JPH08295727A - Production of lactic-acid-based polyether polyester - Google Patents

Abstract

PURPOSE: To provide a biodegradable lactic-acid-based copolymer having a sufficiently high molecular weight, sufficient heat resistance and sufficient heat stability and having rigidity, flexibility and transparency suitable for the object of use by copolymerizing a specified polyether ester with a lactide in the presence of a polymerization catalyst. CONSTITUTION: A polyether polyester comprising repeating units represented by formula I [wherein m, x, y, and z are each an integer of 1 or greater; R1 and R2 are each H or a hydrocarbon group; R3 and R5 are aliphatic hydrocarbon groups provided that the total of their methylenic carbon atoms is 2 or above; R2 , R4 and R6 are each alkylene or a chemical structure of formula II (wherein R8 , R9 and R10 are each alkylene; a, b and c are each 0 or an integer of 1 or greater; and a+b+c is an integer of 1 or greater)] is copolymerized with a lactide (B) in the presence of a polymerization catalyst (C) to obtain a high- molecular-weight biodegradable lactic-acid-based copolymer having strengths high enough to be used as a general-purpose resin, and molding heat stability and having rigidity, transparency and flexibility suitable for the purpose of use.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention enables various molding processes useful for molding resins, sheet / film materials, paint resins, ink resins, adhesive resins, resins for paper lamination, and foamed resin materials. The present invention relates to a method for producing a high molecular weight lactic acid-based copolymer.

The lactic acid type copolymer produced by the production method of the present invention is a high molecular weight lactide type polyether polyester, which has biodegradability and is blow molding, extrusion molding, injection molding, inflation molding, laminate molding. Molding can be performed by various methods such as press molding, extrusion foam molding, etc., and molding can be performed using a molding device for general-purpose resins.

Specifically, the lactic acid-based copolymer produced by the production method of the present invention is used in various applications described above, such as trays, cups, plates and blisters for sheets.
Films include wrap films, food packaging, other general packaging, bags such as garbage bags, plastic bags, general standard bags, and heavy bags, and blow-molded products include shampoo bottles, cosmetic bottles, beverage bottles, and oil containers. For sanitary items such as paper diapers, sanitary items, artificial kidneys, sutures, medical materials, etc.

Agricultural materials include agricultural mulch films, pesticide sustained-release sheets, bird-prevention nets, curing sheets, seedling pots, fruit bags, etc., and fishing materials include fishing nets, seaweed cultivation nets, fishing lines, ship bottom paints. In addition, as an injection molded product,
Golf tee, fake bait, cotton swab core, candy stick,
Brushes, toothbrushes, syringes, dishes, cups, combs, razor handles, tape cassettes, disposable spoons / forks, ballpoint pens, etc.

For the lamination to paper, there are trays,
In addition to binding tapes, prepaid cards, balloons, pantyhose, hair caps, sponges, cellophane tapes, umbrellas, quilts, plastic gloves, hair caps, ropes, non-woven fabrics, tubes, etc.
It is usefully used for foam trays, foam cushioning materials, cushioning materials, packing materials, hot melt adhesives, cigarette filters, T-shirts and the like.

[0006]

2. Description of the Related Art In recent years, due to environmental problems and the like, much research has been conducted to widely utilize lactic acid-based polymers having excellent biodegradability as general-purpose polymers, and many studies and patent applications relating to the production method have been made. ing. However, it is difficult to say that conventionally known polylactic acid, which is a polymer of lactic acid or lactide, or a copolymer of lactic acid and another monomer has sufficiently satisfactory performance in moldability, transparency, and heat resistance. However, except for special uses, there is a problem in using it as a general-purpose resin, and improvement of these lactic acid-based polymers is desired.

JP-A-1-108226 describes a block copolymer comprising a polylactic acid segment and a polypropylene glycol segment, a method for producing the block copolymer, a copolymer film and a copolymer. Further, JP-A-1-108226 describes a copolymer of lactic acid and polyethylene glycol.

However, in these methods, when the copolymerization amount of the polyol is increased, the molecular weight becomes extremely low. For example, Example 4 of JP-A-1-108226
Then, when 10% by weight of polypropylene glycol having a number average molecular weight of 4,000 was copolymerized with lactide, only a copolymer having a number average molecular weight of 30,000 was obtained. Further, the copolymer of lactic acid and polyol loses its strength when the temperature exceeds about 40 ° C., and it is difficult to withstand use at high temperature as a general molded article other than for medical use.

As a copolymer of lactide and an aliphatic polyester, a method of preliminarily polymerizing ε-caprolactone to obtain a homopolymer and further block copolymerizing the lactide is described in JP-A-63-145661. There is.

However, in the method of block-copolymerizing lactide with poly-ε-caprolactone, the obtained copolymer becomes cloudy and opaque. This is due to the poly ε-in the copolymer.
It is considered that the caprolactone block and the polylactic acid block are hard to be compatible with each other, and the aliphatic polyester having a poly-ε-caprolactone chain becomes cloudy due to the generally high crystallinity. In addition, it has a soft property at room temperature, despite the relatively high glass transition point by differential thermal analysis.

Summarizing these conventional techniques, if they have sufficient strength, heat resistance and heat stability, they lack flexibility and transparency, and if they have sufficient flexibility and transparency, they become strong. However, since it has poor heat resistance and thermal stability, a polymer having sufficiently satisfactory properties for use as a material resin for films and sheets has not yet been obtained.

As a means for improving these physical properties, plasticization of the polymer with an additive is considered. However, the improvement of physical properties by these plasticizing methods is, for example, when lactide, which is a residual monomer, is used as a plasticizer as a plasticizing means, the heat resistance is lowered, and an apparatus in the manufacturing process by sublimation scattering of lactide is used. There is a problem of adhesion and contamination to lactide, leakage of plasticizer lactide from the polymer during storage or use of the product, and reduction / disappearance of the plasticizing effect due to disappearance.

Also, in the case of adding a general publicly known and common plasticizer for a polymer, it is necessary to add a large amount of plasticizer for plasticization, and the problem of bleeding out of the plasticizer is unavoidable, and the Problems such as the disappearance of the plasticizing effect have not been solved, and no polymer having sufficiently satisfactory properties has been obtained as a polymer for packaging materials. Also, it was not easy to obtain a high-molecular-weight lactic acid-based polymer.

[0014]

Therefore, the problem to be solved by the present invention is to provide a polymer having sufficient high molecular weight, heat resistance and thermal stability, and having rigidity, flexibility and transparency depending on the use. It is to provide a method for producing a degradable lactic acid-based polyether polyester.

[0015]

In order to solve such a problem, the present inventors have made earnest studies, and as a result, as a result, lactide, a polyether polyol component having various constituent ratios, a polyol component and a dicarboxylic acid component are used. By reacting an ether polyester as an essential component, lactide, a polyether polyol component having various constituent ratios, a polyol component, a dicarboxylic acid component, a polyfunctional carboxylic acid having 3 or more functional groups, and / or an acid anhydride thereof. By reacting a polyether polyester composed of a substance as an essential component, it suppresses decomposition into monomers during molding, has a wide range of molding temperatures, and has high strength and thermal stability during molding,

When copolymerizing with lactide,
When a hard resin having a high molecular weight, a high glass transition point and a high melting point is easily processed into a film by arbitrarily changing the proportion of the polyether polyester or by changing the type of the polyether polyester. Being able to produce various lactic acid-based copolymers that have excellent tear strength, toughness that does not easily break, and resins that have high flexibility and flexibility,

That is, a decomposable high molecular weight lactic acid-based copolymer having sufficient strength that can be used as a general-purpose resin, thermal stability during molding, and rigidity, transparency, and flexibility depending on the application. The present invention has been completed by discovering that it can be manufactured.

[0018]

[Structure] That is, the present invention relates to a polyether polyester (A) having a repeating unit represented by the general formula 1,

Embedded image

(In the formula, m, x, y and z are integers of 1 or more. R ₁ and R ₇ are hydrogen or a hydrocarbon group, and R ₃ and R ₅ are fats having a total of 2 or more methylene carbon atoms. Is a group hydrocarbon group,
R ₂ , R ₄ and R ₆ have an alkylene group or the chemical structure of the general formula 2.

