst used in the method for producing a polyester of the present invention is as described above, and there are polymerization catalysts that can be used by further mixing with them. The polymerization catalyst that can be mixed is not particularly limited as long as it promotes the dehydration polycondensation reaction.

Specific examples thereof are as follows: a) 2, 4, 7, 9, 12, 13, 1 in the periodic table of elements.
Groups 4 and 15 (edited by The Chemical Society of Japan, 199
According to the zero year rule. A) magnesium, titanium, manganese, cobalt, zinc, aluminum, germanium, and lead, a) magnesium oxide, titanium oxide, manganese oxide, cobalt oxide, zinc oxide (A) magnesium chloride, titanium chloride, manganese chloride, cobalt chloride, zinc chloride, aluminum chloride, germanium chloride, and lead chloride; ) Metal sulfates, magnesium sulfate, zinc sulfate,
A) metal carbonates, magnesium carbonate and zinc carbonate; f) organic sulfonic acid metal salts, magnesium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, magnesium methanesulfonate, zinc methanesulfonate Magnesium p-toluenesulfonate, and zinc p-toluenesulfonate; g) magnesium acetate, zinc acetate, which is a metal acetate salt;
Trifluoroacetic acid, sulfuric acid, phosphoric acid and hydrochloric acid.

The amount of the polymerization catalyst used varies depending on the types and ratios of the main raw material and the auxiliary raw material and the production conditions, but is not particularly limited as long as the amount promotes the reaction rate. Normally,
0.00005 to the resulting polyester of the invention
-5% by weight, desirably 0.0001-1% by weight. If the amount is less than 0.00005% by weight, the effect of accelerating the polymerization reaction is small, and if it exceeds 5% by weight, no remarkable effect is exerted on the reaction rate, which is not economically preferable.

The weight average molecular weight of the polyester of the present invention obtained by the production method of the present invention is 10,000 or more, which is preferred. The measurement of the weight-average molecular weight can be determined by a commonly used measuring method. Specifically, gel permeation chromatography analysis is the simplest method, and the weight average molecular weight of the present invention is a value converted using standard polystyrene. When the weight average molecular weight is less than 10,000, the molded article is brittle, has insufficient mechanical properties, and cannot be put to practical use. The preferred weight average molecular weight is determined by the required performance depending on the form of use, and is not uniquely determined. However, from the performance most frequently required, a molecular weight of 70,000 or more is more preferable, and most preferably 120,000. As described above, the upper limit is 200,000 from the viewpoint of molding.

The polyester of the present invention obtained by the production method of the present invention can produce a copolymer by using two or more kinds of raw materials having different structures among the above-mentioned main raw materials and auxiliary raw materials. . The structure of the selected auxiliary material is
It is determined by the required physical properties, and any combination may be used. The copolymerization ratio of the main raw material and the auxiliary raw material, that is, the copolymerization ratio x of the above formulas (1) and (2)
/ Y ranges from 100/0 to 50/50 mol% / mol%. Preferably 100/0 to 70 / 30mo
1% / mol%, more preferably 100 / mol%.
It is in the range of 0 to 90/10 mol% / mol%.

The form of copolymerization is not limited at all, but is determined by the required physical properties. That is, any of random copolymerization, alternating copolymerization, and block copolymerization may be used. Furthermore, the arrangement type of the repeating unit of the copolymer may or may not have regularity, regularity, and periodicity.

As the polymerization method which can be used in the method for producing the polyester of the present invention, all known polymerization methods can be applied, but at least a part of the polymerization reaction is carried out by a solid state polymerization reaction. That is, these are polymerization methods of solution polymerization, interfacial polymerization, and bulk polymerization. The bulk polymerization method is used for any of olefin-based cations, anions, and radical polymerizations mainly composed of vinyl monomers and polycondensation used when synthesizing polyesters, polyamides, polyurethanes, and the like. Whereas polymerization takes place from monomers, the latter are less suitable for polymerization from monomers and are suitable for further polymerization of oligomers and polymers. In the case of polycondensation, it is often referred to as solid state polymerization rather than bulk polymerization. The polymerization in the present invention is also a polymerization mainly based on polycondensation, and is therefore called solid-phase polymerization.

