KR100763987B1 - Aliphatic polyester copolymer - Google Patents

Abstract

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an aliphatic polyester copolymer having excellent heat resistance and having practically sufficient mechanical and melt physical properties.

[Solution] An aliphatic polyester copolymer comprising an aliphatic polycarbonate unit (a), an aliphatic polyester unit (b), and a molded article made of the aliphatic polyester copolymer are provided.

Aliphatic Polyester Copolymer, Aliphatic Polycarbonate

Description

Aliphatic polyester copolymer {ALIPHATIC POLYESTER COPOLYMER}

The present invention relates to a high molecular weight aliphatic polyester copolymer having excellent heat resistance. In general terms (1)

(In formula (1), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

It relates to an aliphatic polyester copolymer comprising an aliphatic polycarbonate unit (a) and an aliphatic polyester unit (b).

Moreover, this invention relates to the molded article which consists of the said aliphatic polyester copolymer, the base for optical discs, the sheet | seat, and a container.

Recently, interest in environmental protection is increasing, and in Japan, the promotion of the purchase of eco-friendly materials by the Law of Promoting Green Purchasing, and the recycling of plastic materials and household appliances by the Containers and Packing Recycling Law It has been shown to promote recycling of electric appliances by the Home Appliance Recycling Law. In such a series of flows, polymers such as aliphatic polyesters and aliphatic polycarbonates with low environmental loads have attracted attention.

Polylactic acid, one of the aliphatic polyesters, has high transparency, toughness, and easily hydrolyzes in the presence of water. Therefore, when used as a general-purpose resin, it is environmentally friendly and medical material because it is decomposed without contaminating the environment after disposal. In the case of retaining in vivo, it is friendly to the living body since it is decomposed and absorbed in vivo without being toxic to the living body after achieving the purpose as a medical material.

However, from the viewpoint of heat resistance, it is difficult to say that polylactic acid is sufficient for use as a general purpose resin. For this reason, the emergence of homopolymers or copolymers of aliphatic polyesters and aliphatic polycarbonates having sufficiently high heat resistance and molecular weight is greatly desired.

As one of aliphatic polycarbonates, Non-Patent Document 1 discloses a polycarbonate made of isosorbide and phosgene. According to this, although this polycarbonate is described as Mw = 32,000, the high molecular weight polycarbonate whose Mw is 35,000 or more is not described. In addition, Patent Document 1 describes a copolymer of an aliphatic cyclic carbonate of 1,2-O-isopropylidene-D-xyclofuranose-3,5-cyclic carbonate (IPXTC) and polylactic acid. have. According to this, the copolymer with polylactic acid which contains 60 mol% of IPXTC of an aliphatic polycarbonate component is described as Tg = 90 degreeC. However, if the composition ratio of the copolymer of PLA and IPXTC containing 60 mol% IPXTC by weight ratio is PLA / IPXTC = 18/82 (wt%), expensive IPXTC must be used in large quantities. Moreover, when the addition amount of IPXTC is increased, there also exists a problem that a yield falls and the molecular weight of the copolymer obtained also falls.

From the above facts, aliphatic polymers having sufficiently high heat resistance and molecular weight and which are economically manufacturable are not known.

Patent Document 1: US-6093792, p. 5-10

[Non-Patent Document 1] Journal Fur Praktische Chemie Chemiker-Zeitung (1992), 334 (4), p. 298-310

[Initiation of invention]

[Problem to Solve Invention]

An object of the present invention is to provide a high molecular weight aliphatic polyester copolymer having excellent heat resistance.

[Means for solving the invention]

The present inventors earnestly examined in view of the problems of the prior art described above, and the general formula (1)

(In formula (1), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

An aliphatic polyester copolymer comprising an aliphatic polycarbonate unit (a) and an aliphatic polyester unit (b) represented by was found to complete the present invention.

That is, the aliphatic polyester copolymer concerning this invention is specified by the matter described in the following [1]-[11].

(1) General Formula (1)

(In formula (1), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

An aliphatic polyester copolymer comprising an aliphatic polycarbonate unit (a) and an aliphatic polyester unit (b) represented by.

(2) The aliphatic polyester copolymer according to (1), wherein the aliphatic polycarbonate unit (a) is a structure derived from one produced from isosorbide and a carbonate precursor.

(3) The aliphatic polyester copolymer according to (1) to (2), wherein the aliphatic polyester unit (b) is a structure derived from lactic acid.

(4) The composition ratio of the aliphatic polycarbonate unit (a) and the aliphatic polyester unit (b) is (a) / (b) = 5/95 to 50/50 wt%, (1) to Aliphatic polyester copolymer as described in (3).

(5) The aliphatic polyester copolymer according to (1), wherein the weight average molecular weight of the aliphatic polyester copolymer is 10,000 to 500,000.

(6) Aliphatic polyester copolymer as described in (1) characterized by higher glass transition temperature than aliphatic polyester which has the same repeating unit as aliphatic polyester unit (b) contained in aliphatic polyester copolymer.

(7) The aliphatic polyester copolymer according to (1), wherein the haze is 5% or less.

(8) A molded article comprising the aliphatic polyester copolymer according to (1).

(9) A substrate for an optical disc, comprising the aliphatic polyester copolymer according to (1).

(10) A sheet made of the aliphatic polyester copolymer according to (1).

(11) A container made of the aliphatic polyester copolymer according to (1).