General formula 2

[Chemical 4] (In the formula, R ₈ , R ₉ , and R ₁₀ are alkylene groups, and a,
b and c are 0 or an integer of 1 or more, and a + b + c is 1
It is an integer above the above. ) A method for producing a lactic acid-based polyether polyester, which comprises copolymerizing lactide (B) in the presence of a polymerization catalyst (C).

The method for producing a lactic acid-based polyether polyester of the present invention also relates to the polyether polyester (A).
Is a polyether polyester having a high molecular weight with a polyfunctional carboxylic acid having a functionality of 3 or more (and / or its acid anhydride) (D), and the polyether polyester (A)
However, the molar ratio of the ether group and the ester group in the polyether polyester is 999/1 to 200/800.

In the method for producing a lactic acid-based polyether polyester of the present invention, the weight ratio of the polyether polyester (A) to the lactide (B) is 60/40 to 5/95.
Is characterized in that.

The present invention further relates to a polyether polyol (E), a polyol (F) and a dicarboxylic acid (G).
And / or a polyether polyester (H) obtained by reacting a polyfunctional carboxylic acid having 3 or more functional groups and / or an acid anhydride thereof (D), and a lactide (B)
Is a method for producing a lactic acid-based polyether polyester, characterized in that and are copolymerized in the presence of a polymerization catalyst (C).

In the method for producing a lactic acid-based polyether polyester of the present invention, the polyether polyester (H) has a molar ratio of ether groups to ester groups in the polyether polyester (H) of 999/1 to 200/800. That is, the weight ratio of the polyether polyester (H) to the lactide (B) is 60/40 to 5/95.

More specifically, the polyether polyol (E) is one or more kinds selected from polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene) glycol which is a copolymer of ethylene oxide and propylene oxide. It is characterized by being an ether polyol. Further, the polyol (F) is characterized in that it is one or more kinds of diols selected from ethylene glycol and propylene glycol.

More specifically, the carboxylic acid (G) is particularly one or more dicarboxylic acids selected from succinic acid, adipic acid, sebacic acid, and acid anhydrides thereof, and their methyl esters and ethyl esters. Is characterized by.

The present invention further relates to a polyester comprising a polyol (F), a dicarboxylic acid (G), and / or a polyfunctional carboxylic acid having at least three functional groups and / or its acid anhydride (D), and a polyether. A lactic acid-based polyether polyester, characterized in that a polyether polyester (I) obtained by transesterification with a polyol (E) and a lactide (B) are copolymerized in the presence of a polymerization catalyst (C). It also includes a manufacturing method of.

In the method for producing a lactic acid-based polyether polyester of the present invention, the polyether polyester (I) has a molar ratio of ether groups to ester groups in the polyether polyester of 999/1 to 200/800, and The weight ratio of the polyether polyester (I) to the lactide (B) is 60/40 to 5/95.

More specifically, the polyether polyol (E) is at least one polyether polyol selected from polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene) glycol which is a copolymer of ethylene oxide and propylene oxide. To be

The polyol (F) is at least one diol selected from ethylene glycol and propylene glycol, the dicarboxylic acid (G) is succinic acid,
The production method is characterized by being adipic acid, sebacic acid, an acid anhydride thereof, and one or more dicarboxylic acids selected from their methyl esters and ethyl esters.

Further, in the present invention, a polyester obtained by reacting a polyol (F) with a dicarboxylic acid (G) and a polyether polyester obtained by reacting a polyether polyol (E) are trifunctional or more. Characterized in that the polyether polyester (J) obtained by reacting the polyvalent carboxylic acid (and / or its acid anhydride) is copolymerized with the lactide (B) in the presence of the polymerization catalyst (C). And a method for producing a lactic acid-based polyether polyester.

In the method for producing a lactic acid-based polyether polyester of the present invention, the polyether polyester (J) is
The molar ratio of the ether groups to the ester groups in the polyether polyester is 999/1 to 200/800, and the weight ratio of the polyether polyester (J) to the lactide (B) is 60/40 to 5/95. It is characterized by being.

More specifically, the polyether polyol (E) is one or more polyethers selected from polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene) glycol which is a copolymer of ethylene oxide and propylene oxide. Be a polyol,

The polyol (F) is one or more kinds of diols selected from ethylene glycol and propylene glycol, the dicarboxylic acid (G) is succinic acid,
It is characterized by being one or more kinds of dicarboxylic acids selected from adipic acid, sebacic acid, and acid anhydrides thereof, and their methyl esters and ethyl esters.

The present invention will be described in detail below. The lactide, the polyether polyester, the dicarboxylic acid, the polyether polyol, the polyol, the trifunctional or higher polyvalent carboxylic acid and / or the acid anhydride thereof used in the present invention will be sequentially described.

The lactide used in the present invention contains 2 parts of lactic acid.
It is a compound having a cyclic esterification between molecules and is a monomer having a stereoisomer. That is, there are two L- for lactide.
There are L-lactide composed of lactic acid, D-lactide composed of D-lactic acid, and MESO-lactide composed of L-lactic acid and D-lactic acid.

A copolymer containing only L-lactide or D-lactide is crystallized to obtain a high melting point. In the method for producing a high-molecular-weight lactic acid-based copolymer of the present invention, these three lactides are used. By combining them, preferable resin properties can be realized according to the application.

In the present invention, since high thermophysical properties are expressed, the lactide used is L-lactide in the total lactide.
The content of 75% or more is preferable, and in order to exhibit higher thermophysical properties, the lactide preferably contains 90% or more of L-lactide in the total lactide.

The polyether polyester (A) used in the present invention has the general formula 1

Embedded image (In the formula, m, x, y, and z are integers of 1 or more. R ₁ ,
R ₇ is hydrogen or a hydrocarbon group, R ₃ and R ₅ are aliphatic hydrocarbon groups in which the total number of methylene carbon atoms is 2 or more, and R ₂ , R ₄ ,
R ₆ has an alkylene group or the chemical structure of general formula 2.

General formula 2

[Chemical 6] (In the formula, R ₈ , R ₉ , and R ₁₀ are alkylene groups, and a,
b and c are 0 or an integer of 1 or more, and a + b + c is 1
It is an integer above the above. )

More specifically, R ₁ and R ₇ in the general formulas 1 and 2 are hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and R ₃
And R ₅ is an aliphatic hydrocarbon group having a total of 2 to 12 methylene carbon atoms and has R ₂ , R ₄ , R ₆ , R ₈ , R ₉ and R carbon atoms.
₁₀ is an alkylene group having a carbon number of 2 to 15 in the alkylene main chain or has the chemical structure of the general formula 2.

Specifically, methylene, ethylene, trime
Tylene [-(CH₂)₃-], Propylene, tetramethyl
, [CH₃CH₂C (CH₂−)₃], [-CH (CH₂
−)₂And divalent hydrocarbon groups such as ethylene,
Pyrene, [CH₃CH₂C (CH ₂−)₃], [-CH (C
H₂−)₂Is mentioned.

The polyether polyester (H) is a polyether polyol, a polyether polyester obtained by a dehydration reaction and a deglycolization reaction of a polyol and a dicarboxylic acid, or a polyether polyol,
It is a polyether polyester obtained by a dehydration reaction and a deglycol reaction of a polyol, a dicarboxylic acid, and a polyfunctional carboxylic acid having three or more functional groups (and / or its acid anhydride).

The polyether polyester (I) used in the present invention is a polyether polyester obtained by transesterifying a polyester obtained by a dehydration reaction and a deglycolization reaction between a polyol and a dicarboxylic acid with a polyether polyol. Alternatively, a polyester obtained by a dehydration reaction and a deglycol reaction of a polyol, a dicarboxylic acid and a polyfunctional carboxylic acid having a functionality of 3 or more (and / or an acid anhydride thereof) and a polyether polyol are transesterified. The obtained polyether polyester.

The polyether polyester (J) used in the present invention is a polyether obtained by transesterifying a polyester obtained by a dehydration reaction and a deglycolization reaction of a polyol and a dicarboxylic acid with a polyether polyol. It is a polyether polyester obtained by transesterifying a polyester with a polyfunctional carboxylic acid having a functionality of 3 or more (and / or its acid anhydride).

