KR20120012930A - Biodegradable polyester and manufacturing method thereof - Google Patents

Abstract

PURPOSE: Biodegradable polyester is provided to improve radiation and elongation due to the change of the composition of inserted material, and the control of molecular weight by using aliphatic acid and aromatic acid. CONSTITUTION: Biodegradable polyester is manufactured by the esterification and the polymerization of diol components, and acid components consisting of aliphatic acid and aromatic acid. The aliphatic acid is one or more mixtures selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, and hexadecanoic acid. The diol component comprises a first diol component selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,6- hexanediol, and a second diol component selected from diethylene glycol, and 1,6-hexnaediol.

Description

Biodegradable polyester and its manufacturing method {BIODEGRADABLE POLYESTER AND MANUFACTURING METHOD THEREOF}

The present invention relates to a biodegradable polyester and a method for producing the same, and more particularly, to a biodegradable poly that is easy to manufacture injection molded articles, fibers, papers, and films due to its excellent radioactivity using aliphatic acid, aromatic acid, alkanediol or oligomer. It relates to an ester and a method for producing the same.

The recent socio-environmental trend shows that environmental pollution is a serious social problem in the world. Especially, plastics used in various industries in various industries cannot be landfilled and incinerated because they are non-degradable materials. In many cases, the incineration of these plastics releases many harmful substances and generates harmful gases, destroying the natural environment.

Conventional plastics, namely synthetic resins, are all non-degradable resins such as polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, or ABS resins, and thus are not decomposed upon disposal, causing environmental pollution.

On the other hand, as the environmental pollution problem caused by the waste plastics as a social problem, the research on the biodegradable plastic resin that can be fully decomposed recently has been actively progressed, attracting a lot of attention around the world. In particular, the limitation of the use of landfills and the problem of recycling has emerged seriously, and development of degradable resins that decompose itself upon disposal after a certain period of time has been actively developed.

As a result of active research on biodegradable polymers, biodegradable polymers such as starch-based polymer, cellulose acetate, polyhydroxy butylate, polylactide, polycaprolactone, polybutylene succinate, etc. have been commercialized and commercialized. Since the polyester has not yet secured the physical properties to produce a film or fiber, it is being manufactured only for injection molded products.

In general, biodegradable polyesters are aliphatic polyesters made of aliphatic acid and diol components, which have poor radioactivity due to the structure and crystallinity of aromatic polyesters and other main chains, and have poor elongation, resulting in a decrease in strength. It is difficult to develop and has a low melting point, which is inadequate for heat resistance.

In order to solve this problem, Japanese Patent Application Laid-Open No. Hei 4-189822, 189823, etc., esterify aliphatic dicarboxylic acids and aliphatic dihydric glycols, perform a condensation polymerization reaction, and then add an isocyanate compound and react to obtain a molecular weight. By increasing the molecular weight and melt viscosity to improve the physical properties compared to the existing aliphatic polyester, but did not secure the physical properties that can be produced by fibers or films.

The present invention was invented to solve the above problems, and an object of the present invention is to provide a biodegradable polyester having improved spinning and elongation properties by changing the composition of the raw materials and controlling the molecular weight by using aliphatic acid and aromatic acid.

It is also an object of the present invention to provide a method for producing a biodegradable polyester capable of producing the biodegradable polyester under optimum production conditions.

It is also an object of the present invention to provide a biodegradable polyester and a method for producing the same, which can be produced by shortening the production time of the biodegradable polyester using an oligomer.

The present invention is oxalic acid (Oxalic acid), malonic acid (Malonic acid), succinic acid (Succinic acid), glutaric acid (Glutaric acid), adipic acid (Adipic acid), citric acid (Citric acid), pimer acid (Pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid One or more aliphatic acids mixed with one or two of terephthalic acid, dimethyl terephthalate, mandelic acid, or an aromatic acid mixed with two or more ethylene glycol, and ethylene glycol, 1 , 2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1,6-hexanediol (1,6 Hexnaediol) mixed with one or two or more of the first diol component, diethylene glycol, triethylene glycol (Triethly glycol) or two or more Provided is a biodegradable polyester, characterized in that it is produced by esterification and polymerization with a diol component composed of a mixed diol second component.

In addition, the aromatic acid and aliphatic acid provides a biodegradable polyester, characterized in that the molar ratio of 1.0: 0.05 ~ 0.3, the acid component and the diol component is prepared by mixing in a molar ratio of 1.0: 1.0 ~ 1.5.

In addition, the present invention is bis-hydroxy ethyl terephthalate (Bis-hydroxy ethyl terephthalate), oxalic acid (Oxalic acid), malonic acid (Malonic acid), succinic acid (Succinic acid), glutaric acid (glutaric acid), Adipic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, One or two of dodecanoic acid, hexanodecanoic acid, or a mixture of two or more aliphatic acids, terephthalic acid, dimethyl terephthalate, mandelic acid, or two Acid component composed of the aromatic acid mixed above, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-propanediol, 1,4- Diethylene primary component and diethylene mixed with one or two or more of butanediol (1,4-Butanediol) and 1,6-hexanediol (1,6-Hexnaediol) Recall (Diethylene glycol), and provides a biodegradable polyester eseutereueul, characterized in that triethylene glycol (Triethly glycol) is one or esterification and polymerization in the diol component is composed of two or more mixed diol of the second component to be produced.

