EP2268704A1

EP2268704A1 - Method for the continuous production of biodegradable polyesters

Info

Publication number: EP2268704A1
Application number: EP09732629A
Authority: EP
Inventors: Uwe Witt; Motonori Yamamoto
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-04-15
Filing date: 2009-04-07
Publication date: 2011-01-05
Also published as: US20110034662A1; JP2011516708A; WO2009127555A1; CN102007160A; EP2628758B1; CN102007160B; JP5675586B2; EP2628758A1; KR20110007186A

Abstract

The invention relates to a method for the continuous production of a biodegradable polyester on the basis of aliphatic or aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds. According to said method, a mixture of the aliphatic dihydroxy compounds, the aliphatic and aromatic dicarboxylic acids and optionally other comonomers (component C) is mixed to give a paste, without adding a catalyst, or alternatively, the liquid esters of the dicarboxylic acids and the dihydroxy compound and optionally other comonomers are fed to the mixture, without adding a catalyst, i) the mixture being continuously esterified or transesterified with the total amount or a partial amount of a titanium catalyst in a first step; ii) the transesterification or esterification product obtained according to i) being continuously precondensed in a second step in a tower reactor and in a uniform flow via a down-flow evaporator, the reaction vapors being removed from the reaction mixture in situ up to a viscosity number of 20 to 80 cm3/g (DIN 53728); iii) the product obtainable according to ii) being continuously polycondensed in a third step up to a viscosity number of 100 to 220 cm3/g (DIN 53728).

Description

Process for the continuous production of biodegradable polyesters

description

The present invention relates to a process for the continuous production of a biodegradable polyester based on aliphatic or aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds, wherein

a mixture of the aliphatic Dyhydroxyverbindungen, the aliphatic and aromatic dicarboxylic acids and optionally other comonomers (component C), without addition of a catalyst, are mixed to form a paste or alternatively the liquid esters of dicarboxylic acids and the dihydroxy compound and optionally other comonomers, without addition of a catalyst to be fed, being

i) in a first stage, this mixture is continuously esterified or transesterified together with the total amount or a partial amount of a titanium catalyst; ii) in a second stage continuously the transesterification or esterification product obtained according to i) in a tower reactor and in cocurrent over a falling film evaporator, wherein the reaction vapors are removed from the reaction mixture in situ up to a viscosity number according to DIN 53728 of 20 to 80 cm ³ / g is precondensed; iii) in a third stage, the product obtainable from ii) is continuously polycondensed to a viscosity number according to DIN 53728 of 100 to 220 cm ³ / g.

In particular, the invention relates to a process for the continuous production of a biodegradable polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds, wherein

a mixture of the aliphatic Dyhydroxyverbindungen, the aliphatic and aromatic dicarboxylic acids and optionally other comonomers (component C), without addition of a catalyst, are mixed into a paste or alternatively the liquid esters of dicarboxylic acids and the dihydroxy compound and optionally other comonomers, without addition a catalyst to be fed, wherein

i) in a first stage, this mixture is continuously esterified or transesterified together with the total amount or a partial amount of a titanium catalyst; (ii) in a second stage, continuously the transesterification or esterification product obtained in (i) in a tower reactor and in cocurrent flow over a falling film evaporator, wherein the reaction vapors are removed in situ from the reaction mixture is precondensed to a viscosity number according to DIN 53728 of 30 to 80 cm ³ / g; iii) in a third stage, the product obtainable from ii) is continuously polycondensed to a viscosity number according to DIN 53728 of 120 to 180 cm ³ / g.

Discontinuous (batch) processes are described in the prior art for the preparation of biodegradable polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds (WO-A 92/09654 and WO-A 96/15173). These have the disadvantage that the aliphatic / aromatic polyester must remain at high temperatures in the reaction vessel for a relatively long time in order to build up a high molecular weight - the desired viscosity number according to DIN 53728 is greater than 120 cm ³ / g. Due to the long residence times at high temperatures, the sensitive aliphatic / aromatic polyesters are partially degraded again. The acid number of the polyester increases rapidly and can easily reach values of greater than 1, 6 mg KOH / g. Biodegradable high acid polyesters have very limited hydrolytic stability.

Efficient, continuous processes for the preparation of aromatic polyesters such as PET and PBT are described in the literature (see, for example, WO 03/042278 and DE-A 199 29 790). However, these can not be directly transferred to aliphatic / aromatic polyesters. On the one hand, the aromatic polyesters often have higher acid numbers and, on the other hand, the problem of hydrolysis stability in aromatic polyesters is not as pronounced as with aliphatic / aromatic polyesters.

It was therefore an object of the present invention to provide a large-scale process which permits the production of biodegradable aliphatic / aromatic polyesters having viscosity numbers according to DIN 53728 of greater than 120 and simultaneously low acid numbers according to DIN EN 12634 (preferably less than 1.0 mg KOH / g, in particular less than 0.9 mg KOH / g, and process capability and cost-effectiveness (product yield and space / time yield) are of great importance for a large-scale process.

Surprisingly, the above-mentioned continuous, 3-stage process solves the problem in every respect.