[Effects of the Invention]

The aliphatic polyester copolymer of the present invention comprising the aliphatic polycarbonate unit (a) and the aliphatic polyester unit (b) represented by the formula (1) has excellent heat resistance and practically sufficient mechanical and melt physical properties, It can be used suitably for an optical disk base material, a container or a packaging material.

Best Mode for Carrying Out the Invention

The present invention relates to a high molecular weight aliphatic polyester copolymer having excellent heat resistance. In general terms (1)

(In Formula (1), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

It relates to an aliphatic polyester copolymer comprising an aliphatic polycarbonate unit (a) and an aliphatic polyester unit (b).

Aliphatic polycarbonate used in the present invention is represented by the general formula (1)

(In Formula (1), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

Preferred is a polycarbonate comprising an aliphatic polycarbonate unit (a) represented by. Among them, the formula (2)

The aliphatic polycarbonate which consists of isosorbide and a carbonate precursor represented by is preferable.

Although the manufacturing method of aliphatic polycarbonate used by this invention is not specifically limited, For example, General formula (3)

(In Formula (3), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

There is a method of reacting the dihydric alcohol represented by the carbonate precursor.

The dihydric alcohol used to prepare the aliphatic polycarbonate used in the present invention is represented by the general formula (3)

(In Formula (3), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

It is preferable that it is represented by. You may use dihydric alcohol individually or in mixture of 2 or more types.

The carbonate precursor used to prepare the aliphatic polycarbonate used in the present invention is a carbonyl equivalent that provides a polycarbonate by reacting with a dihydric alcohol having two hydroxyl groups. Halides, carbonyl esters, haloformates and the like. Specifically, phosgene, diphenyl carbonate, etc. are mentioned.

You may use a carbonate precursor individually or in mixture of 2 or more types.

The aliphatic polycarbonate used in the present invention is produced by a known method such as a solution method or a melting method. Moreover, you may add a suitable molecular weight regulator, a branching agent, another modifier, etc. at that time.

The molecular weight of the aliphatic polycarbonate used in the present invention is not particularly limited. In general, in consideration of the thermal properties and mechanical properties of the obtained aliphatic polyester copolymer, 5,000 to 200,000 are preferred as the weight average molecular weight (Mw), 10,000 to 100,000 are more preferred, and 40,000 to 100,000 are most preferred.

It is preferable that it is 100-300 degreeC, and, as for the glass transition temperature of the aliphatic polycarbonate used by this invention, it is more preferable that it is 140-240 degreeC.

The aliphatic polycarbonate used in the present invention may be either a homopolymer or a copolymer. The arrangement of the copolymer may be any of random copolymers, alternating copolymers, block copolymers, graft copolymers, and the like.

The structure of the aliphatic polycarbonate used in the present invention may be any of linear, branched, molded and three-dimensional mesh.

In the present invention, the aliphatic polyester unit (b) refers to a structure derived from aliphatic hydroxycarboxylic acid and / or aliphatic dihydric alcohol and aliphatic dibasic acid. Hydroxycarboxylic acid refers to a compound containing at least one hydroxyl group and at least one carboxyl group in a molecule.

The aliphatic polyester (B) used by this invention means the polymer containing the said aliphatic polyester unit (b), and is specifically represented by any of following (1)-(3).

(1) Homopolymers and / or copolymers of polyesters prepared from aliphatic hydroxycarboxylic acids or cyclic monomers (lactones) or cyclic dimers of aliphatic hydroxycarboxylic acids (hereinafter referred to as aliphatic polyesters (B1))

(2) homopolymers and / or copolymers of polyesters prepared from aliphatic dihydric alcohols and aliphatic dibasic acids (hereinafter referred to as aliphatic polyesters (B2))

(3) copolymer of aliphatic polyester (Bl) and aliphatic polyester (B2) (hereinafter referred to as aliphatic polyester (B3))

In addition, the structure of an aliphatic polyester (B) may be linear, branched, shaping | molding, or a three-dimensional mesh shape, and even if it uses a suitable branching agent in order to obtain the aliphatic polyester of a branching, shaping | molding, and three-dimensional network structure, do.

Aliphatic polyesters (Bl) to (B3) used in the present invention are produced by a known method using the raw materials described below.

Aliphatic hydroxycarboxylic acid which is a raw material of aliphatic polyester (Bl) is an aliphatic carboxylic acid which has a hydroxyl group in a molecule | numerator, and there is no restriction | limiting in particular. Suitable specific examples include, for example, lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxy valeric acid, 5-hydroxy valeric acid, 6-hydroxycaproic acid, and the like. Lactic acid is preferable at the transparency of the obtained aliphatic polyester copolymer.

Moreover, you may use the cyclic monomer (lactone) and cyclic dimer of the said aliphatic hydroxycarboxylic acid in order to manufacture the aliphatic polyester copolymer which concerns on this invention. Specifically, lactide, glycide, (beta) -propiolactone, (beta) -butyrolactone, (gamma) -butyrolactone, (gamma) -valerolactone, (delta) -valerolactone, (epsilon) -caprolactone, etc. are mentioned.

In addition, although these aliphatic hydroxycarboxylic acids may be used individually or in combination of 2 or more types, when using two or more types of aliphatic hydroxycarboxylic acids in combination, they contain lactic acid by transparency of the aliphatic polyester copolymer obtained (lactic acid and its Combinations of other aliphatic hydroxycarboxylic acids) are preferred.

In addition, in the case of having asymmetric carbon in a molecule such as lactic acid, D-form, L-form, and an equivalent mixture thereof (racemate) are present, and any of them can be used.