In addition, the bis-hydroxyethyl terephthalate, acid component, diol component is molar ratio of 1.0: 0.1 to 0.5: 0.1 to 0.5, the aromatic acid and aliphatic acid of the acid component is characterized in that the mixture is prepared in a molar ratio of 1.0: 0.1 to 0.4 It provides a biodegradable polyester.

In addition, the present invention is bis-hydroxy ethyl terephthalate (Bis-hydroxy ethyl terephthalate), oxalic acid (Oxalic acid), malonic acid (Malonic acid), succinic acid (Succinic acid), glutaric acid (glutaric acid), Adipic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, Dopedanoic acid, hexanodecanoic acid, one or two or more aliphatic acids mixed with ethylene glycol, 1,2-propanediol, 1, Diol first component mixed with one or two or more of 3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1,6-hexanediol (1,6-Hexnaediol) Esterified and polymerized with a diol component composed of one or two or more diols of diethylene glycol and triethylene glycol. Provides a biodegradable poly eseutereueul characterized in that the manufacturing.

In addition, the bis-hydroxyethyl terephthalate, aliphatic acid and diol component provides a biodegradable polyester, characterized in that the mixture is prepared in a molar ratio of 1.0: 0.05 ~ 0.15: 0.04 ~ 0.2.

In addition, the diol first component and the diol second component provides a biodegradable polyester, characterized in that the mixture is prepared in a molar ratio of 1.0: 0.05 to 0.2.

In addition, it provides a biodegradable polyester characterized in that the cycloalkanediol is further added to the diol component.

In addition, the cycloalkanediol provides a biodegradable polyester, characterized in that added to include 5 to 15 mol% in the total diol component.

In addition, the cycloalkanediol is a biodegradable poly, characterized in that at least one of cyclohexane dimethanol (Cyclohexane dimethanol), cyclopropane dimethanol (Cyclopropane dimethanol), cyclobutane dimethanol (Cyclobutane dimethanol) To provide an ester.

In addition, during the esterification and polymerization, one or a mixture of two or more of tetrahydrophthalic anhydride, trimellitic anhydrie, and maleic anhydride may be added as a crosslinking agent. It provides a biodegradable polyester, characterized in that.

In addition, the crosslinking agent provides a biodegradable polyester, characterized in that added 0.1 to 8% by weight of the total weight.

In addition, it provides a biodegradable polyester, characterized in that further addition of a compound comprising a sulfonate group during the esterification and polymerization.

In addition, the compound containing a sulfonate group is dimethyl 5-sodio sulfoisophthalate (dimethyl 5-sodio sulfoisophthalate) or 5-sulfoisophthalic acid monosodium salt (5-sulfoisophthalic acid monosodium salt), characterized in that It provides a biodegradable polyester.

In addition, the present invention is oxalic acid (Oxalic acid), malonic acid (Malonic acid), succinic acid (Succinic acid), glutaric acid (Glutaric acid), adipic acid (Adipic acid), citric acid (Citric acid), pimer acid (Pimeric acid), azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid (Headecanoic acid) ) Or a mixture of two or more aliphatic acids, terephthalic acid, dimethyl terephthalate, mandelic acid, or a mixture of two or more aromatic acids, wherein the aromatic acid and aliphatic acid have a molar ratio of 1.0: 0.05 to 0.2. Acid component, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-propanediol, and 1,4-butanediol -Butanediol), 1,6-hexanediol (1,6-Hexnaediol) or a mixture of diol first component and diethylene glycol (Diethylene glyc) ol), a diol second component of triethylene glycol (Triethly glycol) or a mixture of two or more of the diol first component and the diol second component is a diol component having a molar ratio of 1.0: 0.05 ~ 0.2, the acid component and the diol component Silver molar ratio 1.0: 1.0 to 1.5 by mixing in an esterification step of producing an oligomer at 210 to 330 minutes, 40 to 80 rpm at 200 ~ 240 ℃; And it provides a biodegradable polyester production method comprising a polymerization step of polymerizing the oligomer at 230 ~ 280 ℃ 180 ~ 210 minutes, 40 ~ 100rpm.

In addition, the onset is bis-hydroxyethyl terephthalate (Bis-hydroxy ethyl terephthalate), oxalic acid (Oxalic acid), malonic acid (Malonic acid), Succinic acid (Succinic acid), glutaric acid, ah Adipic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, One or two of dodecanoic acid, hexanodecanoic acid, or a mixture of two or more aliphatic acids, terephthalic acid, dimethyl terephthalate, mandelic acid, or two The aromatic acid and the aliphatic acid mixed with the above-mentioned aromatic acid are an acid component composed of a molar ratio of 1.0: 0.1 to 0.4, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-propanediol. One of (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1,6-hexanediol (1,6-Hexnaediol) Or a diol first component mixed with two or more diethylene glycol, triethylene glycol, or a diol second component mixed with two or more of the diol first component and the diol second component. 1.0: The bis-hydroxyethyl terephthalate, the acid component, and the diol component of the diol component composed of 0.05 to 0.2 are mixed at a molar ratio of 1.0: 0.1 to 0.5: 0.1 to 0.5 at 200 to 240 ° C. for 150 to 190 minutes and 40 An esterification process for preparing the oligomer at ˜80 rpm; And it provides a biodegradable polyester production method comprising a polymerization step of polymerizing the oligomer at 230 ~ 280 ℃ 180 ~ 210 minutes, 40 ~ 100rpm.