Biodegradable polyesters are aliphatic / aromatic polyesters - as described, for example, in WO-A 96/15173 and DE-A 10 2005053068. In particular, biodegradable polyesters are aliphatic / aromatic polyesters which are structured as follows:

A) an acid component

a1) 30 to 99 mol% of at least one aliphatic dicarboxylic acid or its esters or mixtures thereof

a2) 1 to 70 mol% of at least one aromatic dicarboxylic acid or its esters or mixtures thereof and

a3) 0 to 5 mol% of a sulfonate group-containing compound,

wherein the molar percent of components a1) to a3) together give 100% and

B) of a diol component

b1) at least equimolar amounts of component A of a C2 to C12 alkanediol or mixtures thereof and b2) 0 to 2 wt .-% based on the amount of polyester according to step iii (corresponds to the amount of components A and B used minus the separated reaction vapors) of a compound containing at least 3 functional groups,

C) 0 to 30 wt .-% of one or more components C) selected from

d) at least one dihydroxy compound of the formula I containing ether functions

HO - [(CH ₂ ) _n -O] _m -H (I)

where n is 2, 3 or 4 and m is an integer from 2 to 250,

c2) at least one hydroxycarboxylic acid of the formula IIa or IIb

(IIa) (IIb) in which p is an integer from 1 to 1500 and r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, - (CH 2) _q -, where q is an integer from 1 to 5, -C (R) H- and -C (R) HCH ₂ , wherein R is methyl or ethyl

c3) at least one amino-C 2 -C 12 -alkanol or at least one amino-C 6 -C 10 -cycloalkanol or mixtures thereof

c4) at least one diamino-Ci- to Cs-alkane

c5) at least one aminocarboxylic acid compound selected from

A group consisting of caprolactam, 1,6-aminocaproic acid, lauriclactam, 1,1-aminolauric acid and 1,1-aminoundecanoic acid

or mixtures from d) to c5),

D) 0 to 4 wt .-% based on the amount of polyester after stage iii) of a di- or oligofunctional epoxide, oxazoline, oxazine, caprolactam and / or carbodiimides.

In a preferred embodiment, the acid component A of the partially aromatic polyesters contains from 30 to 70, in particular from 40 to 60, mol% of a1 and from 30 to 70, in particular from 40 to 60, mol% of a2. In a particularly preferred embodiment, the acid component A of the partially aromatic polyesters contains more than 50 mol% of aliphatic dicarboxylic acid a1). Such polyesters are characterized by an excellent biological degradation behavior.

As aliphatic acids and the corresponding derivatives a1 are generally those having 2 to 40 carbon atoms, preferably 4 to 14 carbon atoms, into consideration. They can be both linear and branched. The cycloaliphatic dicarboxylic acids which can be used in the context of the present invention are as a rule those having 7 to 10 carbon atoms and in particular those having 8 carbon atoms. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.

Examples which may be mentioned are malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethylglutaric acid , Suberic acid, dimer fatty acid (such as Empol® 1061 from Cognis1, 3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, maleic anhydride and 2,5-norbornanedicarboxylic acid.

Particularly suitable ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which are likewise usable are the di-Ci- to Cβ-alkyl esters, such as dimethyl, diethyl, di-n-propyl, di-isopropyl, di-n-butyl To mention di-iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl ester. Anhydrides of dicarboxylic acids can also be used.

The dicarboxylic acids or their ester-forming derivatives may be used singly or as a mixture of two or more thereof.

Succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof are preferably used. Succinic acid, adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof are particularly preferably used. Particular preference is given to using adipic acid or its ester-forming derivatives, such as their alkyl esters or mixtures thereof. Sebacic acid or mixtures of sebacic acid with adipic acid are preferably used as the aliphatic dicarboxylic acid when polymer mixtures with "hard" or "brittle" components ii), such as, for example, polyhydroxybutyrate or in particular polylactide, are prepared. Succinic acid or mixtures of succinic acid with adipic acid are preferably used as the aliphatic dicarboxylic acid when polymer blends with "soft" or "tough" components ii) are prepared, for example polyhydroxybutyrate covalerate or poly-3-hydroxybutyrate-co-4-hydroxybutyrate.

Succinic acid, azelaic acid, sebacic acid and brassylic acid also have the advantage that they are available as renewable raw materials.

As the aromatic dicarboxylic acid a2, there are generally mentioned those having 8 to 12 carbon atoms, and preferably those having 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2,6-naphthoic acid and 1, 5-naphthoic acid and ester-forming derivatives thereof. In particular, the di-d-Cβ-alkyl esters, e.g. Dimethyl, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, diisobutyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl ester. The anhydrides of dicarboxylic acids a2 are also suitable ester-forming derivatives.

In principle, however, it is also possible to use aromatic dicarboxylic acids a2 having a larger number of carbon atoms, for example up to 20 carbon atoms. The aromatic dicarboxylic acids or their ester-forming derivatives a2 may be used singly or as a mixture of two or more thereof. Particularly preferred is terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate used.

The sulfonate group-containing compound is usually an alkali metal or alkaline earth metal salt of a sulfonate-containing dicarboxylic acid or its ester-forming derivatives, preferably alkali metal salts of 5-sulfoisophthalic acid or mixtures thereof, particularly preferably the sodium salt.