Further, these high molecular weight polyether polyesters (A), (H), (I) or (J) are used for the purpose of increasing the molecular weight of the resulting lactic acid-based copolymer,
The weight average molecular weight of the polyether polyester (A), (H), (I) or (J) is 10,000 to 3
0,000, number average molecular weight of 5,000 to 150,0
It is preferably 00.

Further, from the viewpoint of solubility of the polyether polyester and easiness of production, the polyether polyester (A), (H), (I) or (J) has a weight average molecular weight of 20,000 to 200,000. , Number average molecular weight is 1
It is more preferable that it is about 30,000 to 100,000.

Further, polyether polyester (A),
From the viewpoint of solubility and biodegradability, the structure of (H), (I) or (J) is preferably an aliphatic polyether polyester. Furthermore, an aliphatic polyether polyester in which the polyether polyol is 20 mol% or more based on the total mol% of the polyether polyol and the polyol is preferable because the resulting lactic acid-based copolymer has excellent heat resistance.

When the ratio of the lactide (E) to the polyether polyesters ((A), (H), (I), (J)) is 40/60 to 95/5, the lactic acid series obtained can be obtained. The heat resistance of the copolymer is increased. Furthermore, (A) /
When the ratio of ((A), (H), (I), or (J)) is 50/50 to 80/20, the heat resistance of the obtained high molecular weight lactide copolymer is higher. Very preferable.

The polyether polyesters ((H), (I), (J)) used in the present invention include aliphatic polyether polyesters in which the dicarboxylic acid component is an aliphatic dicarboxylic acid. Further, an aromatic polyether polyester composed of an aromatic dicarboxylic acid component or an aromatic / aliphatic polyether polyester composed of an aromatic dicarboxylic acid component and an aliphatic dicarboxylic acid component can also be used, but is biodegradable. Considering the above, an aliphatic polyether polyester is preferable.

The aliphatic dicarboxylic acid component in the polyether polyester used in the present invention is not particularly specified, but aliphatic dicarboxylic acids having 4 to 14 carbon atoms (and their acid anhydrides), and their methyl esters. And ethyl ester are preferred. Succinic acid,
Adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and their methyl esters, ethyl esters, succinic anhydride, hexahydrophthalic acid and the like are preferable.

The aromatic dicarboxylic acid component in the polyether polyester used in the present invention is not particularly specified, but specifically, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, phthalic anhydride,
Examples thereof include dimer acid. Other than these, alcohols with phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc., and esters with polyols can be mentioned.

With respect to the polyether polyol component in the polyether polyester used in the present invention, any polyether polyol may be used, including diols, triols and higher diols. Among them, polyethylene glycol, polypropylene glycol and ethylene oxide are preferred. Poly (oxyethylene-oxypropylene) glycol, poly (1,2-butylene glycol), poly (1,4-butylene glycol) and polyneopentyl glycol, which are copolymers of propylene oxide, are preferable,
Further considering biodegradability and versatility

Polyethylene glycol,

[Chemical 7]

Polypropylene glycol,

Embedded image

Poly (oxyethylene-oxypropylene) glycol,

[Chemical 9] Etc. are particularly preferable.

The weight average molecular weight of the polyether polyol (A) is preferably 200 to 200,000. Further, from the viewpoint of biodegradability, the polyether polyol (A) has a weight average molecular weight of 200 to 1
More preferably, it is about 10,000.

The polyol component in the polyether polyester is not particularly limited as long as it is a polyol, but among them, a polyol having 2 to 15 carbon atoms is preferable, and specifically, ethylene glycol, propylene glycol, butylene glycol, Pentane polyol, hexamethylene glycol, octane polyol, neopentyl glycol, cyclohexanedimethanol, xylene glycol,

Diethylene glycol, triethylene glycol, dipropylene glycol, dibutanediol,
Examples thereof include 3-hydroxypivalyl pivalate, glycerin, pentaerythritol, and hydrogenated bisphenol A.

The polyfunctional carboxylic acid component having three or more functional groups may be of any type, but among them, trimesic acid, propanetricarboxylic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, benzophenone. Tetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid,
Cyclohexane tetracarboxylic acid anhydride etc. are mentioned.

Particularly, trimellitic anhydride and pyromellitic dianhydride are preferable. The above-mentioned polyvalent carboxylic acids can be used as a mixture, if necessary. In particular, the amount of polycarboxylic acid used will be described below.

The polyether polyol (E), the polyol (F), the dicarboxylic acid (G) and the polyfunctional carboxylic acid having three or more functional groups (and / or its acid anhydride) (D) are dehydrated and removed. When the polyether polyester (H) is obtained by the glycol reaction, the proportion of the trifunctional or higher polycarboxylic acid (D) is 0.001 to 5 mol% with respect to the dicarboxylic acid (G) component. Preferably 0.0
When it is 1 to 1 mol%, the molecular weight and flexibility of the obtained high molecular weight lactic acid-based copolymer will be high.

Polyol (F) and dicarboxylic acid (G)
And a polyfunctional carboxylic acid having a functionality of 3 or more and / or an acid anhydride thereof (D) are dehydrated and deglycolized to give a polyester, and a polyether polyol (E) is subjected to an ester exchange reaction to obtain a polyester. When the ether polyester (I) is obtained, the proportion of the polyfunctional carboxylic acid (D) having 3 or more functional groups is preferably 0.001 to 5 mol% with respect to the dicarboxylic acid (G) component, and particularly 0.01 ~
When it is 1 mol%, the molecular weight and flexibility of the obtained high molecular weight lactic acid-based copolymer will be high.

Polyol (F) and dicarboxylic acid (G)
To the polyether polyester obtained by transesterifying the polyester obtained by dehydration reaction and deglycolization reaction with and the polyether polyol (E).
When a polyether polyester (J) is obtained by transesterification of a polyfunctional carboxylic acid having a functionality or higher and / or its acid anhydride (D),

The proportion of the polyfunctional carboxylic acid (D) having three or more functional groups is the polyester obtained by subjecting the polyol (F) and the dicarboxylic acid (G) to a dehydration reaction and a deglycolization reaction, and a polyether polyol (E). With respect to the components of the polyether polyester obtained by transesterification of and, 0.01 to 5% by weight is preferable, and particularly 0.1 to 1% by weight, the obtained high molecular weight lactic acid-based copolymer Has higher molecular weight and flexibility.

These trifunctional or higher polyvalent carboxylic acids (D)
By using, for example, a branched chain is introduced, the effect of increasing the molecular weight and the molecular weight distribution of the copolymer, the end of the produced copolymer is blocked and the thermal stability is increased, or A metal reacts with a carboxyl group having one or more functional groups of a carboxylic acid to convert the polymer into an ionomer, whereby a high molecular weight can be easily obtained, and a lactic acid-based copolymer that can be formed into a film or sheet having excellent physical properties can be obtained. Polymers can be produced.

When the high-molecular-weight lactic acid-based copolymer obtained by the present invention is formed into a sheet, a sheet having high strength to a flexible sheet can be obtained. Specifically, a sheet having a tensile viscoelasticity of 500 to 50,000 kg / cm ² is obtained.

The obtained lactic acid-based copolymer is further reacted with one or more compounds selected from the group consisting of oxycarboxylic acids, carboxylic acid anhydrides, isocyanates and lactones to further increase the molecular weight. be able to.
Specific examples thereof include oxycarboxylic acids such as citric acid, tartaric acid and malic acid, and carboxylic acid anhydrides such as acetic anhydride, succinic anhydride, propionic anhydride, phthalic anhydride and maleic anhydride. Acids, butyric anhydride, isobutyric anhydride, trimellitic anhydride, pyromellitic anhydride and the like.

As the isocyanates, phenyl isocyanate, hexamethylene diisocyanate, toluene-2,4-diisocyanate, naphthalene-1,
5-diisocyanate, triphenylmethane-4,
Examples of lactones such as 4 ′, 4 ″ -triisocyanate include β-caprolactone, ε-caprolactone, β-butyrolactone and δ-valerolactone.