Aliphatic dihydric alcohol and aliphatic dibasic acid which are raw materials of aliphatic polyester (B2) are not specifically limited. Suitable specific examples of aliphatic dihydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol , 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentylglycol, 1,4-cyclohexanediol, isosorbide, 1,4-cyclo Hexane dimethanol etc. are mentioned. These can be used individually or in combination of 2 or more types. In addition, in the case of having an asymmetric carbon in the molecule, D-form, L-form, and an equivalent mixture (racemate) thereof are present, and any of them can be used.

In addition, suitable specific examples of aliphatic dibasic acids include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanic acid, dodecanic acid, Aliphatic dicarboxylic acids, such as 3, 3- dimethylpentane diacid, and alicyclic dicarboxylic acids, such as cyclohexanedicarboxylic acid, are mentioned. These can be used individually or in combination of 2 or more types. In addition, in the case of having an asymmetric carbon in the molecule, D-form, L-form, and an equivalent mixture (racemate) thereof are present, and any of them can be used.

As a suitable branching agent for obtaining the aliphatic polyester of a branched, molded, and three-dimensional network structure, if it is a compound which has three or more hydroxyl groups and / or a carboxyl group, it will not specifically limit, Even if it is a polymer like polysaccharide, an aliphatic polyhydric alcohol or an aliphatic It may be a low molecular compound such as polybasic acid.

Specific examples of polysaccharides include regenerated cellulose such as cellulose, cellulose nitrate, cellulose acetate, methyl cellulose, ethyl cellulose, CMC (carboxymethyl cellulose), nitrocellulose, cellophane, viscose rayon, cupra, hemicellulose, starch, amylopectin, dextrin, and dex. Tran, glycogen, pectin, chitin, chitosan and the like and mixtures thereof and derivatives thereof. Among these, cellulose acetate which is esterified cellulose and ethylcellulose which are etherified cellulose are especially preferable.

3,000 or more are preferable and, as for the weight average molecular weight of a polysaccharide, 10,000 or more are more preferable. It is preferable that it is 0.3-3.0, and, as for the substitution degree of esterified cellulose and etherified cellulose, it is more preferable that it is 1.0-2.8.

Specific examples of the aliphatic polyhydric alcohol having three or more hydroxyl groups include glycerin, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, xylitol, inositol and the like. These can be used individually or in combination of 2 or more types. In addition, in the case of having an asymmetric carbon in the molecule, D-form, L-form, and an equivalent mixture (racemate) thereof are present, and any of them can be used.

Specific examples of aliphatic polybasic acids having three or more carboxyl groups include 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, tetrahydrofuran 2R, 3T, 4T , 5C-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 4-carboxy-1,1-cyclohexanediacetic acid, 1,3,5-cyclohexanetricarboxylic acid, (1α, 3α, 5β) Cyclic compounds such as -1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid and 2,3,4,5-furantheracarboxylic acid and anhydrides thereof; Butane-1,2,3,4-tetracarboxylic acid, meso-butane-1,2,3,4-tetracarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,3-propanetricarboxylic acid, 1, Linear compounds such as 1,2-ethanetricarboxylic acid and 1,2,4-butanetricarboxylic acid; and anhydrides thereof. These can be used individually or in combination of 2 or more types. In addition, in the case of having an asymmetric carbon in the molecule, D-form, L-form, and an equivalent mixture (racemate) thereof are present, and any of them can be used.

The method for producing aliphatic polyester of branched, molded, three-dimensional network structure is not particularly limited, but for example, aliphatic polyhydric alcohol having aliphatic hydroxycarboxylic acid and three or more hydroxyl groups and aliphatic polybasic acid having two or more carboxyl groups, Or it can obtain by the dehydration polycondensation reaction of aliphatic polybasic acid which has aliphatic hydroxycarboxylic acid, an aliphatic polybasic acid which has 3 or more carboxyl groups, and 2 or more hydroxyl groups.

Aliphatic polybasic acids having at least three hydroxyl groups and aliphatic polybasic acids having at least two carboxyl groups and / or acid anhydrides thereof; And aliphatic polybasic acids having three or more carboxyl groups and / or acid anhydrides thereof and polyhydric alcohols having two or more hydroxyl groups are as follows. That is, the weight of the aliphatic polyhydric alcohol having three or more hydroxyl groups, the aliphatic polybasic acid having three or more carboxyl groups, and / or the acid anhydride thereof is based on the weight of the polymer when the aliphatic polyester is completely polymerized alone. , 0.005 to 10%, preferably 0.01 to 5%, and an equivalent ratio of the carboxyl group of an aliphatic polybasic acid and / or an acid anhydride having a hydroxyl group of two or more carboxyl groups of an aliphatic polyhydric alcohol having three or more hydroxyl groups; And an equivalent ratio of the hydroxyl group of the aliphatic polybasic acid having three or more carboxyl groups and / or the carboxyl group of the acid anhydride thereof and the polyhydric alcohol having two or more hydroxyl groups is 100: 30 to 300, preferably 100: 80 to 120, more preferably 100: It corresponds to 90-110.

The molecular weight of the aliphatic polyester is not particularly limited, but considering the mechanical strength of the resulting aliphatic polyester copolymer, 5,000 to 1,000,000 are preferable, 10,000 to 500,000 are more preferable, and 100,000 are the weight average molecular weight (Mw). Most preferably-300,000.

It is preferable that it is -70-100 degreeC, and, as for the glass transition temperature of the aliphatic polyester used by this invention, it is more preferable that it is 30-70 degreeC.

