JP3448927B2 - Method for producing lactone-based copolymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lactone copolymer by subjecting a polyester polymer containing an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid to a lactone ring-opening addition polymerization and a transesterification reaction. . The lactone copolymer according to the present invention has decomposability, strength and flexibility, and is useful as a molding resin, a film material, an ink / paint resin, a paper lamination, a laminated film and an adhesive.

[0002]

In Japanese Patent Publication No. 48-4115, an aromatic polyester such as polyethylene terephthalate,
A production method for reacting with an intramolecular lactone such as ε-caprolactone or γ-valerolactone lactone is described. This technique attempts to give crystalline, hard polyesters elasticity by reacting them with lactones.

However, when an aromatic polyester such as polyethylene terephthalate is reacted with an intramolecular lactone such as ε-caprolactone or γ-valerolactone lactone, the crystalline and hard aromatic polyester is difficult to mix with the solvent. Moreover, since it is difficult to mix with lactones, it is difficult to carry out the reaction rapidly at low temperature.

Therefore, when the reaction of a polyester such as polyethylene terephthalate, which has fluidity only at high temperature, with ε-caprolactone, the reaction requires a high temperature of 250 ° C. or more, which is the flow starting temperature of polyethylene terephthalate. However, since the boiling point of ε-caprolactone is exceeded at this temperature, it is necessary to carry out the reaction under high pressure. Therefore, in the reaction under high temperature and high pressure, the produced polymer is colored due to decomposition due to a slight amount of residual oxygen in the reaction system.

[0005]

The problem to be solved by the present invention is that it can be reacted at a low temperature and a low viscosity without problems such as pressure reaction and stirring, has a decomposability, and has a molding property. 500 to 2 in tensile viscoelasticity having strength and flexibility applicable to resins, resins for packaging materials such as films and sheets, resins for inks, and lamination resins for paper
It is intended to provide a method for producing a lactone-based copolymer having a strength of 10,000 kg / cm ² .

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have made earnest studies and, as a result, made up of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid component, and a diol component, and had a weight average molecular weight. The polyester having a content of 20,000 to 400,000 is amorphous due to the properties of the dicarboxylic acid constituting it, has fluidity at low temperature, and easily mixes with the lactone to form a homogeneous system. It is found that the lactone copolymer according to the present invention has a high strength, and can be easily dissolved in a solvent and the like, and the reaction content can be reacted with a low viscosity without problems such as stirring. They have found that they have flexibility and can be widely used as general-purpose resins, and completed the present invention.

That is, according to the present invention, a polyester (B) containing a lactone (A), a repeating unit of an aromatic dicarboxylic acid component and a diol component, and a repeating unit of an aliphatic dicarboxylic acid component and a diol component as essential constituents.
Is a reaction method in the presence of a ring-opening polymerization catalyst (C), which is a method for producing a lactone-based copolymer.

More specifically, the production method is such that the weight ratio of the lactone (A) is 70 to 99 parts by weight with respect to the total 100 parts by weight of the lactone (A) and the polyester (B). B) has a weight average molecular weight of 2
The aromatic dicarboxylic acid of 10,000 to 400,000 is terephthalic acid and / or isophthalic acid, and the aliphatic dicarboxylic acid is an aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and the weight average molecular weight is 20,000 to 400,000. A production method of a certain polyester, more preferably a production method of a lactone-based copolymer, wherein the polyester (B) has a melting point or a softening point of 180 ° C. or lower.

Further, the present invention includes a production method in which the lactone (A) and the polyester (B) are reacted in a continuous reaction apparatus equipped with a static mixer. Hereinafter, the present invention will be described in more detail.

In the present invention, in order to improve the crystallinity, high melting temperature, and poor compatibility with other compounds of aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, not only aromatic dicarboxylic acids are used. It is important to polymerize the copolymer using a polyester with an aliphatic dicarboxylic acid component. By incorporating the aliphatic dicarboxylic acid, the non-crystallinity of the polyester is increased, the melting point or the softening point is lowered, and the lactone is easily mixed and reacted at a low temperature.