According to one of the preferred embodiments, the acid component A contains from 40 to 60 mol% of a1, from 40 to 60 mol% of a2 and from 0 to 2 mol% of a3. According to a further preferred embodiment, the acid component A contains from 40 to 59.9 mol% a1, from 40 to 59.9 mol% a2 and from 0 to 1 mol% a3, in particular from 40 to 59.8 mol% a1, from 40 to 59.8 mol% a2 and from 0 to 0.5 mol% a3.

In general, the diols B are selected from branched or linear alkanediols having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms.

Examples of suitable alkanediols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2,4-dimethyl-2 ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2, 2,4-trimethyl-1,6-hexanediol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol and 2,2-dimethyl-1,3-propanediol (neopentyl glycol); Cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Particular preference is given to 1,4-butanediol, in particular in combination with adipic acid as component a1) and 1,3-propanediol, in particular in combination with sebacic acid as component a1). 1, 3 Propandiol also has the advantage that it is available as a renewable raw material. It is also possible to use mixtures of different alkanediols.

As a rule, a ratio of component b1 (diol) to diacids A of from 1.5 to 2.5 and preferably from 1.8 to 2.2 is set in process stages i) and ii).

The compounds b2) preferably contain at least three crosslinkers containing functional groups. Particularly preferred compounds have three to six hydroxyl groups. Examples include: tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; Polyether triols and glycerol, trimellitic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride. Preference is given to polyols such as trimethylolpropane, pentaerythritol and in particular glycerol. The compounds b2 can act as branching or crosslinking agents. By means of the components b2 can be built biodegradable polyester with a structural viscosity. The rheological behavior of the melts improves; The biodegradable polyesters are easier to process, for example, better by melt consolidation to remove films. The compounds b2 have a shear-thinning effect, ie the viscosity under load is reduced.

The compounds b2 are preferably used in amounts of 0.01 to 2, preferably 0.05 to 1, particularly preferably 0.08 to 0.20 wt .-%, based on the amount of polymer after stage iii).

In addition to the components A and B, the polyesters on which the polyester mixtures according to the invention are based can contain further components.

Suitable dihydroxy compounds d are diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran (polyTHF), particularly preferably diethylene glycol, triethylene glycol and polyethylene glycol, mixtures of which or compounds having different variables n (see formula I) For example, polyethylene glycol containing propylene units (n = 3), for example obtainable by polymerization according to known methods of first ethylene oxide and then with propylene oxide, more preferably a polymer based on polyethylene glycol, with different variables n, wherein units formed of ethylene oxide predominate , The molecular weight (M _n ) of the polyethylene glycol is usually selected in the range from 250 to 8000, preferably from 600 to 3000 g / mol.

According to one of the preferred embodiments, for example, from 15 to 98, preferably 60 to 99.5 mol% of the diols B and 0.2 to 85, preferably 0.5 to 30 mol% of the dihydroxy compounds d, based on the molar amount of B and d, be used for the preparation of partially aromatic polyester.

Hydroxycarboxylic acid c2) can be used to prepare copolyesters: glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, whose cyclic derivatives such as glycolide (1,4-dioxane-2,5-dione), D- , L-dilactide (3,6-dimethyl-1, 4-dioxane-2,5-dione), p-hydroxybenzoic acid and their oligomers and polymers such as 3-polyhydroxybutric acid, polyhydroxyvaleric acid, polylactide (for example as NatureWorks® (Fa. Cargill) and a mixture of 3-polyhydroxybutyric acid and polyhydroxy-valeric acid (the latter is available under the name Biopol® from Zeneca), particularly preferred for the preparation of partially aromatic polyesters are the low molecular weight and cyclic derivatives thereof.

The hydroxycarboxylic acids can be used, for example, in amounts of from 0.01 to 50, preferably from 0.1 to 40,% by weight, based on the amount of A and B. As amino-C2-Ci2-alkanol or amino-Cs-do-cyloalkanol (component c3), which should include 4-Aminomethylcyclohexanmethanol here, are preferably amino-C2-C6-alkanols such as 2-aminoethanol, 3-aminopropanol, 4th Aminobutanol, 5-aminopentanol, 6-aminohexanol and amino-Cs-Cβ-cycloalkanols such as aminocyclopentanol and aminocyclohexanol or mixtures thereof.

The diamino-C 1 -C 5 -alkane (component c4) used is preferably diamino-C 4 -C 6 -alkanes, such as 1,4-diminobutane, 1,5-diaminopentane and 1,6-diaminohexane (hexamethylenediamine, "HMD") ,

According to a preferred embodiment, from 0.5 to 99.5 mol%, preferably 0.5 to 50 mol%, of c3, based on the molar amount of B, and from 0 to 50, preferably from 0 to 35 mol% , c4, based on the molar amount of B, are used for the preparation of semiaromatic polyesters see.

As component c5, aminocarboxylic acid compounds selected from the group consisting of caprolactam, 1,6-aminocaproic acid, laurolactam, 1,1-aminolauric acid and 1,1-aminoundecanoic acid can be used.

In general, c5 is used in amounts of from 0 to 20, preferably from 0.1 to 10,% by weight, based on the total amount of components A and B.