When the polyester of the present invention is obtained by solution polymerization, a solvent, a dehydrohalogenation method, a dehydration method,
The temperature, concentration, time, pressure, and atmosphere are not particularly limited, and all known methods and conditions can be applied.

Solvents which can be used are: a) phenolic solvents, phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3 -Xylenol, 2,4-xylenol,
2,5-xylenol, 2,6-xylenol, 3,4
-Xylenol and 3,5-xylenol, b) N, N-dimethylformamide, N, N-dimethylacetamide, N, N
N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, and hexamethylphosphorotriamide; c) 1,2-dimethoxy which is an ether solvent Ethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, and 1,4-dioxane, d) amine System solvents, pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline,
Isophorone, piperidine, 2,4-lutidine, 2,6-
Lutidine, trimethylamine, triethylamine, tripropylamine, and tributylamine f) benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichloro benzene,
Bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, and p-bromotoluene, g ) Other solvents include dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, anisole, and water. These solvents may be used alone or in combination of two or more. When used as a mixture, it is not necessary to select a combination of solvents that are mutually soluble at an arbitrary ratio, and they may be mixed and non-uniform. The concentration of the reaction performed in these solvents (hereinafter, referred to as polymerization concentration) is
There are no restrictions.

In the case of polymerizing using an acid halide, any known method can be used as the dehydrohalogenation method. They can be divided into physical methods, chemical methods, and methods combining them. As a physical method,
A typical example is a method of removing the gas together with an atmosphere gas flow shown below from the system, and the chemical method includes the solvent d) described above.
Imidazole, N, N-
It can be captured and removed as salts or complexes with dimethylaniline, N, N-diethylaniline, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate. Further, they can be used in combination.

In the case where water is generated by the formation of an ester bond with the progress of the polymerization reaction, a known method can be applied to the dehydration method, similarly to the above-mentioned dehydrohalogenation method, and they can be classified into three types. Specific examples of the physical method are, in addition to the method of removing the outside of the system together with the atmosphere gas flow shown below,
A method of azeotropic dehydration using the solvent f) and a method of contacting a substance that adsorbs water, such as silica gel or molecular sieve, are added. Chemical methods include thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, polyphosphoric acid, acids represented by sodium metal, potassium hydroxide, sodium hydroxide, anhydrous potassium carbonate, anhydrous sodium carbonate, and acetic anhydride. Commonly used dehydrating agents such as anhydrides,
The method of contacting inside or outside the polymerization system can be mentioned as a specific method.

The atmosphere of the polymerization reaction system is not particularly limited.
Air, helium, nitrogen, neon, argon and the like are used, but helium and nitrogen are preferably used as the inert gas. Atmospheric gases may be used as a mixture of two or more kinds. In the case of an inert gas, a part thereof may be used as mixed with air. Polymerization catalyst with vapor pressure and / or
Alternatively, when a reducing agent is used, it is also possible to mix those vapors with a gas that flows into the polymerization system. The flow rate of the gas in the atmosphere is arbitrarily determined, and may be any flow rate at which water and other elimination compounds generated by the polymerization reaction can be removed out of the system.

When the polyester of the present invention is obtained by interfacial polymerization, the solvent, dehydrohalogenation method, temperature, concentration, time, pressure and atmosphere are not particularly limited, and all known methods and conditions can be applied. Specifically, the methods and compounds described in the above solution polymerization can be applied as they are.

The molecular weight of the polyester of the present invention used in the solid phase polymerization of the present invention varies depending on the kind thereof, but is usually preferably 5000 or more in terms of weight average molecular weight. When the weight average molecular weight is less than 5,000, the temperature at which solid phase polymerization is performed is higher than the melting temperature, and fusion due to melting occurs to make solid phase polymerization difficult.