Although the composition ratio of aliphatic polycarbonate and aliphatic polyester in this invention is not restrict | limited, It is preferable that it is the ratio of 95-5 weight% of aliphatic polyester with respect to 5-95 weight% of aliphatic polycarbonate, More preferably, Is a ratio of 90 to 50% by weight of aliphatic polyester with respect to 10 to 50% by weight of aliphatic polycarbonate, and more preferably 80 to 60% by weight of aliphatic polyester with respect to 20 to 40% by weight of aliphatic polycarbonate. It is a ratio (but the sum of the weight% of aliphatic polycarbonate and the weight% of aliphatic polyester is 100). If the ratio of aliphatic polycarbonate is raised, the glass transition temperature of an aliphatic polyester copolymer will become high.

Aliphatic polyester copolymers according to the invention are represented by the general formula (1)

(In Formula (1), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and is linear or branched, R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent.

If the aliphatic polycarbonate unit (a) and aliphatic polyester unit (b) represented by are contained, the reaction system will not be restrict | limited in particular. Specifically, aliphatic polycarbonate and aliphatic polyester may be reacted in an organic solvent, or cyclic monomers or cyclic dimers of aliphatic polycarbonate and aliphatic hydroxycarboxylic acid may be reacted in a molten state.

As a manufacturing method of the aliphatic polyester copolymer which concerns on this invention, a well-known public method can be used and it does not restrict | limit in particular. Specifically, a melt polymerization method, a solution polymerization method, a solid phase polymerization method, etc. may be mentioned, and an optimum reaction method can be selected in consideration of the raw materials used and the physical properties of the obtained aliphatic polyester copolymer.

Since the melt polymerization method is excellent in volumetric efficiency, it can be made to react with a comparatively small polymerizer compared with the polymerizer of solution polymerization method. Since the solution polymerization method can react at relatively low temperature, the aliphatic polyester copolymer with relatively little coloring is easy to be obtained. The solid phase polymerization method is excellent in volumetric efficiency and can be reacted at a relatively low temperature. Therefore, it is an effective reaction method if the aliphatic polyester copolymer has crystallinity.

In the preparation of the aliphatic polyester copolymer according to the present invention, for the purpose of suppressing deactivation of the catalyst and coloring of the copolymer, etc., it is generally carried out under vacuum or inert gas atmosphere such as nitrogen or argon. It is preferable to carry out the reaction.

In addition, all the operations for producing the aliphatic polyester copolymer according to the present invention can be carried out either in a batch operation or in a continuous operation.

In the present invention, a catalyst may be used when preparing the aliphatic polyester copolymer. The catalyst is not particularly limited as long as the aliphatic polycarbonate having a ring structure containing a hetero atom in the main chain and / or the side chain reacts with the aliphatic polyester to produce an aliphatic polyester copolymer. As a specific example of a catalyst, metal of the periodic table II, III, IV, group V, its oxide, its salt, etc. are mentioned, for example.

More specifically, metals such as zinc powder, tin powder, aluminum, magnesium and germanium; Metal oxides such as tin oxide (II), antimony (III) oxide, zinc oxide, aluminum oxide, magnesium oxide, titanium oxide (IV), germanium oxide (II), and germanium oxide (IV); Metal halides such as tin chloride (II), tin chloride (IV), tin bromide (II), tin bromide (IV), antimony fluoride (III), antimony fluoride (V), zinc chloride, magnesium chloride and aluminum chloride; Sulfates such as tin sulfate (II) sulfate, zinc sulfate and aluminum sulfate; Carbonates such as magnesium carbonate and zinc carbonate; Borate salts such as zinc borate; Organic carboxylates such as tin acetate (II), tin octanoate (II), tin lactate (II), zinc acetate and aluminum acetate; Organic sulfonates such as trifluoromethanesulfonic acid tin (II), zinc trifluoromethanesulfonic acid zinc, trifluoromethanesulfonic acid magnesium, methane sulfonate tin (II), and p-toluenesulfonic acid tin (II).

As another example, Organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; Organometal oxides of the above metals such as dibutyltin oxide; Or metal alkoxides of the above metals such as titanium isopropoxide; Or alkyl metal of the said metals, such as diethyl zinc, etc. are mentioned.

Among these, a tin catalyst represented by tin powder (metal tin), tin oxide (II), tin octanoate (II), tin lactate (II), tin chloride (II), or the like is preferable. These can be used individually or in combination of 2 or more types.

The amount of the catalyst used in the present invention is not particularly limited as long as the amount of the catalyst can be substantially advanced. Although the usage-amount of a specific catalyst changes with the kind of catalyst to be used, generally the range of 0.00005-5 weight% of the aliphatic polyester copolymer obtained is preferable, and 0.0001-1 weight% is more preferable in consideration of economy. .

When producing the aliphatic polyester copolymer of the present invention by the solution polymerization method, the organic solvent to be used is not particularly limited if the copolymerization reaction of the aliphatic polycarbonate and the aliphatic polyester proceeds, but in order to proceed the reaction efficiently, It is preferable that it is an organic solvent which melt | dissolves both aliphatic polycarbonate and aliphatic polyester.