In addition, the present invention is bis-hydroxy ethyl terephthalate (Bis-hydroxy ethyl terephthalate), oxalic acid (Oxalic acid), malonic acid (Malonic acid), succinic acid (Succinic acid), glutaric acid (glutaric acid), Adipic acid, citric acid, pimeric acid, azelaic acid, sebasic acid, nonanoic acid, decanoic acid, Dopedanoic acid, hexanodecanoic acid, one or two or more aliphatic acids mixed with ethylene glycol, 1,2-propanediol, 1, Diol first component mixed with one or two or more of 3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1,6-hexanediol (1,6-Hexnaediol) And a diol second component of one or two or more of diethylene glycol and triethylene glycol (Triethly glycol), wherein the first diol component and the second diol component have a molar ratio of 1.0: 0. The bis-hydroxyethyl terephthalate, the aliphatic acid, and the diol component of the diol component composed of 05 to 0.2 are mixed at a molar ratio of 1.0: 0.05 to 0.15: 0.04 to 0.2, 150 to 190 minutes at 200 to 240 ° C, and 40 to 80 rpm. Esterification step of preparing an oligomer; And it provides a biodegradable polyester production method comprising a polymerization step of polymerizing the oligomer at 230 ~ 280 ℃ 180 ~ 210 minutes, 40 ~ 100rpm.

In addition, one or more cycloalkanediols of cyclohexane dimethanol, cyclopropane dimethanol, cyclobutane dimethanol, or a mixture of two or more thereof may be further added as the diol component. It provides a method for producing a biodegradable polyester characterized in that.

In addition, the cycloalkanediol provides a biodegradable polyester production method characterized in that it is added so that 5 to 15 mol% in the total diol component.

In addition, the esterification process includes a sulfonate group which is dimethyl dimethyl 5-sodio sulfoisophthalate or 5-sulfoisophthalic acid monosodium salt. It provides a method for producing a biodegradable polyester, characterized in that further compound is added.

In addition, during the esterification and polymerization, one or a mixture of two or more of tetrahydrophthalic anhydride, trimellitic anhydrie, and maleic anhydride may be added as a crosslinking agent. It provides a method for producing biodegradable polyester, characterized in that.

In addition, the crosslinking agent provides a biodegradable polyester production method characterized in that the addition of 0.1 to 8% by weight of the total weight.

The present invention also provides a biodegradable polyester production method characterized by using a titanium catalyst or an antimony catalyst alone as a polymerization catalyst or by mixing a titanium catalyst and an antimony catalyst.

The present invention also provides a biodegradable polyester production method characterized by using a titanium catalyst and an antimony catalyst in a mixture of 25:75 to 50:50.

In addition, the titanium catalyst is tetrabutyl isopropoxide (Tetrabutyl Isopropoxide) or tetrabutyl titanate (Tetrabutyl Titanate), the antimony catalyst is produced biodegradable polyester, characterized in that the antimony trioxide (Antimon Trioxide) Provide a method.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

The present invention is prepared by esterifying and polymerizing an aliphatic acid (Acid) and an aromatic acid (Acid) as an acid component and an alkanediol as a diol component, or a fatty acid in bis-hydroxyethyl terephthalate, or The present invention relates to a biodegradable polyester prepared by adding an aromatic acid or an aliphatic acid and an aromatic acid as an acid component and adding an alkanediol as a diol component to esterification and polymerization.

In general, in order to fiberize a synthetic resin, which is a polymer, at least a certain degree of crystallinity, crystal orientation, and degree of amorphous portion are required.

However, aliphatic polyesters made only of aliphatic acids have high bulk and high viscosity, resulting in poor radioactivity. Unlike general aromatic polyesters, they have low melting point and weak main chain, resulting in poor radioactivity due to winding tension during spinning. Fibrosis is not easy

The present invention is a biodegradable polyester which is radioactively improved by using an aliphatic acid and an aromatic acid together or a bis-hydroxyethyl terephthalate and an aliphatic acid together.

The present invention is prepared with an acid component of an aliphatic acid and an aromatic acid, a diol component, a bis-hydroxyethyl terephthalate, an acid component of an aliphatic acid and an aromatic acid, a diol component, or bis-hydroxyethyl Biodegradable polyester is prepared from bis-hydroxy ethyl terephthalate, aliphatic acid and diol.

A first embodiment of the present invention is a biodegradable polyester prepared from acid components of aliphatic and aromatic acids and diol components of alkanediol.

Aliphatic acid (Acid) used in the first embodiment of the present invention is oxalic acid (Oxalic acid), malonic acid (Malonic acid), Succinic acid (Succinic acid), glutaric acid (Glutaric acid), Adipic acid (Adipic acid) ), Citric acid, Pimeric acid, Azelaic acid, Sebasic acid, Nonanoic acid, Decanoic acid, Dodecanoic acid acid), hexanodecanoic acid, and the like.

The aliphatic acid compound may be used alone or in combination of two or more.

As the aromatic acid, terephthalic acid, dimethyl terephthalate, mandelic acid, or the like may be used.

The aromatic acid compound may be used alone as the aliphatic acid, or may be used by mixing two or more thereof.

When the biodegradable polyester of the present invention is used as a fiber, the aromatic acid and the aliphatic acid preferably constitute an acid component at a molar ratio of 1.0: 0.05 to 0.2, and when used for film purposes, the aromatic acid and the aliphatic acid have a molar ratio of 1.0: 0.05 to 0.05. Since it is preferable to comprise an acid component with 0.3, it is preferable that the said aromatic acid and an aliphatic acid comprise an acid component in molar ratio 1.0: 0.05-0.3.