To further react these compounds with the lactic acid-based copolymer, the lactic acid-based copolymer is mixed with the reaction product after the polymerization reaction of the lactic acid-based copolymer is completed, and the mixture is stirred and mixed in a molten state for a short time. Alternatively, the lactic acid-based copolymer obtained by polymerization may be added again and melt-mixed. Further, both the lactic acid-based copolymer and these compounds are dissolved in a common solvent,
After heating and reacting, it may be obtained by reprecipitation or degassing.

Particularly preferable for oxycarboxylic acids, carboxylic acid anhydrides, and lactones is a method in which these are added to the obtained lactic acid-based copolymer, melt-mixed, and then reacted under reduced pressure. Reaction time becomes faster.

The temperature for mixing and reacting is generally 60.degree.
It is 240 ° C, preferably 80 ° C to 190 ° C. In the reaction, an ester polymerization catalyst such as N, N-dimethylaniline, tin octoate, dibutyltin dilaurate or isopropyl titanate, or a urethane catalyst can be used. The degree of reduced pressure during the reaction is 100 Torr or less, preferably 10 Torr or less, more preferably 3T.
It is less than orr.

The amount of the oxycarboxylic acids, carboxylic acid anhydrides, isocyanates, and lactones used is preferably 0.001% to 5% by weight, more preferably 0.001% by weight to the lactic acid copolymer. It is 0.1% by weight.
This method is also preferable in that the used oxycarboxylic acids, carboxylic anhydrides, isocyanates, and lactones can be bonded to the terminal groups of the lactic acid-based copolymer to prevent the decomposition of the polymer into monomers by heat. .

In the production of the present invention, it is desirable to use the polymerization catalyst (C). Polymerization catalyst (C) used in the present invention
Examples thereof include metals such as tin, zinc, lead, titanium, bismuth, zirconium, and germanium, which are generally known as polymerization catalysts for cyclic esters and transesterification catalysts, and derivatives thereof. Of these derivatives, metal organic compounds, carbonates, oxides and halides are particularly preferable. Specifically, tin octoate, tin chloride, zinc chloride, zinc acetate, lead oxide, lead carbonate, titanium chloride, alkoxy titanium, germanium oxide, and zirconium oxide are suitable.

The polymerization catalyst (C) is used in an amount of lactide (B) and / or polyether polyester ((A),
0.005 to 0.2 with respect to the total of (H), (I) or (J)) and / or polyfunctional carboxylic acid (D) having 3 or more functional groups.
% Is preferable, and in order to obtain a sufficiently high polymerization rate and to reduce the coloring of the obtained lactide-based polyether polyester, 0.01 to 0.1% by weight is particularly preferable.

When a polyether polyester is produced by dehydrating and deglycolizing the trifunctional or higher polyvalent carboxylic acid (D), the dicarboxylic acid and the polyol,
It is also possible to use a catalyst. As the catalyst used in the present invention, any catalyst generally known as an esterification catalyst can be used, and examples thereof include tin, zinc, lead, titanium, antimony, cerium, germanium, and cobalt.
An organic or inorganic metal compound of at least one metal such as manganese, iron, aluminum, magnesium, calcium and strontium can be used.

For example, metal alkoxides, organic acid salts,
Chelates, oxides and the like are used, and organic compounds of titanium such as alkyl titanate, titanium oxyacetylacetonate and titanium oxalate are particularly useful. The amount of the catalyst used is preferably 0.001 to 0.5% by weight based on the total amount of the polyfunctional carboxylic acid (D) having 3 or more functional groups, the dicarboxylic acid and the polyol. The polymerization rate is sufficiently high, and in order to reduce the coloring of the obtained lactide-based polyether polyester, 0.01 to
0.1% by weight is preferred.

Next, a specific manufacturing method of the present invention will be described. When the polyether polyester (A) is reacted with the polyfunctional carboxylic acid having three or more functional groups (and / or its acid anhydride) (D), the reaction proceeds rapidly if the reaction is carried out under reduced pressure after melt mixing. Is preferable. The reaction in which the high molecular weight polyether polyester obtained by the reaction and the lactide (E) are mixed to carry out the polymerization is performed by heating and melting the mixture, or by diluting and mixing the reaction product with a solvent, and then the polymerization catalyst (F)
Is added.

Polyether polyol (E), polyol (F), dicarboxylic acid (G), and / or polyfunctional carboxylic acid having three or more functional groups (and / or its acid anhydride)
For the polymerization with (D), a dehydration reaction and a deglycolization reaction, which are general synthetic methods of polyester, are performed. The reaction in which the obtained polyether polyester (H) and lactide (B) are mixed and polymerized is performed by heating and melting the mixture, or by diluting and mixing the reaction product with a solvent, followed by polymerization catalyst (F).
Is added.

Polyol (F) and dicarboxylic acid (G)
And / or a trivalent or higher functional polycarboxylic acid (and / or its acid anhydride) (D) are polymerized by a dehydration reaction and a deglycolization reaction which are general polyester synthesis methods. Next, the obtained polyester and the polyether polyol (E) are melt-mixed, and then transesterified under reduced pressure. Obtained polyether polyester (I)
And the lactide (B) are mixed to carry out the polymerization,
The mixture is heated and melted, or the reaction product is diluted and mixed with a solvent, and then the polymerization catalyst (F) is added.

Polyol (F) and dicarboxylic acid (G)
Polymerization with and is carried out by a dehydration reaction and a deglycolization reaction which are general methods for synthesizing polyester. Next, the obtained polyester and the polyether polyol (E) are melt-mixed, and then transesterified under reduced pressure. Next, after melt-mixing the obtained polyether polyester and a polyfunctional carboxylic acid having three or more functional groups (and / or its acid anhydride),
The transesterification reaction is carried out under reduced pressure.

Obtained polyether polyester (J)
And the lactide (B) are mixed to carry out the polymerization,
The mixture is heated and melted, or the reaction product is diluted and mixed with a solvent, and then the polymerization catalyst (F) is added. The dehydration reaction and the deglycolization reaction, which are general methods for synthesizing polyesters, will be briefly described below.
It is preferable to carry out at ˜250 ° C. for 3 to 16 hours under an inert gas atmosphere.

In the deglycol reaction, the pressure is gradually reduced, and finally 170 to 26 is obtained under reduced pressure of 5 Torr or less.
It is preferable to carry out at 0 ° C. for 2 to 16 hours. The polyether polyester thus obtained ((A),
(H), (I), or (J)) and lactide (E) are heated and melted or mixed by adding a solvent,
When the polymerization catalyst (F) is added, it is preferable that the polymerization temperature is equal to or higher than the melting point of lactide, because the polymerization system can be homogenized and a high polymerization rate can be obtained.

The polymerization temperature in the solvent-free system is preferably not lower than the melting point of lactide and not higher than 185 ° C. in terms of the equilibrium of the polymerization, and coloring of the lactide polyether polyester due to the decomposition reaction can be prevented. The melting point of lactide is around 100 ° C., and a temperature of 100 ° C. or higher and 185 ° C. or lower, more preferably 145 to 180 ° C. is desirable in terms of polymerization equilibrium, and a decrease in the molecular weight and coloration of the lactide-based polyether polyester due to the decomposition reaction Can be prevented.

In order to prevent decomposition and coloring of lactide,
All reactions are preferably carried out under a dry, inert gas atmosphere. Particularly, it is performed under a nitrogen or argon gas atmosphere or in a bubbling state. At the same time, it is preferable to dry the polyether polyols and polyether polyesters, which are raw materials, by removing water by vacuum drying or the like.

Since lactide can be dissolved in a solvent,
Polymerization can be performed using a solvent, and specific examples of the solvent include benzene, toluene, ethylbenzene, xylene,
Examples thereof include cyclohexanone, methyl ethyl ketone, isopropyl ether and the like.

The high-molecular-weight lactic acid-based copolymer of the present invention can be batch-manufactured using an ordinary polymerization kettle. Further, the continuous manufacturing method can improve the product quality, yield and productivity. As the continuous production method, two or more agitated reactors connected in series, and / or a static mixer, and / or a horizontal reactor are used for all or part of the reaction process.

As the agitation reactor in which two or more are connected in series, the agitation method is changed as the reaction progresses, and the agitation reaction in which two or more tanks are connected in series can be performed with efficient agitation and temperature control. The use of a bath is preferred.