Specific examples of the organic solvent that can be used in the present invention include hydrocarbon solvents such as toluene, xylene and mesitylene; Halogenated hydrocarbon solvents such as chlorobenzene, bromobenzene, iodinebenzene, dichlorobenzene, 1,1,2,2-tetrachloroethane and p-chlorotoluene; Ketone solvents such as 3-hexanone, acetophenone and benzophenone; Ether solvents such as dibutyl ether, anisole, phentol, o-dimethoxybenzene, p-dimethoxybenzene, 3-methoxytoluene, diphenyl ether, dibenzyl ether, benzylphenyl ether, and methoxynaphthalene; Thioether solvents such as phenyl sulfide and thioanisole; Ester solvents such as methyl benzoate, dimethyl phthalate and diethyl phthalate; Alkyl-substituted diphenyl ether, such as 4-methylphenyl ether, 3-methylphenyl ether, and 3-phenoxy toluene; Or halogen-substituted diphenyl ethers such as 4-bromophenyl ether, 4-chlorophenyl ether, 4-bromodiphenyl ether and 4-methyl-4'-bromodiphenyl ether; Or alkoxy substituted diphenyl ethers such as 4-methoxy diphenyl ether, 4-methoxyphenyl ether, 3-methoxyphenyl ether, and 4-methyl-4'-methoxydiphenyl ether; Or diphenyl ether solvents such as cyclic diphenyl ether such as dibenzofuran and xanthene; Nitrogen-containing solvents such as 1,3-dimethyl-2-imidazolidinone and N, N-dimethylacetamide; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; Halogenated hydrocarbon solvents and nitrogen-containing solvents are preferred. Among them, 1,3-dimethyl-2-imidazolidinone is particularly preferable.

One type of these organic solvents or two or more types thereof can be used in combination.

There is no restriction | limiting in particular if the boiling point of the organic solvent used by this invention can be made to react, It is preferable that it is 100 degreeC or more, It is more preferable that it is 140 degreeC or more, It is especially preferable that it is 170 degreeC or more.

The amount of the organic solvent to be used in the present invention is not particularly limited as long as the reaction proceeds substantially.

It is preferable that the usage-amount of the organic solvent used by this invention is 0.1 to 9 times with respect to the weight of the aliphatic polyester copolymer obtained generally.

In the process for producing the aliphatic polyester copolymer according to the present invention, the reaction in the organic solvent is carried out by reducing the water present in the reaction system by batch and / or continuous water removal operation in at least part of the whole process. You may react. The water removal operation may be a circulation type or a reflux type.

As described above, the water removal operation of the present invention is not particularly limited as long as the water present in the reaction system can be reduced. Specifically, there are the following methods.

1) A method in which excess organic solvent is charged into the reactor in advance, and water is removed only by extracting the organic solvent.

2) A method of removing moisture by drying the organic solvent of the reaction system using another organic solvent.

3) At least a part of the organic solvent of the reaction system is taken out and charged into the reaction system at a water content equal to or less than the moisture content of the organic solvent taken out of the reaction system by a treatment of contacting with a desiccant outside the reaction system or distillation treatment using a difference in boiling point. How to remove it.

When water in the reaction system is removed by the above water removal operation, the water content of the organic solvent charged in the reaction system is preferably 50 ppm or less, more preferably 25 ppm or less, and particularly preferably 5 ppm or less.

In the preparation of the aliphatic polyester copolymer according to the present invention, when reacting with a solvent, a desiccant may be used for the purpose of removing water in the solvent. The desiccant to be used is not particularly limited. As a specific example of the drying agent which can be used by this invention, For example, Molecular sheaves, such as Molecular sheave 3A, Molecular sheave 4A, Molecular sheave 5A, Molecular sheave 13X; Ion exchange resins, alumina, silica gel, calcium chloride, calcium sulfate, diphosphate, concentrated sulfuric acid, magnesium perchlorate, barium oxide, calcium oxide, potassium hydroxide, sodium hydroxide; Or metal hydrides such as calcium hydride, sodium hydride and lithium aluminum hydride; Or alkali metals, such as sodium, etc. are mentioned.

These can be used individually or in combination of 2 or more types. Among them, molecular sieves and ion exchange resins are preferred for ease of handling and regeneration.

In the production of the aliphatic polyester copolymer according to the present invention, the reaction temperature is 100 to 240 ° C in any of the solution polymerization method, melt polymerization method and solid phase polymerization method. In general, the reaction temperature is more preferably in the range of 110 to 200 ° C in consideration of the progress of the copolymerization reaction and the color of the aliphatic polyester copolymer obtained.

When using an organic solvent, reaction is normally performed at the distillation temperature of the organic solvent used under normal pressure. In order to make reaction temperature into a preferable range, when using a high boiling point organic solvent, you may carry out under reduced pressure.

Further, even if the boiling point is lowered because the organic solvent is azeotropic with water, there is no problem if the reaction proceeds substantially at a predetermined temperature.

In the present invention, when the aliphatic polyester copolymer is prepared by the solution polymerization method, the method for recovering the aliphatic polyester copolymer as the reaction product from the reaction solution after the completion of the reaction is as long as the reaction product can be substantially recovered to the desired purity. Is not particularly limited.

The method for recovering the reaction product may be any known or public method. Specifically, after removing a catalyst, the reaction liquid is melt | dissolved in a suitable solvent, and it discharge | releases to an excess poor solvent, and collect | recovers, The method of desolvating and recovering | resolving by vaporization after deactivating a catalyst is mentioned. .

The weight average molecular weight of the aliphatic polyester copolymer in the present invention is generally 5,000 to 1,000,000, but considering mechanical properties, thermal properties, and moldability, it is preferably 10,000 to 500,000, more preferably 35,000 to 200,000, It is more preferable that they are 40,000-100,000.