In a preferred embodiment of the process, an acid scavenger (component D) selected from the group consisting of a di- or oligofunctional epoxide, oxazoline, oxazine, caprolactam and / or carbodiimide is added at the beginning, during or preferably at the end of stage iii and at usually 220 to 270 ⁰ C added. Component D is used in 0.01 to 4 wt .-%, preferably in 0.1 to 2 wt .-%, and particularly preferably in 0.2 to 1 wt .-%, based on the biopolymer.

Suitable components d are difunctional or oligofunctional epoxides such as: hydroquinone, diglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether and hydrogenated bisphenol A diglycidyl ether. Other examples of epoxides include diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, di- methyldiglycidylphthalat, Phenylendiglycidylether, Ethylendiglycidylether, trimethylene diglycidyl ether, Tetramethylendiglycidylether, Hexamethylendiglycidylether, sorbitol diglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether rol, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ethers, resorcinol diglycidyl ethers, neopentyl glycol diglycidyl ethers, ethylene glycol diglycidyl ethers, diethylene glycol diglycidyl ethers, polyethylene glycol diglycidyl ethers, pro- polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and polybutydiene glycol diglycidyl ether.

Particularly suitable as component d is an epoxide-group-containing copolymer based on styrene, acrylic ester and / or methacrylic acid ester. The epoxy groups bearing units are preferably glycidyl (meth) acrylates. Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight, of the copolymer have proved to be advantageous. The epoxy equivalent weight (EEW) in these polymers is preferably 150 to 3000, and more preferably 200 to 500 g / equivalent. The weight average molecular weight Mw of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000. The number-average molecular weight M _{n of} the polymers is preferably from 400 to 6,000, in particular from 1,000 to 4,000. The polydispersity (Q) is generally between 1.5 and 5. pen epoxide group-containing copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ^® ADR. Particularly useful as chain extenders are Joncryl ADR 4368 ^®, long-chain acrylates such as in EP Appl. Nos. 08166596.0 and Cardura ^® E10 Fa. Shell.

Bisoxazolines are generally available by the method of Angew. Chem. Int. Ed., Vol. 1 1 (1972), pp. 287-288. Particularly preferred bisoxazolines and bisoxazines are those in which the bridge member is a single bond, a (CHb) Z-alkylene group, where z = 2, 3 or 4, such as methylene, ethane-1, 2-diyl, propane-1, 3 diyl, propane-1, 2-diyl, or a phenylene group. Particularly preferred bisoxazolines are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1, 2-bis (2-oxazolinyl) ethane, 1, 3-bis (2-oxazolinyl) propane or 1,4-bis (2-oxazolinyl) butane, especially 1,4-bis (2-oxazolinyl) benzene, 1,2-bis (2-oxazolinyl) benzene or 1,3-bis (2-oxazolinyl) benzene , Further examples are: 2,2'-bis (2-oxazoline, 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4,4'-dimethyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxazoline), 2,2'-bis (4-propyl-2-oxazoline) , 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), 2 , 2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline), 2,2'-p-phenylene-bis (4-methyl-2-oxazoline) , 2,2'-p-phenylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylene-bis (4-methyl-2-oxazoline), 2,2'-m- Phenylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-hexamethylene-bis (2-oxazoline), 2,2'-octamethylene-bis (2-oxazoline), 2,2'-decamethylene -bis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-9 , 9'-Diphenoxyethane-bis (2-oxazoline), 2,2'-cyclohexylene-bis (2-oxazoline) and 2,2'-diphenylene-bis (2-oxazoline).

Preferred bisoxazines are 2,2'-bis (2-oxazine), bis (2-oxazinyl) methane, 1, 2-bis (2-oxazinyl) ethane, 1, 3-bis (2-oxazinyl) propane or 1, 4 Bis (2-oxazinyl) butane, in particular re 1, 4-bis (2-oxazinyl) benzene, 1, 2-bis (2-oxazinyl) benzene or 1, 3-bis (2-oxazinyl) benzene.

Carbodiimides and polymeric carbodiimides are sold for example by the company. Lanxxess under the tradename Stabaxol ^® or by the company. Elastogran under the trademark Elastostab® ^®.

Examples are: N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-o-tolylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-dioctyldecylcarbodiimide, N, N'-di-2, 6-dimethylphenylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-cyclohexylcarbodiimide, N, N'-di-p-tolylcarbodiimide, p-phenylene-bis-di- o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide, 4,4'-dicyclohexylmethanecarbodiimide, ethylene-bis-diphenylcarbodiimide, N, N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N Benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di -o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'-di-o-isopropylphenylcarbodiimide, N, N'-di-p-isopropylphenylca rbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide, N, N'-di-2-ethyl-6- isopropylphenylcarbodiimid, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimid, N, N'-di-2,4,6-trimethylphenylcarbodiimid, N ₁ N'-di-2,4,6-triisopropylphenylcarbodiimid, N, N '-Di-2,4,6-triisobutylphenylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, di-β-naphthylcarbodiimide and di-t-butylcarbodiimide.

Component d is used in 0.01 to 4% by weight, preferably in 0.1 to 2% by weight, and particularly preferably in 0.2 to 1% by weight, based on the polyester after stage iii. set.