The case where the polyester of the present invention has a weight average molecular weight suitable for the solid phase polymerization of the present invention is as follows:
It will be referred to as "oligomer of the invention".

The solid phase polymerization in the present invention means that the molecular weight of the polyester of the present invention and / or the oligomer of the present invention is reduced by performing a dehydration polycondensation reaction in a temperature range lower than the melting temperature while maintaining a solid state. It is a polymerization method that increases.

The temperature at which the solid phase polymerization is carried out varies depending on the kind of the polyester and / or the oligomer of the present invention, the kind of the polymerization catalyst and the amount of its use, but is usually 100 ° C.
The temperature range is preferably from the temperature at which the polyester of the present invention and / or the oligomer of the present invention melt. 10
If the temperature is lower than 0 ° C., the polymerization rate is low and the polymerization time is long, which is not economically preferable. When the temperature exceeds the melting temperature, fusion occurs due to melting, and it is difficult to take out of the polymerization apparatus after completion of solid-phase polymerization. The ordinary polymerization temperature varies depending on the type of the polyester of the present invention, but is preferably from 100 to 200 ° C, more preferably from 110 to 160 ° C, in consideration of the production rate, the thermal decomposition rate, and the coloring.

The atmosphere in the polymerization system for the solid-phase polymerization is not particularly limited, but it is preferable to carry out the reaction under a stream of an inert gas such as helium, nitrogen or argon and / or under reduced pressure. The inert gas may be used as a mixture of two or more kinds, or a part thereof may be mixed with air. When using a polymerization catalyst and / or a reducing agent having a vapor pressure at the temperature at which the solid-phase polymerization is performed, it is also possible to mix those vapors with a gas flowing into the polymerization system. The flow rate of the gas may be any flow rate at which water and other elimination compounds generated by the polymerization reaction can be removed out of the system. Preferably,
When the polymerization of the polyester of the present invention is completed, the range of the flow rate at which the polymerization catalyst and / or the reducing agent is removed from the obtained polyester of the present invention is desirable. Under these conditions, the treatment for removing the polymerization catalyst and / or the reducing agent can be omitted. When the polymerization catalyst and / or the reducing agent used in performing the solid-phase polymerization does not have a vapor pressure at the temperature at which the solid-state polymerization is performed, the flow rate of the flowing gas may be such that water and other desorbed compounds generated by the reaction are removed. It is sufficient that the flow rate is higher than the flow rate that can be removed outside the system.

The shape of the solid during the solid phase polymerization is not particularly limited as long as the shape does not inhibit the polymerization reaction. However, powders, granules, flakes, beads, spheres, hemispheres, and the like are generally used.
Pellets and lumps. Preferably, they are granules or beads.

The oligomer of the present invention used in the solid-phase polymerization is: a) increasing the molecular weight; a) preventing physical or external force from being applied to the oligomer of the present invention during the solid-phase polymerization; c) having crystallinity It is desirable to raise the melting temperature as high as possible by taking measures such as raising the crystallinity. In particular, in the case of being crystalline, it is preferable to carry out the crystallization treatment before the solid-phase polymerization for the purpose of increasing the crystallinity. Although the treatment temperature varies depending on the type of the polyester of the present invention to be used, it is 30 ° C., preferably 10 ° C., before and after the crystallization peak detected as an exothermic peak by measurement using a usual thermal analyzer such as DSC.
The crystallization treatment time is in the range of 0.1 to 5 hours, and the atmosphere is the same as the atmosphere in the above-described polymerization system for solid-phase polymerization.