When the amount of aliphatic acid in the acid component is less, the biodegradation function is lowered, and when the amount is too high, it is difficult to produce a fiber having low radioactivity.

The diol component is ethylene glycol (Ethylene glycol), 1,2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol ), One or two or more of 1,6-hexanediol (1,6-Hexnaediol) mixed with a diol first component and one or two or more of diethylene glycol, triethylene glycol (Triethly glycol) It is preferable to use it by composition as a diol 2nd component.

The diol second component of the diethylene glycol and triethylene glycol improves the biodegradable function of the biodegradable polyester of the present invention.

When the amount of the diol second component is increased, the radioactivity of the biodegradable polyester of the present invention is lowered, so that the mixing ratio of the diol first component and the diol second component should be appropriately adjusted.

It is preferable that the diol first component and the diol second component constitute diol sulfide in a molar ratio of 1.0: 0.05 to 0.2.

In the first embodiment, the biodegradable polyester made of aliphatic acid, aromatic acid, and alkanediol may take a long time in the esterification process, thereby reducing work efficiency.

Therefore, an oligomer such as bis-hydroxy ethyl terephthalate may be used to shorten the time required for esterification in order to shorten the time required for the esterification process.

The second embodiment is a biodegradable polyester made of bis-hydroxyethyl terephthalate, an acid component of aliphatic and aromatic acids and a diol component of alkanediol.

The bis-hydroxyethyl terephthalate (Bis-hydroxy ethyl terephthalate) is an oligomer prepared by esterification of terephthalic acid (Terephthalic acid) and ethylene glycol (Ethylene glycol) as an intermediate compound of the polyester manufacturing process bis-hydroxyethyl terephthalate Phthalates can be used to effectively reduce the time required for esterification with aliphatic acids, aromatic acids and alkanediols.

In a second embodiment of the present invention, a biodegradable polyester is prepared using bis-hydroxyethyl terephthalate, an acid component of aliphatic and aromatic acids of the first embodiment, and a diol component of alkanediol.

Bis-hydroxyethyl terephthalate, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid Adipic acid, Citric acid, Pimeric acid, Azelaic acid, Sebasic acid, Nonanoic acid, Decanoic acid, Dodecanoic acid (Aliphatic acid) mixed with one or two or more of Dodecanoic acid, hexanodecanoic acid, one or two or more of terephthalic acid, dimethyl terephthalate and mandelic acid. Acid component composed of aromatic acid, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-propanediol, 1,4-butanediol (1 , 4-Butanediol), 1,6-hexanediol (1,6-Hexnaediol) mixed with one or two or more diol first component and diethylene glycol (Diethyle ne glycol), triethylene glycol (Triethly glycol) or a diol component composed of two or more of diol mixed with two or more to prepare a biodegradable polyester by esterification and polymerization, the bis-hydroxyethyl terephthalate, Acid component and diol component are prepared by mixing in a molar ratio of 1.0: 0.1-0.5: 0.1-0.5.

If the amount of the bis-hydroxyethyl terephthalate is used too much, the biodegradation function may be lowered, so the amount of the bis-hydroxyethyl terephthalate should be adjusted.

In addition, the molar ratio of the aromatic acid and aliphatic acid is preferably adjusted according to the amount of bis-hydroxyethyl terephthalate used, and the molar ratio of the aromatic acid and the aliphatic acid of the acid component may be prepared by mixing 1.0: 0.1 to 0.4.

A third embodiment of the present invention is a biodegradable polyester prepared from diol components of bis-hydroxyethyl terephthalate, aliphatic acid and alkanediol.

In a third embodiment of the present invention, a biodegradable polyester is prepared using bis-hydroxyethyl terephthalate, the diol component of the aliphatic acid and alkanediol of the first embodiment.

Bis-hydroxyethyl terephthalate, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid Adipic acid, Citric acid, Pimeric acid, Azelaic acid, Sebasic acid, Nonanoic acid, Decanoic acid, Dodecanoic acid (Dodecanoic acid), aliphatic acid mixed with one or more of hexanodecanoic acid, ethylene glycol, 1,2-propanediol, 1,3-propane Diol first component and diethylene mixed with one or two or more of diol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol) and 1,6-hexanediol (1,6-Hexnaediol) Diol component composed of one or two or more of diethylene glycol and triethylene glycol (Triethly glycol). To prepare an Li ester.

The third embodiment is prepared without using the aromatic acid used in the first and second embodiments, and the amount of bis-hydroxyethyl terephthalate and aliphatic acid should be properly adjusted, and bis-hydroxy If the amount of ethyl terephthalate is too high, the biodegradation function may be lowered. Therefore, the amount of ethyl terephthalate to be used should be adjusted. It would be most desirable to produce a biodegradable polyester by formulating from 0.04 to 0.2.

Bis-hydroxyethyl terephthalate (Bis-hydroxy ethyl terephthalate) used in Examples 2 and 3 can be prepared by reacting terephthalic acid (Terephthalic acid) and ethylene glycol (Ethylene glycol), discarded polyester Bis-hydroxyethyl terephthalate may be prepared as an environmentally friendly method of depolymerizing (Polyester).