The static mixer mentioned here is
In contrast to a mixer with a stirrer, it is a static mixer with no moving parts, i.e. without a stirrer. Specifically, a mixing element with no moving parts fixed in the pipe divides the flow. In addition, it refers to a mixing device that mixes solutions by changing or reversing the flow direction and repeating division, conversion, and reversal of the flow in the vertical and horizontal directions. The horizontal reactor means not only an extruder such as a single-screw or twin-screw extruder used for reactive processing, but also a twin-screw reactor capable of circulation.

In these continuous production methods, polymerization can be carried out using a solvent or the like. As a result, the obtained high-molecular-weight lactic acid-based copolymer has a high melting point and a high melt viscosity, which makes it difficult to polymerize, but the addition of a solvent lowers the viscosity of the polymerization system, facilitates stirring, and facilitates polymerization. It will be easier to do.

Particularly when a continuous polymerization apparatus equipped with a static mixer is used, the extrusion pressure of the polymerization solution is lowered, and a polymerization apparatus having a heat medium internal device for the purpose of temperature control and a baffle plate for the purpose of stirring. Is effective because the equipment can be lightened. Since the stirring is easy, the temperature can be easily controlled, the temperature is uniform in the polymerization apparatus, and a high-molecular-weight lactic acid-based copolymer with less coloring is obtained.

Further, it is desirable to carry out devolatilization under reduced pressure for the purpose of removing lactide, solvent and odorous substances remaining in the latter stage of polymerization. By this devolatilization step, the amount of residual lactide can be reduced, and the storage stability of the obtained high molecular weight lactic acid-based copolymer can be significantly increased.

Residual lactide is not preferable because it causes hydrolysis due to adhesion of water or fusion due to heat when a high molecular weight lactide type polyether polyester is used as a sheet or film. In addition, it is not preferable because it is scattered by sublimation from the film or sheet that is commercialized. Therefore, the amount of residual lactide in the lactic acid-based copolymer of the present invention is preferably 2% by weight or less. More preferably, it is 1% by weight or less.

As a concrete devolatilization method, a single-screw or twin-screw extruder, a thin film distiller, a pot type depressurizing device and the like are used. As a devolatilization condition, a method of taking out while heating under reduced pressure after polymerization is preferable. In order to prevent the molecular weight of the lactic acid-based copolymer from decreasing, the devolatilization condition is that the devolatilization time is 10
Second to 10 minutes, temperature 100 to 230 ° C, decompression degree 0.1
It is preferable to carry out at about 200 Torr.

As another devolatilization method, there is a method in which after the completion of the polymerization, the lactic acid-based copolymer is pelletized or crushed and taken out under reduced pressure while heating. Also in this case, for the purpose of not reducing the molecular weight of the lactic acid-based copolymer, the devolatilization time is preferably 2 to 400 minutes, the temperature is 60 to 200 ° C., and the degree of vacuum is preferably 0.1 to 50 Torr.

When producing the copolymer of the present invention, a cyclic ester other than lactide (E) may be further added to produce a high molecular weight lactic acid-based copolymer. In particular, 1 to 20% by weight of lactone can be added for the purpose of softening. The cyclic ester to be added in addition to the lactide is not particularly limited, but specifically, a cyclic dimer of hydroxy acid such as glycolide or an intramolecular lactide, particularly β-butyrolactone, ε-caprolactone, γ- Examples thereof include valerolactone and γ-undecalactone.
When the amount of lactone increases, the glass transition point and melting point decrease, and the flexibility increases.

When the lactic acid-based copolymer of the present invention is formed into a sheet or film, a general filler such as talc,
An inorganic filler such as calcium carbonate, silica, clay, diatomaceous earth, or perlite, or an organic filler such as wood powder may be mixed and added. Also, 2,6-di-t-butyl-
Use antioxidants such as 4-methylphenol (BHT), butyl hydroxyanisole (BHA), salicylic acid derivatives, UV absorbers such as benzophenone and benzotriazole, and stabilizers such as phosphoric acid ester and carbodiimide. The thermal stability during molding can be improved.

The lactic acid-based copolymer of the present invention alone has sufficient plasticity and has good moldability. However, in order to achieve higher moldability and flexibility, dioctyl adipate and dioctyl sebacate are used. Alternatively, a plasticizer such as trioctyl trimellitate, diethyl phthalate, dioctyl phthalate, polypropylene glycol adipic acid, butanediol adipate may be added.

Metal soaps such as zinc stearate, magnesium stearate and calcium stearate,
Lubricants such as mineral oil, liquid paraffin, ethylene bis-stearyl amide, nonionic surfactants such as glycerin fatty acid ester and sucrose fatty acid ester, ionic surfactants such as alkyl sulfonate, titanium oxide, colorants such as carbon black May be added.

Further, by adding an inorganic foaming agent such as sodium bicarbonate or ammonium bicarbonate, an organic foaming agent such as azodicarbonamide, azobisisobutyronitrile or sulfonylhydrazide, or by adding pentane, butane,
A foaming agent such as freon may be impregnated in advance with the lactic acid-based copolymer of the present invention, or may be directly supplied into the extruder during the extrusion process to give a foam. It is also possible to make a multilayer with paper, aluminum foil, or other degradable polymer film by extrusion laminating, dry laminating or coextrusion.

The lactic acid-based polyether polyester copolymer obtained in the present invention has good biodegradability, and even if it is discarded after being used as a general-purpose resin, packaging material, or the like in the manufacturing process. Helps reduce the amount of waste.
When it is dumped in the soil or seawater, it is hydrolyzed, decomposed by microorganisms, etc., and its strength as a resin deteriorates within a few months, and it can be decomposed before its outer shape is maintained. In addition, if compost is used, it will be biodegraded in a shorter period of time before its original shape is retained.

[0102]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. All polyether polyols used in the examples were of diol type unless otherwise specified.

The molecular weight was measured by a GPC measuring device (hereinafter, abbreviated as GPC, column temperature 40 ° C., tetrahydrofuran solvent) in comparison with a polystyrene standard sample. Glass transition point and melting point are measured by differential scanning calorimeter (hereinafter DSC
Is omitted). Measurement conditions are 2 at 10 ° C / min
The temperature was raised from 0 ° C to 220 ° C.

Further, the measurement conditions of the tensile test were an initial sample length of 50 mm and a crosshead speed of 40 mm / min. The test piece was hot-pressed at 160 to 180 ° C., 20
250 μm prepared under conditions of 0 kg / cm ² and 2 minutes
A thick film was cut into a width of 15 mm and a length of 80 mm and measured.

The following equipment was used as the above equipment. GPC: TOSOH HLC-8020 (manufactured by Toso Corporation) DSC: DSC 200 (manufactured by Seiko Electronics Co., Ltd.) Tensile test: Tensilon (manufactured by Toyo Seiki Co., Ltd.)

Example 1 A 300 ml four-necked flask equipped with a stirrer, a rectifier, and a gas inlet tube was charged with 45 g of polypropylene glycol having a number average molecular weight of 400, 4.1 g of ethylene glycol and 25 g of sebacic acid, and charged with nitrogen. In the atmosphere, the mixture was heated and stirred while the temperature was raised from 150 ° C to 10 ° C / hour.

While distilling off the produced water, the temperature was raised to 220 ° C. After confirming that the water had stopped distilling, 0.01 g of titanium isopropyl titanate was added to 0.5 Torr.
The deglycolization reaction was carried out at 220 ° C. for 3 hours under reduced pressure. The obtained polyether polyester was a viscous liquid having a number average molecular weight of 18,000 and a weight average molecular weight of 33,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid-based polyether polyester obtained was transparent and had a number average molecular weight of 55,000 and a weight average molecular weight of 93,000 by GPC. Glass transition point is about 5
Observed at 0 ° C, melting point was about 156 ° C. The tensile breaking strain is 10% and the tensile breaking strength is 390 kgf / cm.
² , the initial tensile elastic modulus was 13,000 kgf / cm ² .