Especially preferred are biodegradable partially aromatic polyesters containing as aliphatic dicarboxylic acid (component a1)) succinic acid, adipic acid or sebacic acid, their esters or mixtures thereof; as aromatic dicarboxylic acid (component a2)) terephthalic acid or its esters; as diol component (component B) 1, 4-butanediol or 1, 3-propanediol, and as component b2) glycerol, pentaerythritol, trimethylolpropane.

The process according to the invention can also be used for the production of aliphatic polyesters. Aliphatic polyesters include polyesters of aliphatic C 2 -C 12 -alkanediols and aliphatic C 4 -C 36 -alkanedicarboxylic acids, such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate adipate (PBSA), polyisocyanate butylene succinate sebacate (PBSSe), polybutylene sebacate adipate (PBSeA), polybutylene sebacate (PBSe) or corresponding polyesteramides. The aliphatic polyesters are marketed by Showa Highpolymers under the name Bionolle and by Mitsubishi under the name GSPIa. More recent developments are described in EP08165370.1.

The aliphatic polyesters prepared by the process according to the invention generally have viscosity numbers according to DIN 53728 of 100 to 220 cm ³ / g and preferably 150 to 250 cm ³ / g. MVR (melt volume rate) according to EN ISO 1133 (190 ⁰ C, 2.16 kg weight) is generally 0.1 to 70, preferably from 0.8 to 70 and in particular from 1 to 60 cm ^3/10 min.

The acid numbers according to DIN EN 12634 are generally from 0.01 to 1, 5 mg KOH / g, preferably from 0.01 to 1, 0 mg KOH / g and particularly preferably from 0.01 to 0.7 mg KOH / g ,

The abovementioned aliphatic and partially aromatic polyesters and the polyester mixtures according to the invention are biodegradable.

For the purposes of the present invention, the feature "biodegradable" for a substance or a substance mixture is fulfilled if this substance or the substance mixture according to DIN EN 13432 has a percentage degree of biodegradation of at least 90%.

In general, biodegradability causes the polyester (s) to disintegrate in a reasonable and detectable period of time. Degradation can be effected enzymatically, hydrolytically, oxidatively and / or by the action of electromagnetic radiation, for example UV radiation, and mostly for the most part be effected by the action of microorganisms such as bacteria, yeasts, fungi and algae. The biodegradability can be quantified, for example, by mixing polyesters with compost and storing them for a certain period of time. For example, according to DIN EN 13432, C02-free air is allowed to flow through ripened compost during composting and subjected to a defined temperature program. Here, the biodegradability is calculated as the ratio of the net CO 2 release of the sample (after deduction of CO2 release by the compost without sample) to the maximum CO 2 release of the sample (calculated from the carbon content of the sample) as a percentage of CO 2 defined biodegradation. Biodegradable polyesters (mixtures) usually show clear degradation phenomena such as fungal growth, cracking and hole formation after only a few days of composting. Other methods of determining biodegradability are described, for example, in ASTM D 5338 and ASTM D 6400.

The partially aromatic polyesters are usually random copolyesters, i. The incorporation of the aromatic and aliphatic diacid units is purely coincidental. The distribution of the length of the individual blocks can be calculated according to B. Vollmert, ground plan of the macromolecular chemistry. As described by Witt et al. In J. Environ. Pole. Degradation, Vol. 4, No. 1 (1996), s. 9, degradation in the compost of n> 3 aromatic model oligomers is normally very slow. In semi-aromatic polyesters, however, block structures are also degraded rapidly.

The preferred partially aromatic polyesters generally have a molecular weight (Mn) in the range from 1000 to 80,000, in particular in the range from 9,000 to 60,000 g / mol, preferably in the range from 20,000 to 40,000 g / mol, a molecular weight (Mw) of 50,000 to 250000, preferably 75000 to 180000 g / mol and a Mw / Mn

Ratio of 1 to 5, preferably 2 to 4 on. The melting point is in the range of 60 to 170, preferably in the range of 80 to 150 ⁰ C.

MVR (melt volume rate after step iii) is generally from 1, 0 to 15.0 cm ^3/10 min, preferably 2.5 to 12.0, and particularly preferably from 3.5 to 10.0 cm ^3/10 min ,

In addition to a high viscosity number, it is desirable to provide aliphatic-aromatic copolyesters which have a low acid number according to DIN EN 12634. The lower the acid number of the aliphatic / aromatic copolyesters, the more hydrolysis-stable the polyesters are on their own or in mixtures with biopolymers such as starch, polylactide (PLA) or polyhydroxyalkanoates. The storage stability of the upholstery (mixtures) improves accordingly.

The process according to the invention is described in more detail below.

In a preliminary stage, the components A, B and optionally C are mixed. In general, 1, 0 mol equivalents of a mixture of aliphatic and aromatic dicarboxylic acids or their esters (component A), 1, 1 to 1, preferably 5, preferably 1, 2 to 1, 4 mol-equivalent aliphatic Dyhydroxyverbindungen (component b1) .

0 to 2, preferably 0.01 to 0.5 wt .-%, based on the amount of polymer after stage iii of a compound b2 and optionally further comonomers (component C) are premixed.