The cycloalkanediol may be further added as the diol component of the biodegradable polyester of the present invention according to the first, second and third embodiments to improve physical properties of the biodegradable polyester.

As the cycloalkanediol, it is most preferable to use cyclohexane dimethanol, cyclopropane dimethanol, cyclobutane dimethanol, and the like.

When the cycloalkanediol is used, it will be most preferable that 5 to 15 mol% of the total diol component is added.

In addition, compounds containing sulfonate groups can be further added to esterify and polymerize. The compound containing a sulfonate group shortens the ester reaction and polymerization reaction time of the biodegradable polyester, improves the moldability by spreading the molecular weight distribution, and improves the biodegradability by increasing the hydrophilicity.

As the compound containing a sulfonate group, it is most preferable to use dimethyl 5-sodio sulfoisophthalate or 5-sulfoisophthalic acid monosodium salt. something to do.

In the preparation of the biodegradable polyester according to the present invention by mixing the above compounds, a crosslinking agent may be further added to increase the molecular weight of the polyester in esterification and polymerization.

The crosslinking agent may be tetrahydrophthalic anhydride, trimellitic anhydrie, maleic anhydride, or a mixture of two or more thereof.

Since the effect of the crosslinking agent is not large when a predetermined amount or more is used, the amount of the crosslinking agent is preferably added in an amount of 0.1 to 8% by weight of the total weight of the acid component and the diol component as the reactants.

The method for producing the biodegradable polyesters according to the present invention of the first, second and third embodiments as described above is prepared by an esterification process and a polymerization process.

The esterification process is prepared by mixing all the raw materials, in the case of the first embodiment after the acid component of the aromatic acid and aliphatic acid, and the diol component in a composition according to the use of biodegradable polyester, after 210 ~ 200 ~ 200 ℃ It is the process of manufacturing an oligomer at 330 minutes and 40-80 rpm.

In the esterification process, the reaction temperature may be less than 260 ° C. to reduce byproducts and prevent thermal decomposition of raw materials.

In addition, as described above, cycloalkanediol may be further added as the diol component, and a compound including a sulfonate group and a crosslinking agent may be further added.

In the polymerization process, the oligomer prepared by the ester process is polymerized at 230 to 280 ° C. for 210 minutes at 40 to 100 rpm to produce a biodegradable polyester.

In the polymerization step, a titanium catalyst or an antimony catalyst may be used as the polymerization catalyst.

The titanium catalyst is preferably tetrabutyl isopropoxide or tetrabutyl titanate, and the antimony catalyst is preferably antimony trioxide. will be.

The polymerization catalyst may be a titanium catalyst or an antimony catalyst alone, but it is preferable to use a mixture of the two catalysts. When the titanium catalyst and the antimony catalyst are mixed and used, a titanium catalyst and an antimony catalyst are used. It would be preferable to use a mixture of 75 to 50:50.

Bis-hydroxyethyl terephthalate (Bis-hydroxy ethyl terephthalate) by using a bis-hydroxy ethyl terephthalate (Bis-hydroxy ethyl terephthalate) the method of producing a biodegradable polyester according to the present invention of the second embodiment, the third embodiment Ethyl terephthalate (Bis-hydroxy ethyl terephthalate) can be prepared in the same manner as in the first embodiment except that the esterification process time is shortened.

That is, the preparation method of the second and third embodiments using bis-hydroxyethyl terephthalate (bis-hydroxyethyl terephthalate), acid components of bis-hydroxyethyl terephthalate, aromatic acid and aliphatic acid, diol component or aliphatic acid and After the compound is prepared to suit the respective compositions such as the diol component, the esterification process for preparing the oligomer at 200 to 260 ° C. for 150 to 190 minutes and 40 to 80 rpm, and the oligomer prepared by the ester process at 210 to 280 ° C. The biodegradable polyester of this invention is manufactured by the superposition | polymerization process of superposition | polymerization at 40-100 rpm.

In the production methods of the second and third embodiments, as described above, cycloalkanediol may be further added as the diol component, a compound containing a sulfonate group, a crosslinking agent may be further added, and the polymerization catalyst Titanium catalyst and antimony catalyst may be used.

The present invention is prepared by esterifying and polymerizing an aliphatic acid (Acid) and an aromatic acid (Acid) as an acid component and an alkanediol as a diol component, or a fatty acid in bis-hydroxyethyl terephthalate, or Biodegradable polyester is prepared by adding aromatic acid or aliphatic acid and aromatic acid as acid component and alkanediol as diol component, and can produce polyester fiber and film because of its excellent physical properties, high melting point and excellent spinning property. Or there is an effect that can easily prepare the injection molding.

Examples of the process for producing the biodegradable polyesters of the present invention are shown below, although not limited thereto.

Example 1. Evaluation of reaction time by TPA and BHET method

(1) Manufacturing conditions

material Chemical name Remarks Main raw material EG Ethylene Glycol Diol DEG Diethylene Glycol Diol BHET Bis-hydroxyethyl terephthalate Oligomer AA Adipic Acid Diacid additive TI Tetrabutyl Isopropoxide catalyst AT Antimon trioxide catalyst AL Aluminum Acetate basic Metal catalyst TPP Triphenyl Phosphate Heat stabilizer

(2) polymerization conditions table

① esterification reaction (unit / g)

division TPA AA EG DEG catalyst reaction
Temperature Example 1-1 155.4 13.70 74.7 5.40 0.35 240 ℃

division BHET TPA AA EG DEG catalyst reaction
Temperature Examples 1-2 91.80 77.70 12.30 38.0 5.40 0.35 240 ℃

(3) Experiment result

① Polymerization reaction (esterification reaction and polymerization reaction)

-Generally, TPA is applied to the esterification reaction under nitrogen condition because the melting point of TPA is over 300 ℃ during polymerization. In this experiment, the results of ester and polycondensation reaction (PC) reaction time in the TPA process (Example 1-1) and the BHET process (Example 1-2) under conditions not pressurized with nitrogen during the ester reaction are shown. 4 is shown.