In the method for producing the polyester of the present invention and / or the oligomer of the present invention, a reducing agent can be used. Whether or not the reducing agent can be used can be arbitrarily determined according to the situation. When using a reducing agent, if the reducing agent has the effect of suppressing or preventing the coloring of the polyester of the present invention, or has the effect of adsorbing oxygen mixed in the main raw material, the auxiliary raw material and the solvent, the type of the reducing agent is There is no particular limitation. Specific examples of the reducing agent include: a) an inorganic compound, sodium sulfite, sodium bisulfite, disulfite, sodium dithionite, sodium chlorite, a) a food additive, erythorbic acid, erythorbic acid Sodium, isopropyl citrate, dibutylhydroxytoluene, dl-α-tocopherol, nordihydroguaiaretic acid, butylhydroxyanisole, propyl gallate, ascorbic acid, c) Antioxidants used as plastic additives (specific examples) Is the Chemical Daily, January 28, 1998
Book published in Japan "13398 Chemicals", 1038-1
Page 046. ), D) IRGAN manufactured by Ciba Specialty Chemicals
OX (trade name) 1010, 245, 259, 107
6, 1222, 1425WL, 3114 and IRGA
FOS (trade name) P-EPQFF, 168, e) Sumitomo Chemical's Sumilizer (trade name) GA
-80, TPL-R, TPM, TPS, TP-D, T
L, MB, and F) A of Adekastab (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.
O-20, -30, -40, -50, -51, -60,
-70, -80, -330, -611, -612, -6
13, -616, -15, -18, -23, 412S,
-503A, PEP-8W, 4C, 11C, 24G,-
36, 36Z, HP-10, 2112, 260, 522
A, 329K, -1500, LA-31, -51, -5
2, -57, -62, -67, -63P, -68LD,
−82, −87, and the like. These reducing agents may be used alone or in combination of two or more. Among them, those specified as food additives are desirable, but not limited thereto.

The amount of the reducing agent to be used varies depending on the types and amounts of the main raw materials and auxiliary raw materials, the ratio of the raw materials, and the production conditions. The amount is not particularly limited as long as it is a certain amount or an amount capable of adsorbing or removing oxygen mixed or dissolved in the main raw material, the auxiliary raw material, and the solvent. Usually, for the resulting polyester of the invention and / or oligomer of the invention,
It is 0.001 to 10% by weight, preferably 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight.
If the amount is less than 0.001% by weight, the effect of suppressing coloring is poor. If the amount exceeds 10% by weight, no remarkable effect on coloration is observed, so that not only is it not economical, but also the mechanical properties of the obtained polyester of the present invention. It is not preferable because there is a possibility that the surface properties and the like of the molded body subjected to the molding process may be deteriorated.

The timing of adding the polymerization catalyst used in the method for producing the polyester of the present invention varies depending on the types of the main raw materials and auxiliary raw materials used.
Alternatively, the initial stage and the intermediate stage of the production of the oligomer of the present invention may be performed, but the initial stage of the production of the oligomer of the present invention is most desirable. The same applies to the timing of adding the reducing agent. It is most preferable to add the polymerization catalyst and / or reducing agent in the polymerization system in a molten state or a solution state from the viewpoint of uniform dispersion, uniform dissolution or uniform melting. It can be added in a heterogeneous state or a solid state.

The polymerization catalyst and / or reducing agent remaining in the polyester of the present invention and / or the oligomer of the present invention obtained by the above-mentioned production method may be, if necessary,
It can be removed by a known method. Specifically, a) a method in which the polyester of the present invention is dissolved in a good solvent and then contacted with a poor solvent in which a polymerization catalyst and / or a reducing agent is dissolved to perform extraction; a) a polymerization catalyst and / or a reducing agent is dissolved A method of separating the polymerization catalyst and / or the reducing agent by filtration after dissolving using a good solvent of the polyester of the present invention, and c) a poor solvent of the polyester of the present invention in which the polymerization catalyst and / or the reducing agent is dissolved A) a method of eluting or extracting a polymerization catalyst and / or a reducing agent by using the above-mentioned method. D) a method of dissolving the polyester of the present invention in a good solvent and then adsorbing the polymerization catalyst and / or the reducing agent to zeolite, molecular sieve, or the like. , And the like.