Regarding the lactones used in the present invention,
The type is not particularly limited, but propiolactone, butyrolactone, caprolactone, valerolactone, undecalactone, methylcaprolactone and the like are preferable. In particular, among caprolactone, valerolactone, undecalactone, methylcaprolactone, etc., those having a 5- to 7-membered ring structure are preferable, and in order to obtain a highly pure lactone and obtain a high molecular weight copolymer, Epsilon-caprolactone is particularly preferred.

As for the lactone used in the present invention, ε-caprolactone has a boiling point of around 230 ° C., but a high reaction rate can be obtained at a high temperature of 210 ° C. or higher. On the other hand, the boiling point of valerolactone is around 205 ° C., and it tends to evaporate from around 195 ° C., making it difficult to carry out the reaction at high temperatures. Moreover, it is difficult to obtain high-purity undecalactone, methylcaprolactone and the like. Therefore, the lactone used in the present invention is
Those containing 75% or more of ε-caprolactone in the total lactone are preferable, and in order to realize a higher molecular weight copolymer,
Those containing 90% or more of ε-caprolactone in the total lactone are preferable.

The polyester (B) used in the present invention is
It has structural units of both aromatic dicarboxylic acid and aliphatic dicarboxylic acid. Polyester (B) used in the present invention
Is particularly preferably an amorphous polyester having a melting point or softening point of 180 ° C. or lower, which is easy to mix with lactones and allows the reaction to be carried out quickly. When the polyester used is transparent, the obtained lactone-based copolymer is semitransparent, and depending on the use, it is preferable to use transparent polyester.

Further, in order to obtain a high-molecular-weight lactone-based copolymer, it is preferable that the polyester (B) has a high molecular weight, specifically, a weight average molecular weight of 20,000-.
It is preferably 400,000 , and the molar ratio of the dicarboxylic acid component and the diol component is preferably about 1.
The amount ratio of the aliphatic carboxylic acid and the aromatic carboxylic acid is not particularly limited, but it is preferable that the aliphatic dicarboxylic acid is contained in the total dicarboxylic acid in a molar ratio of 10 to 50%.

Further, more specifically, the aromatic dicarboxylic acid in the polyester (B) is preferably phthalic acid, isophthalic acid and / or terephthalic acid, and other examples include 2,6-naphthalenedicarboxylic acid. . The aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Specific examples include succinic acid, adipic acid, azelaic acid, sebacic acid, brassic acid, and cyclohexanedicarboxylic acid. In addition to these, dimer acid and the like can also be mentioned.

The diol component is not particularly limited so long as it is a diol, but ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexamethylene glycol, octanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol. A, xylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, dibutanediol, 3-hydroxypivalyl pivalate and the like can be mentioned.

According to the production method of the present invention, a lactone-based copolymer can be obtained irrespective of the amount ratio of the lactone (A) and the polyester (B), but one having a flexible property at room temperature is obtained. To achieve this, the weight ratio (A) / (B) is 1
It is preferably 5/85 to 99/1. More preferably, the weight ratio (A) / (B) is preferably 25/75 to 95/5.

It is desirable to use a ring-opening polymerization catalyst (C) in the polymerization reaction, and when the polymerization is traced by GPC, initially,
A low molecular weight fraction attributable to the polyester (B) and a relatively high molecular weight fraction attributable to the copolymer containing the lactone (A) or the homopolymer of the lactone were observed. It is considered that the transesterification reaction is occurring due to a single fraction of. By sufficiently performing this transesterification reaction, a lactone-based copolymer containing no homopolymer is obtained.

As the ring-opening polymerization catalyst (C) used in the present invention, any esterification catalyst that can be used in polyester synthesis can be used without any problems, but among them, it is also known as a ring-opening polymerization catalyst for cyclic esters and a transesterification catalyst. Tin,
Metals such as zinc, lead, titanium, bismuth, zirconium, and germanium and derivatives thereof are preferable, and metal organic compounds, carbonates, oxides, and halides of the derivatives, more specifically, tin octoate, tin chloride, Zinc acetate, zinc chloride, lead oxide, lead carbonate, titanium chloride, alkoxy titanium, germanium oxide and zirconium oxide are preferred.

In producing the lactone copolymer of the present invention, in addition to lactone (A), polyester containing aromatic dicarboxylic acid and aliphatic dicarboxylic acid (B) and ring-opening polymerization catalyst (C), lactide and the like. It is also possible to prepare a lactone-based copolymer by adding the intermolecular cyclic ester (1) or lactone having an aromatic ring.