Item Esterification reaction time PC response time IV Example 1-1 190 minutes No polymerization reaction - Examples 1-2 150 minutes 180 minutes 0.633

As shown in Table 4, in the case of the TPA method, the esterification time was increased by 40 minutes compared to the BHET method, and it was observed that the TPA was not completely dissolved. In addition, in the case of the PC reaction, the BHET process proceeded smoothly, but in the case of the TPA method, the TPA was not dissolved in the ester reaction, and thus the polymerization did not proceed. Therefore, the application of BHET significantly shortened the polymerization time compared to TPA, and the polymerization proceeded smoothly in the PC reaction.

Example 2 Preparation of Biodegradable Polyesters According to Aliphatic Acid Types

(1) Manufacturing conditions

material Chemical name Remarks Main raw material EG Ethylene Glycol Diol DEG Diethylene Glycol Diol BHET Bis-hydroxyethyl terephthalate Oligomer GA Glutaric acid Diacid SA Succinic acid Diacid AA Adipic Acid Diacid SBA Sebacic acid Diacid TPA Terephthalic Acid Diacid additive TI Tetrabutyl Isopropoxide catalyst AT Antimon trioxide catalyst AL Aluminum Acetate basic Metal catalyst TPP Triphenyl Phosphate Heat stabilizer

(2) polymerization conditions table

① esterification reaction (unit / g)

division BHET TPA GA EG DEG catalyst reaction
Temperature Example 2-1 91.80 77.70 13.70 38.0 5.40 0.35 240 ℃

* Glutaric Acid (GA) applied

division BHET TPA SA EG DEG catalyst reaction
Temperature Example 2-2 91.80 77.70 12.30 38.0 5.40 0.35 240 ℃

* Succinic Acid (SA) applied

division BHET TPA AA EG DEG catalyst reaction
Temperature Example 2-3 91.80 77.70 15.20 38.0 5.40 0.35 240 ℃

* Adipic Acid (AA) applied

division BHET TPA SBA EG DEG catalyst reaction
Temperature Examples 2-4 91.80 77.70 21.03 38.0 5.40 0.35 240 ℃

* Sebacic Acid (SBA) applied

② Polymerization reaction (unit: ℃ / torr / rpm)

division Reaction temperature Vacuum degree Full vacuum Stirring speed Closing point Example 2-1-4 270 1 or less Within 30 minutes 80 Torque Reach

(3) Experiment result

① Polymerization reaction (esterification reaction and polymerization reaction)

-In order to investigate the properties of the final polymer according to the type of aliphatic acid, glutaric acid, succinic acid, adipic acid and sebacic acid were added.

Esterification reaction time
And rpm Polymerization reaction time
And rpm IV 150 minutes, 70 rpm 180 minutes, 80 rpm Example 2-1 0.681 Example 2-2 0.608 Example 2-3 0.633 Examples 2-4 0.638

② NMR analysis

Table 12 shows the results of NMR analysis according to the addition of aliphatic acid and DEG. In order to give biodegradability to the polymer, 10 mol% of aliphatic acid compared to TPA, which is aromatic, was added, and 3 mol% of EG was added to DEG. The NMR analysis results for the polymers are shown in Table 12. The results of the analysis showed that the aliphatic acid was very similar to the added one, but the DEG showed slightly higher value than the added amount. This may be due to DEG, a reaction by-product generated during the polymerization.

Sample Name Analysis Example 2-1 GA content: 9.56 mol% compared to TPA
DEG content: 4.60mol% compared to EG Example 2-2 SA content: 9.40 mol% compared to TPA
DEG content: 4.50mol% compared to EG Example 2-3 AA content: 9.90 mol% compared to TPA
DEG content: 4.50mol% compared to EG Examples 2-4 SBA content: 9.70mol% compared to TPA
DEG content: 5.20 mol% compared to EG

③ Tg and Tm

Table 13 shows the results of T _g and T _m according to the type of aliphatic acid. In general, in the case of polyester (PET), T _g value was 72 ℃ and T _m value was 262 ℃, but when modified with aliphatic acid and DEG to give biodegradation was lower than 10 ℃ and 20 ℃.