Example 2 A 300 ml four-necked flask equipped with a stirrer, a rectifier, and a gas introduction tube was charged with 21 g of ethylene glycol and 50 g of sebacic acid, and the temperature was changed from 150 ° C. to 10 ° C./hour in a nitrogen atmosphere. The mixture was heated and stirred while raising the temperature. While distilling off the produced water, the temperature was raised to 220 ° C, and after confirming that the distillation of water had stopped, 0.01 g of titanium isopropyl titanate was added and a deglycolization reaction was performed at 220 ° C under a reduced pressure of 0.5 Torr. Was carried out for 3 hours.
The obtained polyester (A-1) has a number average molecular weight of 20,
And a white solid having a weight average molecular weight of 35,000.

13 g of the obtained polyester (A-1),
Polypropylene glycol 6 with number average molecular weight of 3,000
0g 200ml with stirrer, rectifier, gas inlet pipe
In a 4-necked flask, and under a reduced pressure of 0.5 Torr,
The deglycol reaction was performed at 220 ° C. for 3 hours. The obtained polyether polyester (A-2) has a number average molecular weight of 2
It was a viscous liquid having a weight average molecular weight of 1,000 and 1,000.

Polyether polyester 10 obtained
g, L-lactide 85 g, D-lactide 5 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid-based polyether polyester obtained was transparent and had a number average molecular weight of 87,000 and a weight average molecular weight of 150,000 as measured by GPC. A glass transition point was observed at about 53 ° C and a melting point was about 158 ° C. Also,
Tensile breaking strain is 6%, Tensile breaking strength is 490kgf / cm
² , the initial tensile elastic modulus was 21,000 kgf / cm ² .

[Example 3] 30 g of the polyether polyester (A-2) obtained in Example 2 and L-lactide 6
8 g, D-lactide 2 g, toluene 10 ml, 20
Place in a 0 ml separable flask and under nitrogen atmosphere, 1
The mixture was melted and mixed at 75 ° C. for 0.25 hours, and 0.03 g of tin octoate was added.

After reacting for 3 hours, the produced copolymer was taken out. The obtained lactic acid-based polyether polyester was transparent and had a number average molecular weight of 72,000 and a weight average molecular weight of 120,000 as measured by GPC. The glass transition point was observed at about 53 ° C, although slightly, and the melting point was about 158 ° C. The tensile breaking strain is 11% and the tensile breaking strength is 420.
kgf / cm ² , initial tensile elastic modulus is 19,000 kgf
Was / cm ² .

Example 4 50 g of the polyether polyester (A-2) obtained in Example 2 and L-lactide 4
8 g, D-lactide 2 g, toluene 10 ml, 20
Place in a 0 ml separable flask and under nitrogen atmosphere, 1
The mixture was melted and mixed at 75 ° C. for 0.25 hours, and 0.03 g of tin octoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid-based polyether polyester obtained was transparent and had a number average molecular weight of 52,000 and a weight average molecular weight of 71,000 by GPC. The glass transition point was observed at about 53 ° C, although it was slight, and the melting point was about 153 ° C. The tensile breaking strain is 200%, and the tensile breaking strength is 3
50 kgf / cm ² , initial tensile elastic modulus is 6,200 kg
f / cm ² .

Example 5 In a 300 ml four-necked flask equipped with a stirrer, a rectifier, and a gas introduction tube, 90 g of polypropylene glycol having a number average molecular weight of 3,000, 2.0 g of ethylene glycol, and 8.7 g of sebacic acid. Charge
Under a nitrogen atmosphere, the mixture was heated and stirred while increasing the temperature from 150 ° C to 10 ° C / hour. 220 ° C while distilling off the water produced
After confirming that the temperature has risen to 0 and the distillation of water has stopped, 0.01 g of titanium isopropyl titanate is added to 0.5 Torr.
The deglycolization reaction was carried out at 220 ° C. for 3 hours under reduced pressure of r.

The obtained polyether polyester was a viscous liquid having a number average molecular weight of 19,000 and a weight average molecular weight of 32,000. 30 g of the obtained polyether polyester, 68 g of L-lactide, 2 g of D-lactide, and 10 ml of toluene were placed in a 200 ml separable flask, and melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours to obtain tin octanoate. 0.03 g was added.

After reacting for 3 hours, the produced copolymer was taken out. The obtained lactic acid-based polyether polyester was transparent and had a number average molecular weight of 45,000 and a weight average molecular weight of 88,000 as measured by GPC. A glass transition point was observed at about 50 ° C and a melting point was about 156 ° C. The tensile strain at break of 10%, a tensile break strength of 360 kgf / cm ^2, the tensile initial modulus of 18,000kgf / cm ^2.

Example 6 A 300 ml four-necked flask equipped with a stirrer, a rectifier, and a gas inlet tube was charged with 26 g of propylene glycol and 50 g of sebacic acid, and under a nitrogen atmosphere at 150 ° C. to 10 ° C./hour. The mixture was heated and stirred while raising the temperature. While distilling off the produced water, the temperature was raised to 220 ° C, and after confirming that the distillation of water had stopped, 0.01 g of titanium isopropyl titanate was added and a deglycolization reaction was performed at 220 ° C under a reduced pressure of 0.5 Torr. Was carried out for 3 hours.

The resulting polyester has a number average molecular weight of 1.
It was a viscous liquid having a molecular weight of 7,000 and a weight average molecular weight of 28,000. 14 g of the obtained polyester and 60 g of polypropylene glycol having a number average molecular weight of 3,000 were charged into a 200 ml four-necked flask equipped with a stirrer, a rectifier, and a gas introduction tube, and 220 ° C. under a reduced pressure of 0.5 Torr.
The deglycolization reaction was carried out for 3 hours. The obtained polyether polyester was a viscous liquid having a number average molecular weight of 20,000 and a weight average molecular weight of 35,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

Lactic acid-based polyether polyester obtained
Is transparent and has a number average molecular weight of 61,000 from GPC and a weight of
The average molecular weight was 120,000. Glass transition point is approx.
It was observed at 53 ° C and the melting point was found to be about 152 ° C. Well
Also, tensile breaking strain is 15%, tensile breaking strength is 330kgf
/ Cm² , Initial tensile elastic modulus is 12,000 kgf / cm
² Met.

Example 7 A 300 ml four-necked flask equipped with a stirrer, a rectifier and a gas inlet tube was charged with 110 g of polyethylene glycol having a number average molecular weight of 2,000, 3.2 g of ethylene glycol and 16 g of sebacic acid. The mixture was heated and stirred under a nitrogen atmosphere while increasing the temperature from 150 ° C to 10 ° C / hour.

While distilling off the produced water, the temperature was raised to 220 ° C., and after confirming that the water had stopped distilling, 0.01 g of titanium isopropyl titanate was added and dewatered at 220 ° C. under a reduced pressure of 0.5 Torr. The glycol reaction was carried out for 3 hours.
The obtained polyether polyester has a number average molecular weight of 1
The solid was 8,000 and the weight average molecular weight was 33,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid-based polyether polyester obtained was transparent and had a number average molecular weight of 45,000 and a weight average molecular weight of 88,000 as measured by GPC. Glass transition point is about 5
Observed at 0 ° C, melting point was about 156 ° C. The tensile breaking strain is 120% and the tensile breaking strength is 200 kgf / c.
m ² , and the initial tensile elastic modulus was 7,100 kgf / cm ² .

Example 8 In a 300 ml four-necked flask equipped with a stirrer, a rectifier, and a gas introduction tube, 140 g of polyethylene glycol having a number average molecular weight of 20,000, 1.0 g of ethylene glycol, and 2.0 g of sebacic acid. Was charged and heated and stirred under a nitrogen atmosphere while raising the temperature from 150 ° C. to 10 ° C./hour.

While distilling off the produced water, the temperature was raised to 220 ° C. After confirming that the water had stopped distilling, 0.01 g of titanium isopropyl titanate was added to 0.5 Torr.
The deglycolization reaction was carried out at 220 ° C. for 3 hours under reduced pressure. The obtained polyether polyester was a solid having a number average molecular weight of 42,000 and a weight average molecular weight of 58,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid type polyether polyester obtained was transparent and had a number average molecular weight of 72,000 and a weight average molecular weight of 130,000 as measured by GPC. A glass transition point was observed at about 50 ° C and a melting point was about 152 ° C. Also,
Tensile breaking strain is 94%, Tensile breaking strength is 210kgf / c
m ² and initial tensile elastic modulus were 6,800 kgf / cm ² .