In a preferred procedure, the dicarboxylic acids are used as free acids (component A). In this case, the mixture in the abovementioned mixing ratios - without addition of a catalyst - to a usually tempered at 20 - 70 ⁰ C paste mixed.

Alternatively, the liquid esters of dicarboxylic acids (component A) and the dihydroxy compound and optionally other comonomers, in the above-mentioned mixing ratios - without the addition of a catalyst - usually mixed at a temperature of 140 - 200 ⁰ C.

In a further alternative, one or both dicarboxylic acids with the aliphatic Dyhydroxyverbindungen esterified to a purely aliphatic or aromatic polyester in a precursor and this then mixed with the other dicarboxylic acid and other aliphatic Dyhydroxyverbindung and optionally compound b2. For example, polybutylene terephthalate and / or polybutylene adipate can be used in this precursor.

In step i), the previously described paste, slurry and / or liquid (precursor) of aliphatic and aromatic dicarboxylic acids (A) and an aliphatic dihydroxy compound (b1), optionally compound (b2) and further comonomers (component C) in the presence of 0.001 to 1 wt .-%, preferably 0.03 to 0.2, based on the amount of polymer after stage iii of a catalyst to a viscosity number according to DIN 53728 of usually 5 to 15 cm ³ / g esterified.

The excess diol component is distilled off as a rule and fed back to the circulation, for example, by distillation Aufreiningung.

In stage i), either the total amount or a partial amount, preferably 50 to 80 parts of the catalyst, is metered in. Titanium compounds are used in particular as catalysts. Titanium catalysts such as tetrabutyl orthotitanate or tetra (isopropyl) orthotitanate also have the advantage over the tin, antimony, cobalt and lead compounds such as tin dioctanate frequently used in the literature that residual amounts of the catalyst or secondary products of the catalyst remaining in the product remain Catalyst are less toxic. This fact is particularly important in the case of biodegradable polyesters, since they are released directly into the environment, for example as composting bags or mulch films.

At the same time in stage i) a temperature of 180 and 260 ⁰ C and preferably 220 to 250 ⁰ C and a pressure of 0.6 to 1, 2 bar and preferably 0.8 to 1, 1 bar set. Stage i) can be carried out in a mixing unit such as a hydrocylon. Typical residence times are 1 to 2 hours. Advantageously, stages i) and ii) are carried out in a single reactor such as a tower reactor (see, for example, WO 03/042278 and DE-A 199 29 790), the reactor having the internals suitable for the respective stage.

Optionally, in stage i) and / or ii) further component b1 and the optional component c) may be added. In general, in stage i), a ratio of component B (diol) to diacids A is adjusted from 1.5 to 2.5 and preferably from 1.8 to 2.2.

In stage ii), the liquid obtained in stage i (esterification) together with optionally the residual amount of catalyst is fed into a reactor suitable for the precondensation. Reactors such as a shell-and-tube reactor, a tank cascade or a bubble column and, in particular, a downflow cascade, if appropriate with a degassing unit, have proven suitable for precondensation (procedure iia). In general, reaction temperatures of 230 to 270 ⁰ C, preferably 240 to 260 ⁰ C and pressures at the beginning of stage ii) from 0.1 to 0.5, preferably 0.2 to 0.4 bar and at the end of stage ii ) from 5 to 100 mbar, preferably 5 to 20 mbar. It can be at residence times of 60 to 160 minutes aliphatic / aromatic prepolyesters having a viscosity number according to DIN 53728 of 30 to 80 and preferably 40 to 60 cm ³ / g produced. The acid numbers according to DIN EN 12634 of the prepolyester can still vary greatly after stage ii), depending on the method of preparation. If one starts in the precursor with the free dicarboxylic acids, the acid numbers at the end of stage ii) are still relatively high; however, they still decrease in stage iii). If it has been started in the precursor with the corresponding dicarboxylic acid ester, the acid number m at the end of stage ii) is comparatively small. Here, however, the acid numbers increase during the course of stage iii). As a rule, the acid numbers according to DIN EN 12634 at the end of stage ii) are 0.7 to 2 mg KOH / g.

An essential feature of precondensation ii) is the procedure described in detail in WO-A 03/042278 and WO-A 05/042615 in a tower reactor in which the product stream is passed in cocurrent over a single-stage or multistage falling-film evaporator, wherein the reaction vapors In particular, water, THF and when using dicarboxylic acid esters - are withdrawn distributed over the reactor at several points (driving way üb). The direct current method described in WO-A 03/042278 and WO-A 05/042615 with a continuous removal of the reaction vapors - at least at several points - is expressly incorporated herein by reference. This driving style has the following advantages in particular:

one can largely dispense with pumps for conveying the product stream; the product flow is easier to control as a gravimetric flow; Of the

Reactor can be operated at a slight overpressure, atmospheric pressure or at a low negative pressure (see above) The continuous removal of the reaction vapors in situ from the reaction mixture pushes the balance with already very gentle driving on the side of the reaction products. The rapid removal of the reaction vapors further side reactions are avoided or at least suppressed;

As a rule, aliphatic / aromatic prepolyesters with a viscosity number according to DIN 53728 of 30 to 80 cm ³ / g can be produced by the above-described procedure. Furthermore, these prepolyesters have very low acid numbers according to DIN EN 12634.