Sample Name Analysis Example 2-1 Tg: 61.0 ℃
Tm: 231.0 ℃ Example 2-2 Tg: 63.0 ℃
Tm: 228.6 ℃ Example 2-3 Tg: 57.8 ° C.
Tm: 228.4 ℃ Examples 2-4 Tg: 52 ℃
Tm: 224 ℃

Example 3 Preparation of Biodegradable Polyester by DMS Addition

(1) Manufacturing conditions

material Chemical name Remarks Main raw material EG Ethylene Glycol Diol DEG Diethylene Glycol Diol BHET Bis-hydroxyethyl terephthalate Oligomer GA Glutaric acid Diacid TPA Terephthalic Acid Diacid additive TI Tetrabutyl Isopropoxide catalyst AT Antimon trioxide catalyst DMS Dimethyl 5-sodio sulfoisophthalate additive AA Aluminum Acetate basic Metal catalyst TP Triphenyl Phosphate Heat stabilizer

(2) polymerization conditions table

① esterification reaction (unit / g)

division BHET TPA GA EG DEG DMS catalyst reaction
Temperature Example 3 89.7 77.7 13.7 40.2 5.4 3.0 0.35 240 ℃

② Polymerization reaction (unit: ℃ / torr / rpm)

division Reaction temperature Vacuum degree Full vacuum Stirring speed Closing point Example 3 270 1 or less Within 30 minutes 60 Torque Reach

(3) Experiment result

① Polymerization reaction (esterification reaction and polymerization reaction)

-In order to select the optimum stirring speed in the esterification reaction and the polymerization reaction, the experiment was conducted at 60 rpm, which was performed in the existing polyester, and the esterification reaction and the polymerization reaction times are shown in Table 17.

Esterification time and rpm Polymerization time and rpm IV 150 minutes, 70 rpm 180 minutes, 80 rpm 0.650

② NMR analysis

Table 18 shows the NMR analysis values for Example 3. Glutaric acid and DMS showed similar reaction values compared to the dosage, but DEG showed very high values compared to the dosage. It is believed that this was produced by byproduct during the ester reaction. It is considered that DMS produced DEG as a by-product in the reaction, and it is thought that it is more effective to inject the EG and DMS into the esterification reaction primarily.

Analysis Sample Name Example 3 GA content: 9.78 mol% compared to TPA
DMS content: 0.65mol% compared to TPA
DEG content: 11.42 mol% compared to TPA

Claims (25)