The solution or suspension containing the polyester of the present invention and / or the oligomer of the present invention is used for shaping such as solution processing and melt molding. The solution or suspension can be prepared using the polyester of the present invention and / or the oligomer of the present invention and a solvent.

Solvents that can be used include, in addition to the solvents described in the above-mentioned polymerization solvents, a) to g), h) acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol , Isobutanol, pentane, hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene,
Methyl acetate, ethyl acetate, butyl acetate, methyl formate, and ethyl formate. These solvents may be used alone or in combination of two or more. When used as a mixture, it is not always necessary to select a combination of solvents that dissolve each other at an arbitrary ratio, and they may not be mixed.

The preparation of the solution or suspension containing the polyester of the present invention and / or the oligomer of the present invention is optional and there is no particular limitation. That is, there is no limitation on the temperature, time, concentration and pressure in the preparation conditions, and known methods can be applied to preparation means such as stirring, mixing and dispersion, and the preparation methods are also the same. Specific examples of the preparation method include: a) a method in which a solution or suspension after the completion of the polymerization reaction is used as it is, a) a method of obtaining an isolated powder, granules, or a lump and dissolving or dispersing them in the above solvent. And the method of making it. At the time of preparation, a dispersion accelerator or an emulsifier can be added.

The solution or suspension containing the polyester of the present invention and / or the oligomer of the present invention obtained as described above can be used by mixing them. To describe a specific method, the solutions after the completion of the polymerization reaction, the powders obtained by isolation once, the solutions thereof,
Alternatively, the solution and the powder are mixed by a known method. Both solutions and powders to be mixed have different types of repeating units,
There are no restrictions on the molecular weight, molecular weight distribution, concentration in the case of a solution, and the mixing ratio, and there are no restrictions on the mixing conditions or the method.

The polyester of the present invention and / or the oligomer of the present invention can be shaped by various melt molding methods. Applicable molding methods include extrusion molding, injection molding, compression molding, sinter molding, blow molding, vacuum molding, rotational molding, powder molding, reaction injection molding, lamination molding, and cast molding.

The polyester of the present invention and / or the oligomer of the present invention can be blended with other resins and blended or alloyed as long as their properties are not impaired. As the resin used, for example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polystyrene, polyvinyl acetate, ABS resin,
Polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polycarbonate, P
TFE, fluororesin, celluloid, polyarylate, polyether nitrile, polyamide, polysulfone, polyethersulfone, polyetherketone, polyphenylsulfide, polyamideimide, polyetherimide,
Modified polyphenylene oxide, thermoplastic polyimide, thermosetting polybutadiene, formaldehyde resin, amino resin, polyurethane, silicone resin, SBR, NBR,
Unsaturated polyester, epoxy resin, polycyanate,
Examples include phenolic resins and polybismaleimide. They are used in an appropriate amount of one or more resins according to the purpose, and the blending method and the alloying method are not particularly limited, and known methods can be applied.

The polyester of the present invention and / or the oligomer of the present invention may be mixed with carbon fiber, glass fiber, wholly aromatic polyamide fiber, potassium titanate fiber, or the like at an arbitrary ratio for the purpose of modifying its properties. Can be fiber reinforced. A preferable ratio is in the range of 10 to 50% by weight of the fibers, and particularly, an improvement in mechanical properties can be achieved.

Further, the polyester of the present invention and / or the oligomer of the present invention may be used for the purpose of modifying its properties.
It can be mixed with various fillers or additives.
Examples thereof include graphite, carborundum, silica powder, abrasion resistance improvers such as molybdenum disulfide, antimony trioxide, magnesium carbonate, calcium carbonate and the like, flame retardant improvers, clay, mica and the like. Property improver, tracking resistance improver such as asbestos, silica, graphite, etc., acid resistance improver such as barium sulfate, silica, calcium metasilicate, etc., thermal conductivity improver such as iron powder, zinc powder, aluminum powder, copper powder, And besides, glass beads, glass spheres, talc, diatomaceous, alumina,
Silasbaln, hydrated alumina, metal oxides, colorants, pigments, lubricants, stabilizers, bluing agents, ultraviolet absorbers, infrared absorbers, antistatic agents, surface modifiers and the like. The mixing method is not particularly limited, and a known method can be applied. Furthermore, for the same purpose, irradiation treatment with radiation such as infrared rays, ultraviolet rays, α, β, and γ rays, electron beams, and X-rays, plasma treatment, doping treatment, and heat treatment may be performed.