Example 9 A 300 ml four-necked flask equipped with a stirrer, a rectifier, and a gas inlet tube was charged with 57 g of ethylene glycol and 100 g of adipic acid, and the temperature was changed from 150 ° C. to 10 ° C./hour in a nitrogen atmosphere. The mixture was heated and stirred while raising the temperature. The temperature was raised to 200 ° C. while distilling off the produced water, and after confirming that the distillation of water had stopped, a deglycolization reaction was carried out at 200 ° C. for 30 minutes under reduced pressure of 3 Torr.

714 g of polypropylene glycol having a number average molecular weight of 3,000 and 0.01 g of titanium isopropyl titanate were added thereto, and the pressure was reduced to 0.5 Torr.
The deglycol reaction was carried out at 00 ° C. for 3 hours. The resulting polyether polyester (A-3) has a number average molecular weight of 2
It was a viscous liquid having a weight average molecular weight of 5,000 and 40,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid-based polyether polyester obtained was transparent and had a number average molecular weight of 610,000 and a weight average molecular weight of 11,000 according to GPC. A glass transition point was observed at about 50 ° C and a melting point was about 152 ° C. Also,
Tensile breaking strain is 27%, Tensile breaking strength is 280kgf / c
m ² and initial tensile elastic modulus were 10,000 kgf / cm ² .

Example 10 A 3 l four-necked flask equipped with a stirrer, a rectification unit, and a gas introduction tube was charged with 71 g of ethylene glycol and 100 g of succinic acid, and the mixture was placed under a nitrogen atmosphere.
The mixture was heated and stirred while the temperature was raised from 150 ° C to 10 ° C / hour. While distilling off the produced water, the temperature was raised to 200 ° C., and after confirming that the distillation of water had stopped, under reduced pressure of 3 Torr,
The deglycol reaction was performed at 200 ° C. for 30 minutes.

To this, 890 g of polypropylene glycol having a number average molecular weight of 3,000 and 0.01 g of titanium isopropyl titanate were added, and the pressure was reduced to 0.5 Torr.
The deglycol reaction was carried out at 00 ° C. for 3 hours. The obtained polyester was a viscous liquid having a number average molecular weight of 22,000 and a weight average molecular weight of 39,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid-based polyether polyester obtained was transparent and had a number average molecular weight of 720,000 and a weight average molecular weight of 12,000 according to GPC. A glass transition point was observed at about 50 ° C and a melting point was found to be about 152 ° C. The tensile breaking strain is 29% and the tensile breaking strength is 270 kgf.
/ Cm ² , initial tensile elastic modulus is 10,000 kgf / cm ²
Met.

Example 11 In a 300 ml four-necked flask equipped with a stirrer, a rectifier, and a gas introduction tube, 30 g of the polyether polyester (A-3) obtained in Example 9 was added.
0.18 g of pyromellitic dianhydride (hereinafter abbreviated as PMDA) was charged, and a deglycol reaction was carried out at 200 ° C. for 3 hours under a reduced pressure of 0.5 Torr. The obtained polyester was a viscous liquid having a number average molecular weight of 33,000 and a weight average molecular weight of 90,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The obtained lactic acid type polyether polyester was transparent, and the number average molecular weight was 65,000, the weight average molecular weight was 13,000, the glass transition point was observed at about 53 ° C. and the melting point was about 150 ° C. by GPC. . The tensile breaking strain was 43%, the tensile breaking strength was 220 kgf / cm ² , and the initial tensile elastic modulus was 9,100 kgf / cm ² .

Example 12 A 300-ml four-necked flask equipped with a stirrer, a rectifier, and a gas inlet tube was charged with 57 g of ethylene glycol, 100 g of adipic acid, and 0.6 g of pyromellitic dianhydride, and under a nitrogen atmosphere, 150 ° C to 1
The mixture was heated and stirred while raising the temperature at 0 ° C./hour. The temperature was raised to 200 ° C. while distilling off the produced water, and after confirming that the distillation of water had stopped, a deglycolization reaction was carried out at 200 ° C. for 30 minutes under reduced pressure of 3 Torr.

719 g of polypropylene glycol having a number average molecular weight of 3,000 and 0.01 g of titanium isopropyl titanate were added thereto, and the pressure was reduced to 0.5 Torr.
The deglycol reaction was carried out at 00 ° C. for 3 hours. The obtained polyether polyester has a number average molecular weight of 25,000,
It was a viscous liquid having a weight average molecular weight of 40,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out. The resulting lactic acid-based polyether polyester was transparent and had a number average molecular weight of 51,000 and a weight average molecular weight of 110,000 as measured by GPC. A glass transition point was observed at about 50 ° C and a melting point was about 152 ° C. The tensile breaking strain is 31%, the tensile breaking strength is 330 kgf / cm ² , and the initial tensile elastic modulus is 1.
It was 50,000 kgf / cm ² .

Example 13 13 g of the polyester (A-1) obtained in Example 2 and a block copolymer of polyethylene glycol and polypropylene glycol having a number average molecular weight of 4,025 (PE-75 manufactured by Sanyo Chemical Industry Co., Ltd.) )
200m with 80g equipped with stirrer, rectifier, gas inlet pipe
It was charged in a 4-necked flask having a volume of 1 and subjected to a deglycolization reaction at 220 ° C. for 3 hours under a reduced pressure of 0.5 Torr. The obtained polyether polyester has a number average molecular weight of 25,0.
And a viscous liquid having a weight average molecular weight of 44,000.

Polyether polyester 30 obtained
g, L-lactide 68 g, D-lactide 2 g, and toluene 10 ml were charged in a 200 ml separable flask, melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours, and 0.03 g of tin octanoate was added. After reacting for 3 hours, the produced copolymer was taken out.

The obtained lactic acid type polyether polyester was transparent, and the number average molecular weight was 57,000, the weight average molecular weight was 83,000, the glass transition point was observed at about 50 ° C. and the melting point was about 152 ° C. by GPC. . The tensile strain at break of 32%, a tensile break strength of 310kgf / cm ^2, the tensile initial modulus of 10,000kgf / cm ^2.

Example 14 11 g of the polyester (A-1) obtained in Example 2 and a block copolymer of polyethylene glycol and polypropylene glycol having a number average molecular weight of 4,025 (PE-75 manufactured by Sanyo Chemical Industry Co., Ltd.) )
90 g, triol type block copolymer of polyethylene glycol and polypropylene glycol having a number average molecular weight of 3,000 (GL-3000 manufactured by Sanyo Kasei Co., Ltd.)
200 g equipped with a stirrer, rectifier and gas inlet pipe
It was charged in a 4-necked flask having a volume of 1 and the deglycolization reaction was carried out at 220 ° C. for 3 hours under a reduced pressure of 0.5 Torr.

The obtained polyether polyester was a viscous liquid having a number average molecular weight of 31,000 and a weight average molecular weight of 59,000. 30 g of the obtained polyether polyester, 68 g of L-lactide, 2 g of D-lactide, and 10 ml of toluene were placed in a 200 ml separable flask, and melted and mixed under a nitrogen atmosphere at 175 ° C. for 0.25 hours to obtain tin octanoate. 0.03 g was added. After reacting for 3 hours, the produced copolymer was taken out.

The lactic acid type polyether polyester obtained was transparent and had a number average molecular weight of 79,000 and a weight average molecular weight of 130,000 by GPC. A glass transition point was observed at about 51 ° C and a melting point was about 152 ° C. Also,
Tensile breaking strain is 40%, tensile breaking strength is 290kgf / c
m ² and initial tensile elastic modulus were 10,000 kgf / cm ² .

The lactic acid-based copolymerized polyether polyester obtained in Example 3 was hot pressed to a thickness of 10 c.
A m × 10 cm, 100 μm sheet was prepared. 165
The weight average molecular weight of the sheet obtained under the pressing conditions of 200 ° C., 200 kg / cm ² and 2 minutes was 117,000. This sheet was embedded in soil and a biodegradation test was tried. The results are shown in Table 1.