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, pimeric acid, One or two of azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid, or 2 An acid component composed of an aliphatic acid, terephthalic acid, dimethyl terephthalate, mandelic acid, or an aromatic acid mixed with two or more mixed aliphatic acids,
Ethylene glycol, 1,2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1, Diol first component mixed with one or two or more of 6-hexanediol (1,6-Hexnaediol) and diol second component mixed with one or two or more of diethylene glycol, triethylene glycol (Triethly glycol) Biodegradable polyester, characterized in that produced by esterification and polymerization with a diol component. The method of claim 1,
The aromatic acid and aliphatic acid is a molar ratio of 1.0: 0.05 to 0.3, the acid component and the diol component is a biodegradable polyester, characterized in that the mixture is prepared in a molar ratio of 1.0: 1.0 to 1.5. Bis-hydroxyethyl terephthalate,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, pimeric acid, One or two of azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid, or 2 An acid component composed of a mixed aliphatic acid, terephthalic acid, dimethyl terephthalate, mandelic acid, or an aromatic acid mixed with two or more of
Ethylene glycol, 1,2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1, Diol first component mixed with one or two or more of 6-hexanediol (1,6-Hexnaediol) and diol second component mixed with one or two or more of diethylene glycol, triethylene glycol (Triethly glycol) Biodegradable polyester, characterized in that produced by esterification and polymerization with a diol component. The method of claim 3,
The bis-hydroxyethyl terephthalate, acid component, diol component is a molar ratio of 1.0: 0.1 to 0.5: 0.1 to 0.5, biodegradation, characterized in that the aromatic acid and aliphatic acid of the acid component is prepared by mixing in a molar ratio of 1.0: 0.1 to 0.4 Sex polyester. Bis-hydroxyethyl terephthalate,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, pimeric acid, One or two of azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid, or 2 Mixed aliphatic acid,
Ethylene glycol, 1,2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1, Diol first component mixed with one or two or more of 6-hexanediol (1,6-Hexnaediol) and diol second component mixed with one or two or more of diethylene glycol, triethylene glycol (Triethly glycol) Biodegradable polyester, characterized in that produced by esterification and polymerization with a diol component. The method of claim 5,
The bis-hydroxyethyl terephthalate, the aliphatic acid and the diol component is biodegradable polyester, characterized in that the mixture is prepared in a molar ratio of 1.0: 0.05 ~ 0.15: 0.04 ~ 0.2. The method according to any one of claims 1 to 6,
Biodegradable polyester, characterized in that the diol first component and the diol second component is prepared by mixing in a molar ratio of 1.0: 0.05 ~ 0.2. The method according to any one of claims 1 to 6,
A biodegradable polyester, characterized by further adding cycloalkanediol to the diol component. The method according to any one of claims 1 to 6,
The cycloalkanediol is biodegradable polyester, characterized in that added to include 5 to 15 mol% in the total diol component. The method of claim 8,
The cycloalkanediol is a biodegradable polyester, characterized in that one or two or more of cyclohexane dimethanol (Cyclohexane dimethanol), cyclopropane dimethanol (Cyclopropane dimethanol), cyclobutane dimethanol (Cyclobutane dimethanol). The method according to any one of claims 1 to 6,
At the time of esterification and polymerization, one or a mixture of two or more of tetrahydrophthalic anhydride, trimellitic anhydrie, and maleic anhydride is added as a crosslinking agent. Biodegradable polyester made of. The method of claim 11,
Biodegradable polyester, characterized in that the crosslinking agent is added 0.1 to 8% by weight of the total weight. The method according to any one of claims 1 to 6,
Biodegradable polyester, characterized in that further adding a compound containing a sulfonate group in the esterification and polymerization. The method of claim 13,
The compound comprising a sulfonate group is dimethyl 5-sodio sulfoisophthalate or 5-sulfoisophthalic acid monosodium salt. Sex polyester. Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, pimeric acid, One or two of azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid, or 2 The above-mentioned aliphatic acid, terephthalic acid, dimethyl terephthalate, and mandelic acid may be mixed with one or two or more aromatic acids. The aromatic acid and aliphatic acid may be composed of an acid component having a molar ratio of 1.0: 0.05 to 0.2. ,
Ethylene glycol, 1,2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1, Diol first component mixed with one or two or more of 6-hexanediol (1,6-Hexnaediol) and diol second component mixed with one or two or more of diethylene glycol, triethylene glycol (Triethly glycol) The diol first component and the diol second component is a diol component composed of a molar ratio of 1.0: 0.05 to 0.2, and the acid component and the diol component are mixed at a molar ratio of 1.0: 1.0 to 1.5 at 200 to 240 ° C. for 210 to 330 minutes and 40 Esterification process for preparing oligomer at ˜80 rpm; And
Biodegradable polyester production method characterized in that it comprises a polymerization step of polymerizing the oligomer at 230 ~ 280 ℃ 180 ~ 210 minutes, 40 ~ 100rpm. Bis-hydroxyethyl terephthalate,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, pimeric acid, One or two of azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid, or 2 The aliphatic acid, terephthalic acid, dimethyl terephthalate, mandelic acid, or a mixture of two or more of the aliphatic acids mixed with the above-mentioned aliphatic acid and aliphatic acid has an molar ratio of 1.0: 0.1 to 0.4. Branch,
Ethylene glycol, 1,2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1, Diol first component mixed with one or two or more of 6-hexanediol (1,6-Hexnaediol) and diol second component mixed with one or two or more of diethylene glycol, triethylene glycol (Triethly glycol) The diol first component and the diol second component are the diol component having a molar ratio of 1.0: 0.05 to 0.2, and the bis-hydroxyethyl terephthalate, the acid component, and the diol component are molar ratio of 1.0: 0.1 to 0.5: 0.1 to 0.5. Esterification step of preparing an oligomer by mixing at 200-240 ° C. for 150-190 minutes and 40-80 rpm; And
Biodegradable polyester production method characterized in that it comprises a polymerization step of polymerizing the oligomer at 230 ~ 280 ℃ 180 ~ 210 minutes, 40 ~ 100rpm. Bis-hydroxyethyl terephthalate,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, pimeric acid, One or two of azelaic acid, sebasic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexanodecanoic acid, or 2 Mixed aliphatic acid,
Ethylene glycol, 1,2-propanediol (1,2-propanediol), 1,3-propanediol (1,3-propanediol), 1,4-butanediol (1,4-Butanediol), 1, Diol first component mixed with one or two or more of 6-hexanediol (1,6-Hexnaediol) and diol second component mixed with one or two or more of diethylene glycol, triethylene glycol (Triethly glycol) The diol first component and the diol second component may be a diol component having a molar ratio of 1.0: 0.05 to 0.2, and the bis-hydroxyethyl terephthalate, an aliphatic acid and a diol component may have a molar ratio of 1.0: 0.05 to 0.15: 0.04 to 0.2. Esterification step of preparing an oligomer by mixing at 200-240 ° C. for 150-190 minutes and 40-80 rpm; And
Biodegradable polyester production method characterized in that it comprises a polymerization step of polymerizing the oligomer at 230 ~ 280 ℃ 180 ~ 210 minutes, 40 ~ 100rpm. The method according to any one of claims 15 to 17,
As the diol component, cyclohexane dimethanol, cyclopropane dimethanol, cyclobutane dimethanol, cyclobutane dimethanol, or a mixture of two or more cycloalkanediols may be further added. Biodegradable polyester production method. The method of claim 18,
The cycloalkanediol is biodegradable polyester production method characterized in that it is added so as to include 5 to 15 mol% in the total diol component. The method according to any one of claims 15 to 17,
In the esterification process, a compound containing a sulfonate group which is dimethyl dimethyl 5-sodio sulfoisophthalate or 5-sulfoisophthalic acid monosodium salt Biodegradable polyester production method characterized in that it further added. The method according to any one of claims 15 to 17,
At the time of esterification and polymerization, one or a mixture of two or more of tetrahydrophthalic anhydride, trimellitic anhydrie, and maleic anhydride is added as a crosslinking agent. Biodegradable polyester production method to be. The method of claim 21,
The crosslinking agent is a biodegradable polyester production method characterized in that the addition of 0.1 to 8% by weight of the total weight. The method according to any one of claims 15 to 17,
A method for producing a biodegradable polyester, characterized by using a titanium catalyst or an antimony catalyst alone as a polymerization catalyst in the polymerization step, or by mixing a titanium catalyst and an antimony catalyst. The method of claim 23, wherein
When the titanium-based catalyst and antimony-based catalysts are mixed and used, a biodegradable polyester production method characterized by using a mixture of titanium-based catalysts and antimony-based catalysts from 25:75 to 50:50. The method of claim 23, wherein
The titanium catalyst is tetrabutyl isopropoxide (Tetrabutyl Isopropoxide) or tetrabutyl titanate (Tetrabutyl Titanate), the antimony catalyst is a biodegradable polyester production method characterized in that the antimony trioxide (Antimon Trioxide).