[0061]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto.

Test methods of various tests common to the examples and comparative examples are as follows. The abbreviations used hereinafter are shown in parentheses. 1) Polymerization average molecular weight (Mw): Showa Denko KK Sh
Using an Odex GPCsystem-11, the measurement was performed by conversion using chloroform as a mobile phase solvent and standard polystyrene. 2) Yellow index (YI): A 2 mm-thick press sheet obtained by preheating and melting at 200 ° C. for 9 minutes and then pressing at a pressure of 10 MPa for 1 minute as a test sample was manufactured by Suga Test Instruments Co., Ltd. It was measured by SM color computer SM5.

The abbreviations of raw materials, solvents and the like common to the examples and comparative examples are as follows. 1) LA; L-2-hydroxypropanoic acid 2) LTD; 1,4-dioxa-3,6-dimethylcyclohexane-2,5-dione 3) PRA; pyruvic acid 4) HBA; 2-hydroxy-n-butyric acid 5) LEE; lactate ethyl ester 6) MSA; methanesulfonic acid 7) PTS; p-toluenesulfonic acid 8) SIT; sodium sulfite 9) 3HB; DL-3-hydroxy-n-butanoic acid 10) 2HOC; -N-octanoic acid

Tables 1 and 2 show the qualities of the raw materials common to the examples and comparative examples and the abbreviations of the raw materials.

[0065]

[Table 1]

[0066]

[Table 2]

Example 1 50 equipped with a thermometer, a distilling tube with a cooling tube and a stirring device
41% of a 90% aqueous solution of LA1 was placed in a 0 ml four-necked flask.
6.69g, tin 0.002wt% (6mg) is inserted,
Under a nitrogen atmosphere, the mixture was heated at 100 ° C. and a normal pressure for 1 hour to dissolve the tin, and then cooled to room temperature.
(1.52 g), and heated at 140 ° C. and normal pressure for 1 hour to perform dehydration.
Dehydration was performed under reduced pressure for 2 hours. Thereafter, the temperature was raised to 160 ° C., the degree of pressure reduction was increased to 1.3 kPa, and the mixture was reacted for 10 hours to obtain an oligomer having Mw of 7,600. The obtained oligomer was crushed, and an oligomer particle having a particle size of 0.71 mm to 1.7 mm was obtained with a sieve.

60 g of the oligomer particles are packed into a glass cylinder into which nitrogen gas can be blown from the lower part having an inner diameter of 4 cm, and nitrogen gas heated to 100 ° C. at 100 ° C. in an oil bath at a flow rate of 35 ml / min for 1 hour Heated. Thereafter, the temperature of the oil bath and the temperature of the heated nitrogen were increased to 140 ° C., and solid phase polymerization was performed for 50 hours to obtain a polyester having an Mw of 132,000. The YI of this polyester was 5.0.

Examples 2 to 7 An oligomer was obtained in exactly the same manner as in Example 1 except that various LAs having different total contents of organic impurities were used.
Further, solid-state polymerization was performed under exactly the same conditions. The evaluation results of the obtained oligomer and polyester are shown in Example 1.
The results are shown in Table 3 below.

[0070]

[Table 3]

[0071]

[Table 4]

Examples 8 to 19 Using various LAs shown in Table 5 and polymerization catalysts or reducing agents shown in Table 4, under various solid-phase polymerization conditions shown in Table 5, the oligomers were obtained in the same manner as in Example 1. And polyester. Table 5 shows the results.