The cyclic ester to be added further includes
Lactides such as dilactide and glycolide, aromatic rings
Trisalicylide and hexasalicid as lactones
Carbolactones such as lids, phthalides and coumarins are listed.
You can When the amount of glycolide and lactone increases
The glass transition temperature becomes high and the hardness becomes high. When the total weight of the lactone (A) and the polyester (B) is 100 parts, the addition amount is preferably 50 parts or less, and when hardness and transparency are required, it is preferably 50 parts or more. .

Next, the manufacturing method will be specifically described. The lactone (A) and the polyester (B) are melted or uniformly mixed with a solvent, and then the ring-opening polymerization catalyst (C) is added.
The reaction temperature is preferably 120 ° C or higher and 280 ° C or lower so that a sufficient reaction rate can be obtained and the obtained lactone-based copolymer is not easily decomposed. Particularly, when the temperature is 150 ° C or higher and 250 ° C or lower, the reaction is completed within 8 hours. However, it is possible to prevent the lactone-based copolymer from being colored due to the decomposition reaction.

Particularly, since the melting point or softening point of the polyester (B) used in the present invention is 180 ° C. or lower, both are mixed at about 180 ° C. before the reaction with the lactone (A) is started to obtain a homogeneous system. And then the ring-opening polymerization catalyst (C)
Is preferably added, the temperature is further raised, and the polymerization reaction is performed at a higher temperature.

Among the lactones used in the present invention, those having a relatively low boiling point include ε-caprolactone having a boiling point of about 230 ° C., valerolactone having a boiling point of about 205 ° C., butyrolactone having a boiling point of about 205 ° C., and propiolactone having a boiling point of about 205 ° C. The temperature is around 155 ° C., and in a state where there are many lactone monomers in the initial stage of the reaction, lactone evaporates sharply and it is difficult to carry out the reaction at a high temperature. Therefore, the polymerization reaction is started at a temperature not higher than the boiling point of the lowest lactone contained in the reaction system, and after the polymerization reaction has proceeded 20 to 50%, the reaction temperature is set to 150 to 25
It is also possible to raise the temperature to 0 ° C. to carry out the reaction promptly.

The lactone copolymer of the present invention can be produced by using an ordinary reaction kettle, but in order to increase the viscosity accompanying the increase in molecular weight, a copolymerization reaction using an ordinary reaction tank is performed. However, mixing and stirring are hindered, and local alteration is likely to occur due to local heating. Even when the product is withdrawn from the reaction tank, the product adheres to the vessel wall or the stirring blade, leading to a decrease in yield.

Generally, in a high viscosity region where the resin viscosity exceeds 10,000 poise, not only polymerization heat but also stirring heat generated by stirring shear stress is intense, and in dynamic stirring, local stirring occurs in the stirring section. Since the heat generation becomes remarkable, it is preferable to use a static mixer which has a small shearing stress and acts uniformly.

The static mixer referred to 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 a solution by reversing or reversing the flow direction and repeating division, conversion, and reversal of the flow in the vertical and horizontal directions.

The static mixer is usually tubular, and a plurality of static mixers are linearly connected to each other, and the raw materials are continuously supplied from a raw material charging port under an inert gas atmosphere. By continuously moving the reactor, it is possible to carry out the reaction continuously, from the charging of the raw materials to the reaction, delustration and pelletization of the polymer, without any contact with the outside atmosphere.

Depending on the type of static mixer, there are those equipped with a jacket for heat exchange on the outer peripheral portion of the pipe, and a tube for heat exchange for passing a heat medium through the mixing element itself. Some are.

In the production method of the present invention, all the polymerization reactions can be carried out only with a reaction device equipped with a static mixer, but the static mixer has a stirring effect particularly in the latter half of the reaction in which the polymer has a high viscosity. Since it remarkably exhibits, at the stage where the polymer viscosity is relatively low in the initial stage of the reaction, the reaction is carried out in a reaction tank equipped with an ordinary stirrer, and the latter half of the process of increasing the viscosity is performed in a reaction device equipped with a static mixer. Since it is also possible to use a continuous reaction apparatus equipped with a stirring type reaction tank and a static mixer connected thereto.