Although the glass transition temperature (Tg) of the aliphatic polyester copolymer which concerns on this invention is higher than Tg of the homopolymer of aliphatic polyester contained in this copolymer, it will not specifically limit, 40-220 degreeC is preferable, More preferably, It is 60-200 degreeC, More preferably, it is 80-150 degreeC. The glass transition temperature (Tg) shown by this invention means what performed the differential thermal analysis (DSC analysis) in the temperature range of 10 degree-C / min, 30-250 degreeC in temperature rising rate with a differential scanning calorimeter (DSC-60 by Shimadzu Corporation).

The haze of the aliphatic polyester copolymer according to the present invention is preferably 10% or less at a thickness of 100 µm, more preferably 5% or less, and most preferably 1% or less. In order to obtain the aliphatic polyester copolymer excellent in transparency, it is preferable that the structure derived from lactic acid or lactide is included as the aliphatic polyester unit (b) in an aliphatic polyester copolymer.

The mechanical properties of the aliphatic polyester copolymer according to the present invention are preferably 30 to 100 MPa, more preferably 40 to 80 MPa, in the tensile test.

The melt physical property of the aliphatic polyester copolymer according to the present invention preferably has a melt flow index (MI) of 15 (g / min) or more, more preferably 20 (g / min) or more, at a measurement temperature of 240 ° C. It is more preferable that it is 30 (g / min) or more. In addition, about the measuring method of MI, it shall conform to JIS K7210.

The molding processing method of the aliphatic polyester copolymer obtained by the present invention is not particularly limited, and specifically, injection molding, extrusion molding, inflation molding, extrusion blow molding, foam molding, calender molding, blow molding, balloon molding, vacuum molding, Molding methods such as spinning are applied.

The sheet in the present invention shall include both the sheet or the film having a thickness of about 10 μm to 10 mm.

Although the use of the aliphatic polyester copolymer in this invention is not specifically limited, Taking advantage of the outstanding heat resistance and transparency, it can be used suitably as a substitute of resin used for a container, a packaging material, and general use.

Specifically, the absence of writing utensils, such as ballpoint pens, pencils, and pencils, the absence of stationary, golf tees, oral fuming golf balls, oral pharmaceutical capsules, suppositories for anal and vaginal suppositories, and skin / mucosa plasters Carrier, Pesticide Capsule, Fertilizer Capsule, Seedling Capsule, Compost, Fishing Reel, Bobber, Fishing Lure, Lure, Fishing Buoy, Hunting Decoy, Hunting Pellets ( shot gun) Camping supplies such as capsules and tableware, nails, piles, binding materials, slip stoppers for sludge and snow, blocks, lunch boxes, tableware, lunch boxes, side dish containers, chopsticks and disposable Chopsticks, forks, spoons, skewers, toothpicks, cup noodle cups, cups used in vending machines, fish, meats, fruits and vegetables, tofu, side dishes, food containers and trays, fish market boxes, milk yogurt Dairy products, such as lactobacillus beverages Bottles, soft drinks such as carbonated drinks and soft drinks, bottles for liquor drinks such as beer and whiskey, bottles with or without running pumps for shampoo or liquid soap, toothpaste tubes, cosmetic containers, detergent containers , Bleach containers, cool boxes, pots, casings of water purifier cartridges, casings such as artificial kidneys and artificial soy sauce, absence of syringes, cushioning materials for use in transporting household telephone products such as televisions and stereos Although it can be used as a buffer material for transportation of precision machines such as printers and watches, and a buffer material for transportation of ceramic products such as glass and ceramics, it is used for packaging films, food containers, egg packs, Blister Pack, Compact Disc (CD), CD-R, CD-ROM, LD, DVD, Transparent Conductive Film, Mini Disc (MD), Cassette Tape, Video Tape, Personal Computer or Portable It can be suitably used for telephone housing, feeding bottles, spout cups, etc.

An Example is given to the following and this invention is demonstrated to it in detail. In addition, description of the Example in the specification of this application is description for aiding understanding of the content of this invention, and this description is not a thing of the character used as the basis for narrowly interpreting the technical scope of this invention. The evaluation method used in this Example is as follows.

1) Weight average molecular weight (Mw)

The weight average molecular weight (Mw) of the aliphatic polyester copolymer of Examples 1 and 2 was measured by gel permeation chromatography (column temperature 40 degreeC, chloroform solvent), and the weight average molecular weight was calculated | required by comparison with a polystyrene standard sample. . In addition, the weight average molecular weight (Mw) of the aliphatic polyester copolymer of Example 5 and the polyglycolic acid of Comparative Example 2 is measured by gel permeation chromatography (column temperature 35 degreeC, hexafluoroisopropanol solvent), The weight average molecular weight was calculated | required by comparison with the polymethylmethacrylate standard sample.

2) glass transition temperature (Tg)

Except for Comparative Example 2, the sample prepared by heating at 210 ° C. for 1 minute and cooling with ice was subjected to a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) at a temperature increase rate of 10 ° C./min at a temperature range of 30 to 250 ° C. Differential thermal analysis (DSC analysis). In addition, about the comparative example 2, the sample manufactured by heating up to 250 degreeC by the temperature increase rate of 10 degree-C / min, and then quenching in liquid nitrogen was subjected to the differential thermal analysis (DSC analysis) at the temperature increase rate of 10 degree-C / min, 20-250 degreeC. )did.