The reaction vapors, which consist essentially of water and with the use of dicarboxylic acid esters of alcohol, excess diol and by-product THF - when using the diol 1, 4-butanediol - are purified by conventional methods by distillation and recycled back into the process.

In the polycondensation step iii), the precondensed polyester is optionally mixed with a deactivator for the catalyst. Particularly suitable deactivators are phosphorus compounds, either organophosphites, such as phosphonic acid or phosphorous acid. The use of deactivators is particularly advisable when highly reactive titanium catalysts are used. The deactivators may be added in an amount of 0.001 to 0.1% by weight, preferably 0.01 to 0.05% by weight, based on the amount of polymer after stage iii). Preferably, a Ti / P ratio of 1, 3-1, 5: 1 and particularly preferably 1, 1-1, 3: 1 is set.

In the polycondensation step iii), the precondensed polyester is optionally mixed with a color stabilizer for the condensation. Suitable color stabilizers are, in particular, phosphorus compounds. Examples are phosphoric acid, phosphorous acid, triphenyl phosphite, triphenyl phosphate, IrgafosPEPQ and sodium hypophosphite and sodium phosphite. These phosphorus compounds can also be used as a mixture. The use of color stabilizers generally leads to a slowing of the condensation rate. A particular suitable color stabilizer is triphenyl phosphate, since the rate of condensation is not affected.

The color stabilizers can be added in an amount of 0.001 to 1, 5 wt .-%, preferably 0.01 to 1, 0 wt .-%, based on the amount of polymer after step iii). Preferably, a Ti / P ratio (mol / mol) of 1, 0: 0.3-1, 0 and particularly preferably 1, 0: 0.5-1, 0 is set.

In the polycondensation step iii), the precondensed polyester is optionally mixed with an activator for the condensation. Suitable activators are, in particular, phosphorus compounds. Examples are di-sodium hydrogen phosphate, calcium umpypophosphite, calcium phosphite, calcium phosphate, sodium hypophosphite, sodium phosphite, triphenyl phosphite, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, Irgafos 168. These phosphorus compounds can also be used as mixtures. Particularly suitable activators are di-sodium hydrogen phosphate and sodium phosphite.

The activators may be added in an amount of 0.001 to 1, 5 wt .-%, preferably 0.01 to 1, 0 wt .-%, based on the amount of polymer after step iii). Preferably, a Ti / P ratio (mol / mol) of 1, 0-1, 5: 1 and more preferably 1, 1-1, 3: 1 is set.

Of particular interest is the combined use: color stabilizer and activator such as triphenyl phosphate / di-sodium hydrogen phosphate.

The polycondensation takes place in a so-called finisher. In particular, reactors such as an annular disk reactor or a cage reactor, as described in US Pat. No. 5,777,986 and EP 719,582, have proven suitable as finishers. In particular, the latter accounts for the increasing viscosity of the polyester with increasing reaction time. As a rule, reaction temperatures of 220 to 270 ^° C., preferably 230 to 250 ^° C., and pressures of 0.2 to 5 mbar, preferably 0.5 to 3 mbar, are set.

It can be at residence times of 30 to 90 minutes, preferably 40 to 80 minutes aliphatic / aromatic polyester having a viscosity number according to DIN 53728 from 120 to 180 cm ³ / g and acid numbers according to DIN EN 12634 from 0.5 to 1, preferably 2 0 , 6 to 0.9 mg KOH / g produce. Typical molecular weights (Mn) are at 9000 to 60,000 molecular weights (Mw) at 50,000 to 250,000 The MVR (melt volume rate) is generally from 1, 0 to 15.0 cm ^3/10 min, preferably 2.5 to 12, 0 and particularly preferably at 3.5 to 10.0 cm ^3/10 min.

Measurement Methods:

The acid number was determined according to DIN EN 12634 of October 1998. The solvent mixture used was a mixture of 1 part by volume DMSO, 8 parts by volume propan-2-ol and 7 parts by volume toluene. The sample was heated to 50 ° C and combined with a single electrode with potassium chloride filling. The standard solution used was a tetramethylammonium hydroxide custom solution.

The determination of the viscosity number is carried out according to DIN 53728 Part 3, January 3, 1985. The solvent used was the mixture: phenol / dichlorobenzene in a weight ratio of 50/50. The determination of the melt volume flow rate (MVR) was carried out according to ISO 1133. The test conditions were 190 ⁰ C, 2.16 kg. The melting time was 4 minutes. The MVR indicates the rate of extrusion of a molten plastic molding through an extrusion tool of fixed length and fixed diameter under the conditions described above: temperature, load and position of the piston. The volume extruded in a specified time in the cylinder of an extrusion plastometer is determined.