Lactone (A) and polyester used in the present invention
The ter (B) and the lactone copolymer are easily dissolved in a solvent, and the reaction can be performed using the solvent. By adding a solvent, the viscosity of the reaction product can be lowered, and the reaction can be easily carried out. Further, since the stirring and mixing are easy, the temperature control is easy and the temperature is uniform in the reaction apparatus, and a lactone-based copolymer without coloring is obtained.

As specific examples of the solvent used in the present invention, benzene, toluene, ethylbenzene, xylene, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and isopropyl ether are preferably used. The amount of solvent used depends on the need for desolvation after the reaction and the solvent amount is 2
When it exceeds 0%, phase separation occurs with the copolymer component, and the reaction temperature is lowered in some cases, so that it is preferably used in the range of 2% to 20%.

When the reaction is carried out using a solvent, the reaction rate becomes slow. Further, if the reaction temperature is too high, the solvent is likely to volatilize. In order to improve this, the reaction temperature is 1
It is preferably carried out at 65 to 230 ° C. When a solvent is used, it is possible to carry out the reaction in a pressurized system for the purpose of preventing the solvent from volatilizing.

During the reaction, if water enters the reaction system, the polymerization is hindered, so that the reaction is preferably performed in a dry inert gas atmosphere. In particular, the reaction is performed under a nitrogen or argon gas atmosphere or in a bubbling state. At the same time, it is preferable to remove water from the polyester-based polymer, which is a raw material, and to dry it.

It is also possible to devolatilize under reduced pressure for the purpose of removing the lactone, solvent and odorous substances remaining in the latter stage of the polymerization. By this devolatilization step, the amount of residual lactone can be reduced, and the storage stability of the obtained lactone copolymer can be significantly increased. When the lactone-based copolymer is formed into a sheet, it is possible to prevent hydrolysis due to adhesion of water and fusion due to heat. For this purpose it is desirable to keep the residual lactone below 1%.

As a method of devolatilization, a method of taking out while heating under reduced pressure after polymerization is preferable. In this case, it is preferable that the devolatilization time is 2 to 30 minutes, the temperature is 50 to 250 ° C., and the degree of vacuum is 0.1 to 50 Torr for the purpose of not reducing the molecular weight of the taken out lactone-based copolymer.

As another devolatilization method, after completion of the polymerization, the lactone copolymer is pelletized or pulverized,
A method of taking out while heating is preferable. Also in this case, the devolatilization time is 10 to 400 minutes and the temperature is 30 to 23 for the purpose of not reducing the molecular weight of the taken out lactone-based copolymer.
The degree of pressure reduction and the degree of reduced pressure are preferably 0.1 to 50 Torr.

As another method for reducing the residual lactone, there is a reprecipitation method in which the lactone copolymer is dissolved in a solvent after completion of the polymerization and then added to a poor solvent to obtain a polymer. In this method, the solvent that dissolves the lactone copolymer is benzene, toluene, ethylbenzene, xylene, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, methyl isobutyl ketone, methyl ethyl ketone, isopropyl ether, dichloromethane, chloroform.

Carbon tetrachloride, chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene and the like and mixed solvents thereof are preferable because of good solubility, and the poor solvent is water, methanol, ethanol, propanol, butanol, pentane, hexane, heptane. , Octane, nonane, decane, diecyl ether and the like and mixed solvents thereof.

The reprecipitation is carried out by adding the solvent to the solvent at room temperature or while heating.
A method is preferred in which after dissolution at a concentration of -20% by weight, the mixture is gradually added to a poor solvent of 2 to 15 times the amount with stirring, and the mixture is allowed to stand for 10 to 180 minutes to form a precipitate and then taken out. The precipitated precipitate is removed under reduced pressure or under heating to remove the residual solvent. Also by this method, the lactone remaining by several% or more can be reduced to 1% or less and further to 0.5% or less.

The lactone-based copolymer of the present invention alone has a sufficient plasticizing action and has moldability, but as a plasticizer,
Further good thermoplasticity can be imparted by adding a polyester, an epoxy derivative, a phthalic acid ester, a polyether or the like after polymerization or at the time of molding. Specifically, adipic acid type polyester, sebacic acid type polyester, epoxy derivative of fatty acid, diethyl phthalate, dioctyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, polyethylene glycol and the like are preferably used.