[0154]

[Table 1]

Comparative Example 1 100 g of L-lactide,
Toluene (15 ml) was added, and the mixture was mixed under nitrogen atmosphere to give 17
The mixture was dissolved and mixed at 5 ° C. for 0.25 hours, 0.03 g of tin octoate was added as a ring-opening polymerization catalyst, and polymerization was performed for 3 hours. After the reaction, toluene was removed under reduced pressure. Generated L-
Polylactic acid was a colorless and transparent resin having a weight average molecular weight of 273,000 and a number average molecular weight of 140,000. It had a glass transition point of about 57 ° C and a melting point of about 158 ° C. The tensile breaking strain is 3% and the tensile breaking strength is 500 kgf / c.
m ² and initial tensile elastic modulus were 16,000 kgf / cm ² .

Comparative Example 2 To 70 g of L-lactide, 30 g of polycaprolactone (“Tone” manufactured by UCC) and 15 g of toluene were added, and 175 were added under a nitrogen gas atmosphere.
The mixture was dissolved and mixed at 0 ° C. for 0.25 hours, 0.03 g of tin octoate was added as a ring-opening polymerization catalyst, and polymerization was carried out for 3 hours. After the reaction, toluene was removed under reduced pressure. The lactide-based copolymerized polyether polyester thus produced was a white resin having a weight average molecular weight of 223,000 and a number average molecular weight of 110,000. It has a glass transition point of about 47 ° C, a melting point of about 149 ° C, a tensile breaking strain of 30%, a tensile breaking strength of 250 kgf / cm ² , and an initial tensile elastic modulus of 13,000.
It was kgf / cm ² .

The measurement results of the lactic acid-based copolymers obtained in Examples and Comparative Examples are shown in Tables 2 to 3. The abbreviations in the table indicate the following contents.

Sebacic acid: SeA Adipic acid: AA Succinic acid: SA Pyromellitic dianhydride: PMDA

Ethylene glycol: EG Propylene glycol: PG Polyethylene glycol: PEG Polypropylene glycol: PPG Block copolymer of PEG and PPG: EbP Triol type block copolymer of PEG and PPG: tE
bP

[0160]

[Table 2]

[0161]

[Table 3]

[0162]

[Table 4]

[0163]

[Table 5]

[0164]

[Table 6]

[0165]

INDUSTRIAL APPLICABILITY The present invention provides a method for producing a biodegradable lactic acid-based polyether polyester having sufficient high molecular weight, heat resistance and heat stability, and having rigidity, flexibility and transparency depending on the use. Can be provided.

Claims (22)

[Claims] 1. A polyether polyester (A) having a repeating unit represented by the general formula 1, and a general formula 1 (In the formula, m, x, y, and z are integers of 1 or more. R ₁ ,
R ₇ is hydrogen or a hydrocarbon group, R ₃ and R ₅ are aliphatic hydrocarbon groups in which the total number of methylene carbon atoms is 2 or more, and R ₂ , R ₄ ,
R ₆ has an alkylene group and / or the chemical structure of general formula 2. General formula 2 (In the formula, R ₈ , R ₉ , and R ₁₀ are alkylene groups, and a,
b and c are 0 or an integer of 1 or more, and a + b + c is 1
It is an integer above the above. ) A method for producing a lactic acid-based polyether polyester, which comprises copolymerizing lactide (B) in the presence of a polymerization catalyst (C). 2. The polyether polyester (A) is 3
Functional polycarboxylic acid (and / or its acid anhydride)
The method for producing a lactic acid-based polyether polyester according to claim 1, which is a polyether polyester having a high molecular weight in (D). 3. The lactic acid according to claim 1, wherein the polyether polyester (A) has a molar ratio of ether groups to ester groups in the polyether polyester of 999/1 to 200/800. Of producing a polyether polyether polyester. 4. The lactic acid according to claim 1, wherein the weight ratio of the polyether polyester (A) and the lactide (B) is 60/40 to 5/95. Of producing a polyether polyether polyester. 5. A polyether polyol (E), a polyol (F), a dicarboxylic acid (G), and / or 3.
Copolymerization of a polyether polyester (H) obtained by reacting a polyfunctional carboxylic acid having a functionality or higher and / or its acid anhydride (D) with a lactide (B) in the presence of a polymerization catalyst (C). A method for producing a lactic acid-based polyether polyester, which comprises: 6. The polyether polyester (H) according to claim 5, wherein the molar ratio of the ether group to the ester group in the polyether polyester (H) is 999/1 to 200/800. Method for producing lactic acid-based polyether polyester. 7. The lactic acid-based polyether polyester according to claim 5 or 6, wherein the weight ratio of the polyether polyester (H) and the lactide (B) is 60/40 to 5/95. Production method. 8. The polyether polyol (E) is one or more polyether polyols selected from polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene) glycol which is a copolymer of ethylene oxide and propylene oxide. The method for producing a lactic acid-based polyether polyester according to any one of claims 5 to 7, wherein 9. The lactic acid-based polyether polyester according to claim 5, wherein the polyol (F) is one or more kinds of diols selected from ethylene glycol and propylene glycol. Production method. 10. The dicarboxylic acid (G) is one or more dicarboxylic acids selected from succinic acid, adipic acid, sebacic acid, and acid anhydrides thereof, and their methyl esters and ethyl esters. The method for producing a lactic acid-based polyether polyester according to any one of claims 5 to 7. 11. A polyester comprising a polyol (F), a dicarboxylic acid (G), and / or a polyfunctional carboxylic acid having 3 or more functional groups and / or its acid anhydride (D),
A lactic acid-based polycharacterized by copolymerizing a polyether polyester (I) obtained by transesterification with a polyether polyol (E) and a lactide (B) in the presence of a polymerization catalyst (C). Method for producing ether polyester. 12. The polyether polyester (I) is
The method for producing a lactic acid-based polyether polyester according to claim 11, wherein the molar ratio of the ether group to the ester group in the polyether polyester is 999/1 to 200/800. 13. The lactic acid-based polyether polyester according to claim 11 or 12, wherein the weight ratio of the polyether polyester (I) and the lactide (B) is 60/40 to 5/95. Production method. 14. The polyether polyol (E) is one or more polyether polyols selected from polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene) glycol which is a copolymer of ethylene oxide and propylene oxide. The method for producing a lactic acid-based polyether polyester according to any one of claims 11 to 13, characterized in that it is present. 15. The lactic acid-based polyether polyester according to claim 11, wherein the polyol (F) is one or more kinds of diols selected from ethylene glycol and propylene glycol. Production method. 16. The dicarboxylic acid (G) is one or more dicarboxylic acids selected from succinic acid, adipic acid, sebacic acid, and acid anhydrides thereof, and their methyl esters and ethyl esters. Claim 11
13. The method for producing a lactic acid-based polyether polyester according to any one of 1 to 13. 17. A polyether polyester obtained by reacting a polyester obtained by reacting a polyol (F) with a dicarboxylic acid (G), and a polyether polyester obtained by reacting a polyether polyol (E), with a polyfunctionality of 3 or more. Lactic acid characterized by copolymerizing a polyether polyester (J) obtained by reacting a carboxylic acid (and / or its acid anhydride) with a lactide (B) in the presence of a polymerization catalyst (C). Of producing a polyether polyether polyester. 18. The polyether polyester (J) comprises:
The method for producing a lactic acid-based polyether polyester according to claim 17, wherein the molar ratio of the ether group and the ester group in the polyether polyester is 999/1 to 200/800. 19. The lactic acid-based polyether polyester according to claim 17 or 18, wherein the weight ratio of the polyether polyester (J) and the lactide (B) is 60/40 to 5/95. Production method. 20. The polyether polyol (E) is one or more polyether polyols selected from polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene) glycol which is a copolymer of ethylene oxide and propylene oxide. The method for producing a lactic acid-based polyether polyester according to any one of claims 17 to 19, wherein: 21. The lactic acid-based polyether polyester according to claim 17, wherein the polyol (F) is one or more kinds of diols selected from ethylene glycol and propylene glycol. Production method. 22. The dicarboxylic acid (G) is one or more kinds of dicarboxylic acids selected from succinic acid, adipic acid, sebacic acid, and acid anhydrides thereof, and their methyl esters and ethyl esters. Claim 17
20. The method for producing a lactic acid-based polyether polyester according to any one of 1 to 19.