Examples

1. Continuous production of polybutylene adipate-co-terephthalate

To prepare the biodegradable polyester, 19 kg / h of terephthalic acid, 19 kg / h of adipic acid, 32 kg / h of 1,4-butanediol and 0.05 kg / h of glycerol were physically mixed at 35 ° C., and then the mixture continuously in an esterification boiler (eg designed as a hydrocyclone, such as described in WO 03/042278 A1) converted. With the addition of an additional 16 kg / h of 1, 4-butanediol and 0.022 kg / h of tetrabutyl orthotitanate (TBOT), the mixture was esterified at a temperature of 240 ⁰ C, a residence time of 2.0 h and a pressure of 0.85 bar and the resulting condensation product water, and distilled off parts of the excess of butanediol. The resulting low molecular weight polyester had a viscosity number (VZ) of 14 cm ³ / g.

The reaction mixture was then added with the addition of another 0.012 kg TBOT / h, at a rising from 250 to 265 ⁰ C temperature, a residence time of 2.5 h and a decreasing from 250 mbar to 10 mbar pressure via a falling current cascade (as described, for example in WO 03/042278 A1) and distilled off the majority of excess butanediol. The polyester thus obtained had a viscosity number (CV) of 56 cm ³ / g. After addition of 0.01 kg / h of phosphorous acid, the reaction mixture was transferred to a polycondensation reactor (as described, for example, in EP 0719582), and polycondensed at a temperature of 255 ° C. and a pressure of 1 mbar for a further 70 minutes, and remaining excess of butanediol distilled off. The polyester thus obtained had a VZ of 158 cm ³ / g and an acid number (SZ) of 0.70 mg KOH / g. The MVR was 12.0 cm ^3/10 min (190 ⁰ C, 2.16 kg weight).

Claims

claims

1. A process for the continuous production of a biodegradable polyester based on aliphatic or aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds, wherein

a mixture of the aliphatic Dyhydroxyverbindungen, the aliphatic and aromatic dicarboxylic acids and optionally other comonomers (component C), without addition of a catalyst, are mixed to form a paste or alternatively the liquid esters of dicarboxylic acids and the dihydroxy compound and optionally other comonomers, without addition of a catalyst can be fed

i) in a first stage, this mixture is continuously esterified or transesterified together with the total amount or a partial amount of a titanium catalyst; ii) in a second stage continuously the transesterification or esterification product obtained according to i) in a tower reactor and cocurrently over a falling film evaporator, the reaction vapors being removed from the reaction mixture in situ up to a viscosity number according to DIN 53728 of 20 to 80 cm ³ / g is precondensed; iii) in a third stage, the product obtainable from ii) is continuously polycondensed to a viscosity number according to DIN 53728 of 100 to 220 cm ³ / g.

2. The method of claim 1, wherein the biodegradable polyester is composed of:

A) an acid component

a3) 0 to 5 mol% of a sulfonate group-containing compound,

wherein the molar percent of components a1) to a3) together give 100% and

B) a diol component of: b1) at least equimolar amounts to component A of a C2 to C12

Alkanediol or mixtures thereof and b2) 0 to 2% by weight, based on the components A and b1), of a compound containing at least 3 functional groups;

0 to 30 wt .-% of one or more components selected from

c1) at least one dihydroxy compound of the formula I containing ether functions

HO - [(CH ₂ ) _n -O] _m -H (I)

where n is 2, 3 or 4 and m is an integer from 2 to 250,

c2) at least one hydroxycarboxylic acid of the formula IIa or IIb

(IIa) (IIb)

in which p is an integer from 1 to 1500 and r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, - (CH 2) _q -, where q is an integer from 1 to 5, -C (R) H- and -C (R) HCH ₂ , wherein R is methyl or ethyl

c3) at least one amino-C 2 - to C 12 -alkanol or at least one amino-C 10 - to C 10 -cycloalkanol or mixtures thereof

c4) at least one diamino-Ci- to Cs-alkane

c5) at least one aminocarboxylic acid compound selected from the group consisting of caprolactam, 1,6-aminocaproic acid, laurolactam, 1,1-aminolauric acid and 1,1-aminoundecanoic acid

or mixtures from d) to c5), D) 0 to 4 wt .-% based on the amount of polyester after stage iii) of a di or oligofunctional epoxide, oxazoline, oxazine, caprolactam and / or carbodiimide.

3. The method of claim 1, wherein the biodegradable polyester as aliphatic dicarboxylic acid (component a1)) succinic acid, adipic acid or sebacic acid, their esters or mixtures thereof; as aromatic dicarboxylic acid (component a2)) terephthalic acid or its esters; as diol component (component B) 1, 4-butanediol or 1, 3-propanediol, and as component b2) glycerol, pentaerythritol, trimethylolpropane.

4. Process according to claims 1 to 3, wherein the esterification / transesterification (step i)) - is carried out in the form of a hydrocyclone with attached heat exchanger.

5. The method according to any one of claims 1 to 4, wherein between step ii) and iii) the product stream from 0.001 to 0.1 wt .-% of a deactivating phosphorus compound or 0.001 to 1, 5 wt .-% of a color-stabilizing or activating phosphorus compound be added.

6. The method according to any one of claims 1 to 5, wherein step iii) is carried out in an annular disk reactor or cage reactor.

7. The method according to any one of claims 1 to 6, wherein at the beginning, during or after step iii) 0 to 4 wt .-% based on the polyester amount of a di- or o-ligofunktionellen epoxide, oxazoline, oxazine, caprolactam and / or carbodiimide is added.