The addition amount of these plasticizers is not particularly limited, but for the purpose of avoiding bleeding, which is a phenomenon in which excess plasticizer comes out of the resin, relative to the weight of the lactone copolymer. It is preferable to add it in an amount of 1 to 30%. Further, although the lactone-based copolymer of the present invention has high thermal stability, it is possible to improve thermal stability at the time of molding by using a phosphoric acid ester, isocyanate, carbodiimide or the like as a stabilizer. The amount of these stabilizers added is not particularly limited, but it is preferably added in an amount of 1 to 10% with respect to the weight of the lactone copolymer.

The lactone copolymer obtained in the present invention has high strength. That is, tensile viscoelasticity is 500 to 2
It has 50,000 kg / cm ² (measurement condition: 23 ° C., 50% relative humidity, measuring device: solid viscoelasticity measuring device DMS200 manufactured by Seiko Denshi KK) and can be widely used as a general-purpose resin. It can be used for ink / paint resins, adhesives, laminated film resins, heat seal resins, foaming resins, extrusion molding resins, injection molding resins, sheet and film resins, and is particularly useful for packaging materials and food packaging. Is.

[0044]

EXAMPLES The present invention will be described more specifically by showing Examples and Comparative Examples below. All parts in the examples are on a weight basis unless otherwise specified.

Example 1 Polyester containing aromatic carboxylic acid and aliphatic dicarboxylic acid (terephthalic acid 14
80 parts of ε-caprolactone was added to 20 parts of mol%, 16 mol% of isophthalic acid, 20 mol% of adipic acid, 28 mol% of ethylene glycol, 22 mol% of neopentyl glycol, and a number average molecular weight of 19,800 (in terms of polystyrene). Then, the atmosphere was replaced with an inert gas, both were melted and mixed at 155 ° C. for 1 hour, and 0.02 part of tin octoate was added as a ring-opening polymerization catalyst.

When the reaction was traced by GPC, initially, a low molecular weight fraction attributable to the polyester polymer and a relatively high molecular weight fraction attributable to the copolymer containing caprolactone or the homopolymer of caprolactone were found. However, it was considered that transesterification occurred with the reaction into a single fraction having an intermediate molecular weight. The reaction was carried out at 200 ° C. for 4.5 hours, and the produced copolymer was taken out. The obtained lactone-based copolymer was a slightly yellowish white resin.

From the results of gel permeation chromatography (hereinafter abbreviated as GPC), ε-having a number average molecular weight of 24,300, which is larger than the molecular weight of the polyester containing the starting aromatic carboxylic acid and the aliphatic dicarboxylic acid.
A lactone-based copolymer copolymerized with caprolactone was confirmed. From the result of GPC after 4.5 hours of reaction, it was confirmed that the copolymer-derived fraction was single and a single copolymer was produced, and the residual small fraction derived from ε-caprolactone was also confirmed. Was done. Almost no ε-caprolactone monomer remained. As a result of differential calorimetric analysis (hereinafter abbreviated as DSC) of this lactone-based copolymer, the melting point was 62.0.
It turned out to be ° C.

This lactone-based copolymer is made to have a thickness of 200 μm.
Seiko Denshi's solid viscoelasticity measuring device D
A tensile viscoelasticity test was conducted with MS200. Result 3
It was 30,000 kg / cm ² (23 ° C., 50% relative humidity). This lactone copolymer is 10 cm x 10 c
A biodegradation test was attempted by immersing a sheet having a thickness of m and a thickness of 100 μm in seawater at 25 ° C. The results are shown below.

[0049]        Number of days of immersion Weight average molecular weight Appearance            0 days 24,200 Flexible            3 days 19,900 brittle            5th 11,200 It collapsed considerably          10th Sheet collapses and measurement is not possible Collapse

Example 2 Polyester containing aromatic carboxylic acid and aliphatic dicarboxylic acid (terephthalic acid 33
Mol%, adipic acid 17 mol%, ethylene glycol 2
3 mol%, neopentyl glycol 27 mol%, number average molecular weight 26,700 (in terms of polystyrene) 7.5 parts valerolactone 12.5 parts and ε-caprolactone 80 parts were added, and an atmosphere of an inert gas was added. Replace 1
Both were melted and mixed at 55 ° C. for 1 hour, and 0.02 part of tin octoate was added as a ring-opening polymerization catalyst.