3) transparency

The transparency of the film samples in Examples 3 and 4 was measured by a haze meter TC-H III (Tokyo Denshoku Co., Ltd.) according to JIS K6714 for haze (cloudiness).

4) Tensile fracture strength, tensile yield strength

Tensile strength in Examples 3 and 4 Measured according to JIS K7113.

[Production Example 1]

106.12 g of reagent isosorbide, 80.15 g of acetonitrile, and 126.40 g of pyridine from Tokyo Chemical Industries were charged into a 500 ml round bottom flask, and isosorbide was dissolved at room temperature. Since the internal temperature rose after starting charging of phosgene, 74.02 g of phosgenes were charged over 2 hours, keeping internal temperature at 50 degreeC. After 1 hour of aging at 50 ° C., the reaction mass was transferred to a 1 L beaker, the reaction mass was diluted with 400 g of acetonitrile, and the reaction mass was diluted with 41.41 g of methanol. The polymerized reaction mass was discharged into 3 L of water containing 150 ml of 1N hydrochloric acid. After filtration, washing with water was repeated several times and washed with methanol. After filtration, it dried at 50 degreeC and nitrogen atmosphere, and obtained 111.88 g (= 89.5%) of aliphatic polycarbonates.

Obtained aliphatic polycarbonate was Mw = 19,000 and glass transition temperature = 163.1 ° C.

[Production Example 2]

106.19 g of reagent isosorbide and 376.28 g of pyridine from Tokyo Chemical Industries were charged in a 1000 ml round bottom flask, and isosorbide was dissolved at room temperature. Since the internal temperature rose after charging the phosgene, the phosgene was further charged while maintaining the internal temperature at 50 ° C. Since the viscosity of the reaction mass rose during phosgene charging, 103.44 g of pyridine was added and finally 89.0 g of phosgene was charged over 9 hours. After completion of the phosgene charging, the reaction mass was transferred to a 2 L beaker, 750 g of chloroform and 100 g of methanol were charged to dilute the reaction mass. The reaction mass was discharged into 4 L of methanol to reprecipitate the polymer, and the polymer was recovered by filtration. The recovered polymer and 1000 ml of 0.5 N hydrochloric acid were charged to a 2 L beaker and stirred at room temperature for 30 minutes. After filtration, the recovered polymer was washed three times with 1000 ml of methanol. After filtration, it dried at 50 degreeC and nitrogen atmosphere, and obtained 106.73 g (= 85.4%) of aliphatic polycarbonates.

Obtained aliphatic polycarbonate was Mw = 81,000 and glass transition temperature = 175.5 ° C.

Example 1

18.06 g of polylactic acid (H-100 grade) manufactured by Cargill Dow, 12.00 g of aliphatic polycarbonate synthesized in Preparation Example 1, and 91.22 g of 1,3-dimethyl-2-imidazolidinone were charged into a 300 ml round bottom flask. did. After nitrogen-substituting the system, it heated up from room temperature to 140 degreeC by atmospheric pressure / nitrogen atmosphere. When the polylactic acid and the aliphatic polycarbonate synthesized in Preparation Example 1 were dissolved, 0.5552 g of tin octanoate reagent from Wako Pure Chemical Company was charged and reacted at 140 ° C / atmospheric pressure under a nitrogen atmosphere for 23 hours.

After the reaction was completed, the reaction mass was charged into 770 ml of 1N hydrochloric acid, and the polymer was precipitated. After filtration, 700 ml of distilled water was charged and the polymer was washed with water. After filtration, the polymer was washed again with isopropyl alcohol. After filtration, it was dried under a nitrogen atmosphere to obtain 20.92 g (= 69.6%) of an aliphatic polyester copolymer.

The obtained aliphatic polyester copolymer was Mw = 8,800 and glass transition temperature = 82.7 degreeC.

Example 2

A polylactic acid (H-100 grade, Mw = 149,000) made by Cargill Dow's in a 300 ml round bottom flask with a refluxed solvent connected to a flask filled with 40.09 g of Molecular Sieves 3A. 7.22 g, 32.83 g of the aliphatic polycarbonate synthesized in Preparation Example 1 and 80.09 g of 1,3-dimethyl-2-imidazolidinone were charged. After nitrogen-substituting the system, it heated up at 140 degreeC after pressure-reducing to 60 mmHg at room temperature. After holding at 140 ° C./60 mmHg for 3 hours, 0.1061 g of tin octanoate reagent from Wako Pure Chemical was charged and reacted at 140 ° C./60 mmHg for 19 hours.

After the completion of the reaction, the reaction mass was charged into 1000 ml of 1N hydrochloric acid to precipitate a polymer. After filtration, 1000 ml of distilled water was charged and the polymer was washed with water. After filtration, the polymer was washed again with 1000 ml of isopropyl alcohol. After filtration, it dried in nitrogen atmosphere and obtained 28.84 g (= 72.0%) of aliphatic polyester copolymers.

The obtained aliphatic polyester copolymer was Mw = 26,000 and glass transition temperature = 152.3 ° C.

Example 3

Polylactic acid (H-100 grade, Mw = 149,000) made by Cargill Dow, in a 500 ml round-bottomed flask connected with a device where refluxed solvent was passed back through the bed filled with 30.07 g of Molecular Sieves 3A. 36.06 g) and 24.02 g of the aliphatic polycarbonate synthesized in Production Example 2 and 120.05 g of 1,3-dimethyl-2-imidazolidinone were charged. After nitrogen-substituting the system, it heated up at 140 degreeC after pressure-reducing to 60 mmHg at room temperature. After holding at 140 degreeC / 60mmHg for 3 hours, 1.0238g of reagent octanoate from Wako Pure Chemical Co., Inc. was charged, and it was made to react at 140 degreeC / 60mmHg for 18 hours.