[0073]

[Table 5]

Examples 20 to 21 The 90% aqueous solution of LA1 in Example 1 was used at 416.69.
Using an aqueous solution shown in Table 6 instead of g, an oligomer was obtained in exactly the same manner as in Example 1, and solid-state polymerization was performed under exactly the same conditions. Table 6 shows the evaluation results of the obtained oligomer copolymer and polyester copolymer.

Comparative Examples 1 to 9 In place of LA1 in Example 1, LA4, LA3,
Using LA9 and LA10, oligomers and polyesters were obtained in the same manner as in Example 1 under various solid-phase polymerization conditions shown in Table 7. Table 7 shows the results.

[0076]

[Table 6]

[0077]

[Table 7]

[0078]

Industrial Applicability According to the production method of the present invention, usefulness is demonstrated as a substitute for a medical material or a general-purpose resin, and it is possible to produce a biodegradable aliphatic polyester and a copolymer thereof with little coloring in a short time. became. According to the present invention, the field of application of the obtained biodegradable aliphatic polyester and its copolymer is expanded as compared with the related art.

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[Procedure amendment]

[Submission date] October 22, 1999 (1999.10.
22)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Title of the Invention Biodegradable aliphatic polyester and / or
Or a method for producing the copolymer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Mitsunori Shimamatsu, Incorporated Mitsui Chemicals, Inc., 30 Asamuta-cho, Omuta-shi, Fukuoka (72) Inventor Kazunari Okada, 30 Asamuta-cho, Omuta-shi, Fukuoka F term (reference) 4J029 AA02 AB04 AC02 AD01 AE06 EA01 EA02 HA01 HB05 HB06 JC361 JF371 KA02 KE12 KF09

Claims (3)

[Claims] 1. A main raw material having a total content of organic impurities having 1 to 10 carbon atoms contained in the main raw material of not more than 0.2 mol% with respect to the main raw material in the presence of a reducing agent. Or both in the absence of at least one tin compound selected from tin, tin oxide, and tin chloride, and at least one acidic organic sulfone compound having a logarithm of the reciprocal of the acid dissociation constant of 3.66 or less. A biodegradable aliphatic polyester and / or a copolymer thereof, in which a polymerization reaction is carried out in the presence of a polymer as a polymerization catalyst, and at least a part of the polymerization reaction is carried out by a solid-phase polymerization reaction. 2. The total content of organic impurities having 1 to 10 carbon atoms contained in the main raw material is 0.2 mol% or less in total with respect to the main raw material, and the number of carbon atoms contained in the main raw material is 1 mol. To 10 organic impurities, the contents of pyruvic acid, 2-hydroxy-n-butyric acid, and ethyl lactate are 0.06 mol% or less, 0.02 mol% or less, respectively, based on the main raw material, and Using a main raw material of not more than 0.02 mol%, in the presence or absence of a reducing agent, at least one or more tin compounds selected from tin, tin oxide, and tin chloride, and a reciprocal of an acid dissociation constant. Biodegradability in which a polymerization reaction is carried out in the presence of both one or more acidic organic sulfone compounds having a logarithmic value of 3.66 or less as a polymerization catalyst at the same time, and at least a part of the polymerization reaction is carried out by a solid-state polymerization reaction Aliphatic polyester Beauty / or methods of making the copolymer. 3. The biodegradable aliphatic polyester and / or a copolymer thereof is represented by the formula (1): ## STR1 ## And one or more formulas (2) (In the formulas (1) and (2), R1 and R2 represent monovalent selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl. May be the same or different from each other, a is an integer of 0 to 6, may be the same or different from each other, and x and y represent a copolymerization ratio.) A repeating unit represented by a copolymerization ratio x / y of 100/0 to 50/50 mol% / m
The production method according to claim 1 or 2, wherein the weight average molecular weight is 10,000 or more.