Thereafter, the reaction was carried out at 175 ° C. for 7 hours, and the produced copolymer was taken out. From the result of GPC, a lactone-based copolymer copolymerized with a lactone having a number average molecular weight of 32,700 was confirmed. The peak of high molecular weight GPC based on the lactone-based copolymer was single, and a single copolymer was formed. Almost no lactone monomer remained.
As a result of DSC of this copolymer, the glass transition point was found to have a melting point of 52.3 ° C.

Example 3 A polyester containing an aromatic carboxylic acid and an aliphatic dicarboxylic acid (terephthalic acid 26
Mol%, isophthalic acid 9 mol%, sebacic acid 15 mol%, ethylene glycol 25 mol%, neopentyl glycol 25 mol%, number average molecular weight 22,000 (polystyrene conversion) 5 parts by adding ε-caprolactone 95 parts , Replace the atmosphere with an inert gas, at 165 ℃ for 1 hour,
Both were melted and mixed, 0.04 part of tin octoate was added as a ring-opening polymerization catalyst, and the reaction was carried out at 185 ° C. for 6 hours.

The obtained lactone copolymer was a white resin. From the result of GPC, number average molecular weight 86,100
A lactone-based copolymer copolymerized with ε-caprolactone was confirmed. The peak of high molecular weight GPC based on the lactone-based copolymer was single, and a single copolymer was formed. 2.0% of ε-caprolactone monomer remained. As a result of DSC, the melting point was found to be 60.6 ° C.

Example 4 Polyester containing aromatic carboxylic acid and aliphatic dicarboxylic acid (terephthalic acid 14
95 parts of valerolactone was added to 5 parts of mol%, 16 mol% of isophthalic acid, 20 mol% of adipic acid, 28 mol% of ethylene glycol, 22 mol% of neopentyl glycol, and a number average molecular weight of 19,800 (in terms of polystyrene). , Replace the atmosphere with an inert gas, at 165 ℃ for 1 hour,
Both were melted and mixed, 0.04 part of tin octoate was added as a ring-opening polymerization catalyst, and the reaction was carried out at 230 ° C. for 4 hours.

The lactone-based copolymer obtained was a white resin. A lactone-based copolymer copolymerized with valerolactone having a number average molecular weight of 27,400 was confirmed. The peak of high molecular weight GPC based on the lactone-based copolymer was single, and a single copolymer was formed. 12.6% of ε-caprolactone monomer remained. The melting point was found to be 62.0 ° C.

Example 5 A polyester containing an aromatic carboxylic acid and an aliphatic dicarboxylic acid (terephthalic acid 17
75 parts of ε-caprolactone was added to 25 parts of mol%, isophthalic acid 10 mol%, azelaic acid 33 mol%, ethylene glycol 40 mol%, neopentyl glycol 60 mol%, number average molecular weight 36,500 (in terms of polystyrene). Then, add 15 parts of toluene as a solvent, replace the atmosphere with an inert gas, and melt both at 175 ° C. for 1 hour.
After mixing, 0.08 tin octoate was used as a ring-opening polymerization catalyst.
A portion was added and the reaction was carried out at 170 ° C. for 7 hours.

Thereafter, the stirring was continued under reduced pressure (3 to 8 mmHg) for 3 hours to remove the residual monomer. The obtained resin was white. A lactone-based copolymer having a molecular weight of 45,900 was confirmed. The peak of high molecular weight GPC based on the lactone-based copolymer was single, and a single copolymer was formed. 0.78% of ε-caprolactone monomer remained. The melting point was found to be 58.2 ° C.

[Embodiment 6] In this embodiment, a circulation polymerization line in which four static mixers having an inner diameter of 0.5 inch and a length of 60 cm are connected in series, an inner diameter of 3/4 inch,
Four 50 cm long static mixers (Noritake, 15 mixing elements built-in) in series,
A continuous polymerization apparatus having a polymerization region consisting of a circulation polymerization line equipped with a circulation gear pump and a polymerization line continuously connected thereto was used.