After the completion of the reaction, the reaction mass was charged into 1000 ml of 1N hydrochloric acid to precipitate a polymer. After filtration, 1000 ml of methanol was charged and the operation of washing the polymer was repeated three times. After filtration, it dried under 50 degreeC / nitrogen atmosphere, and obtained 45.06g (= 75.0%) of aliphatic polyester copolymers.

The obtained aliphatic polyester copolymer was Mw = 52,000 and glass transition temperature = 89.3 ° C.

This aliphatic polyester copolymer was heat-pressed at 160 degreeC, and the press film of thickness 100micrometer was created. Transparency (haze) was less than 1%.

The tensile yield strength of this aliphatic polyester copolymer was 65 MPa.

Example 4

A polylactic acid (H-100 grade, Mw = 149,000) manufactured by Cargill Dow, in a 500 ml round-bottomed flask, in which a refluxed solvent was passed through a layer filled with 30.07 g of Molecular Sieves 3A and returned to the flask. 30.03 g, 30.02 g of the aliphatic polycarbonate synthesized in Production Example 2, and 120.05 g of 1,3-dimethyl-2-imidazolidinone were charged. After nitrogen-substituting the system, it heated up at 140 degreeC after pressure-reducing to 60 mmHg at room temperature. After hold | maintaining at 140 degreeC / 60mmHg for 3 hours, 1.0237g of tin octanoate reagents from Wako Pure Chemical were charged, and it was made to react at 140 degreeC / 60mmHg for 18 hours.

After the completion of the reaction, the reaction mass was charged into 1000 ml of 1N hydrochloric acid to precipitate a polymer. After filtration, 1000 ml of methanol was charged and the operation of washing the polymer was repeated three times. After filtration, it dried under 50 degreeC / nitrogen atmosphere, and obtained 46.23 g (= 77.0%) of aliphatic polyester copolymers.

The obtained aliphatic polyester copolymer was Mw = 45,000 and glass transition temperature = 100.2 ° C.

This aliphatic polyester copolymer was heat-pressed at 170 degreeC, and the press film of thickness 100micrometer was created. Transparency (haze) was less than 1%.

The tensile yield strength of this aliphatic polyester copolymer was 50 MPa.

Example 5

30.11 g of Glycolide and 20.02 g of the aliphatic polycarbonate synthesized in Production Example 1 were charged to a 200 ml separable flask and kept at room temperature / 6 mmHg for 3 hours. After returning to normal pressure with nitrogen, it heated up at 220 degreeC in nitrogen atmosphere. 1.5 hours after the start of temperature rising, 0.0229 g of tin octanoate reagent from Wako Pure Chemical Co., Ltd. was charged and reacted for 5 hours under a nitrogen atmosphere at 220 ° C / atm.

After completion of the reaction, the reaction mass was discharged from an enamel bat to obtain 40.12 g (= 80.0%) of an aliphatic polyester copolymer.

The obtained aliphatic polyester copolymer was Mw = 26,000, glass transition temperature = 60.1 ° C, crystallization temperature = 143.6 ° C, melting point = 199.7 ° C.

Comparative Example 1

The glass transition temperature of polylactic acid having a weight average molecular weight of 143,000 was 61.7 ° C.

Comparative Example 2

The glass transition temperature of the polyglycolic acid of weight average molecular weight = 200,000 was 37.7 degreeC.

The aliphatic polyester copolymer of the present invention consisting of an aliphatic polycarbonate unit and an aliphatic polyester unit according to the present invention has excellent heat resistance and is suitable for an optical disc base material, a container or a packaging material, and can be used as a substitute for a general purpose resin. Can be.

Claims (11)

General formula (1)

(In formula (1), X <_1> , X <_2> is O, N-R7, or S, and may mutually be same or different. Moreover, R <1>, R <2> is a C1-C10 alkylene chain and may be linear or branched. R3 to R7 may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and the alkyl group may be linear or branched, and the cycloalkyl group and the phenyl group may have a substituent. An aliphatic polyester copolymer comprising an aliphatic polycarbonate unit (a) and an aliphatic polyester unit (b) represented by. The method of claim 1, Aliphatic polyester copolymer, characterized in that the aliphatic polycarbonate unit (a) is a structure derived from that prepared from isosorbide and a carbonate precursor. The method according to claim 1 or 2, The aliphatic polyester copolymer (b) is a structure derived from lactic acid. The method of claim 1, An aliphatic polyester copolymer, wherein the composition ratio of the aliphatic polycarbonate unit (a) and the aliphatic polyester unit (b) is (a) / (b) = 5/95 to 50/50% by weight. The method of claim 1, An aliphatic polyester copolymer having a weight average molecular weight of 10,000 to 500,000. The method of claim 1, The aliphatic polyester copolymer characterized by higher glass transition temperature than the aliphatic polyester which has the same repeating unit as the aliphatic polyester unit (b) contained in an aliphatic polyester copolymer. The method of claim 1, Aliphatic polyester copolymer, characterized in that the haze is 5% or less. The molded article which consists of an aliphatic polyester copolymer of Claim 1. An optical disc base material comprising the aliphatic polyester copolymer according to claim 1. The sheet which consists of an aliphatic polyester copolymer of Claim 1. The container which consists of an aliphatic polyester copolymer of Claim 1.