Polyester containing aromatic carboxylic acid and aliphatic dicarboxylic acid (terephthalic acid 14 mol%, isophthalic acid 16 mol%, adipic acid 20 mol%, ethylene glycol 28 mol%, neopentyl glycol 22 mol%, number average molecular weight 90 parts of ε-caprolactone was added to 10 parts of 19,800 (polystyrene equivalent), the atmosphere was replaced with an inert gas, and the mixture was heated at 165 ° C. for 1 hour.
It was mixed and adjusted in advance in the main raw material tank. The catalyst is supplied by the catalyst supply pump, and the inner diameter is 1 just before the main raw material supply pump.
The mixture was mixed with the main raw material by a static mixer having a length of / 4 inch and a length of 15.5 cm (manufactured by Noritake Co., Ltd. with 12 mixing elements).

Using 0.04 part of tetraisopropyl titanate as a catalyst, polymerization was continuously carried out under the following conditions. Main raw material supply flow rate: 400 ml / hour Catalyst supply flow rate: 1.6 ml / hour Reaction temperature: 175 ° C. Flow rate circulated in circulation polymerization line: 2 l / hour Reflux ratio: 5 Measurement of various properties and physical properties of the obtained polymer I went. A lactone-based copolymer having a number average molecular weight of 32,900 was confirmed. The peak of high molecular weight GPC based on the lactone-based copolymer was single, and a single copolymer was formed. 0.3% of ε-caprolactone monomer remained. Melting point is 6
It was 0.6 ° C.

Comparative Example 1 To 90 parts of polyethylene terephthalate (sheet form), 10 parts of poly ε-caprolactone was added, and 0.02 part of tin octoate was added, and the atmosphere was replaced with an inert gas. The reaction was carried out for 3 hours. During the reaction, the poly ε-caprolactone melted and became a very brown color. Polyethylene terephthalate softened only slightly and no copolymer was formed.

Comparative Example 2 10 parts of polyethylene terephthalate (weight average molecular weight 18,300) was added with 10 parts of ε-caprolactone, 0.02 part of tin octanoate was added, and the atmosphere was replaced with an inert gas. 8 hours at 165 ° C
The reaction was performed to obtain a copolymer having a molecular weight of 45,800, which was a white opaque resin.

[0063]

EFFECT OF THE INVENTION Lactone in which lactone is subjected to ring-opening addition polymerization and transesterification reaction with a lactone copolymer and a polyester containing an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid.
Those concerning the manufacturing method of the emission copolymer. The lactone-based copolymer according to the present invention has high strength and tensile viscosity.
It has elasticity of 500 to 20,000 kg / cm ² ,
It can be widely used as a general-purpose resin. Foaming resin, extrusion
Molding resin, injection molding resin, sheet and film
It can be used for resins and is useful for packaging materials and food packaging.

Claims (6)

(57) [Claims] 1. A 20,000 to 40 weight average molecular weight having lactone (A), a repeating unit of an aromatic dicarboxylic acid component and a diol component, and a repeating unit of an aliphatic dicarboxylic acid component and a diol component as essential constituents. A method for producing a lactone-based copolymer, which comprises reacting the polyester (B) in the presence of a ring-opening polymerization catalyst (C). 2. The weight ratio of lactone (A) to 100 parts by weight of the total of lactone (A) and polyester (B) is
The manufacturing method according to claim 1, wherein the amount is 70 to 99 parts by weight. 3. A polyester (B), wherein the aromatic dicarboxylic acid is terephthalic acid and / or isophthalic acid,
The production method according to claim 1, wherein the aliphatic dicarboxylic acid is a polyester composed of an aliphatic dicarboxylic acid having 4 to 20 carbon atoms and having a weight average molecular weight of 20,000 to 400,000. 4. A polyester (B), wherein the aromatic dicarboxylic acid is terephthalic acid and / or isophthalic acid,
The production method according to claim 2, wherein the aliphatic dicarboxylic acid is a polyester composed of an aliphatic dicarboxylic acid having 4 to 20 carbon atoms and having a weight average molecular weight of 20,000 to 400,000. 5. The production method according to claim 1, wherein the polyester (B) is a polyester having a melting point or a softening point of 180 ° C. or lower. 6. A lactone (A) and a weight average molecular weight of 20,000 to.
Polyester (B) which is 400,000
The method according to any one of claims 1 to 5, wherein the reaction is carried out in a continuous reaction device equipped with a mixer.