EP2268704A1 - Procédé de fabrication en continu de polyesters biodégradables - Google Patents

Procédé de fabrication en continu de polyesters biodégradables

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Publication number
EP2268704A1
EP2268704A1 EP09732629A EP09732629A EP2268704A1 EP 2268704 A1 EP2268704 A1 EP 2268704A1 EP 09732629 A EP09732629 A EP 09732629A EP 09732629 A EP09732629 A EP 09732629A EP 2268704 A1 EP2268704 A1 EP 2268704A1
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EP
European Patent Office
Prior art keywords
acid
aliphatic
component
mixtures
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP09732629A
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German (de)
English (en)
Inventor
Uwe Witt
Motonori Yamamoto
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BASF SE
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BASF SE
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Priority to EP13167642.1A priority Critical patent/EP2628758B1/fr
Priority to EP09732629A priority patent/EP2268704A1/fr
Publication of EP2268704A1 publication Critical patent/EP2268704A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/785—Preparation processes characterised by the apparatus used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/247—Suited for forming thin films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • 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
  • 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.
  • 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
  • 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.
  • Biodegradable polyesters are aliphatic / aromatic polyesters - as described, for example, in WO-A 96/15173 and DE-A 10 2005053068.
  • biodegradable polyesters are aliphatic / aromatic polyesters which are structured as follows:
  • 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
  • n 2, 3 or 4 and m is an integer from 2 to 250,
  • 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.
  • 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.
  • malonic acid succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimel
  • ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which are likewise usable are the di-Ci- to C ⁇ -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.
  • 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.
  • 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.
  • di-d-C ⁇ -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.
  • 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.
  • 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.
  • the diols B are selected from branched or linear alkanediols having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms.
  • alkanediols examples include 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-
  • 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.
  • 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.
  • 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).
  • 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)
  • 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.
  • 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.
  • 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.
  • 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-C ⁇ -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”) ,
  • 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.
  • 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.
  • 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.
  • an acid scavenger 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.
  • 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,
  • 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 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) ,
  • 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® ®.
  • 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,
  • 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.
  • 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.
  • 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.
  • PBS polybutylene succinate
  • PBA polybutylene adipate
  • PBSA polybutylene succinate adipate
  • PBSSe polyisocyanate butylene succinate sebacate
  • PBSeA polybutylene sebacate
  • PBSe polybutylene sebacate
  • the aliphatic polyesters are marketed by Showa Highpolymers under the name Bionolle and by
  • 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
  • EN ISO 1133 190 0 C, 2.16 kg weight
  • 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.
  • 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%.
  • 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.
  • 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
  • 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 ,
  • aliphatic-aromatic copolyesters which have a low acid number according to DIN EN 12634.
  • biopolymers such as starch, polylactide (PLA) or polyhydroxyalkanoates.
  • the components A, B and optionally C are mixed.
  • the dicarboxylic acids are used as free acids (component A).
  • component A the mixture in the abovementioned mixing ratios - without addition of a catalyst - to a usually tempered at 20 - 70 0 C paste mixed.
  • 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.
  • dicarboxylic acids with the aliphatic Dyhydroxytheticen esterified to a purely aliphatic or aromatic polyester in a precursor and this then mixed with the other dicarboxylic acid and other aliphatic Dyhydroxythetic and optionally compound b2.
  • polybutylene terephthalate and / or polybutylene adipate can be used in this precursor.
  • 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.
  • 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.
  • 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.
  • 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.
  • stage i) and / or ii) further component b1 and the optional component c) may be added.
  • 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.
  • 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).
  • 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.
  • 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;
  • 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.
  • 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.
  • the precondensed polyester is optionally mixed with a deactivator for the catalyst.
  • a deactivator for the catalyst is particularly suitable deactivators.
  • 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).
  • a Ti / P ratio of 1, 3-1, 5: 1 and particularly preferably 1, 1-1, 3: 1 is set.
  • 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).
  • a Ti / P ratio (mol / mol) of 1, 0: 0.3-1, 0 and particularly preferably 1, 0: 0.5-1, 0 is set.
  • 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).
  • a Ti / P ratio (mol / mol) of 1, 0-1, 5: 1 and more preferably 1, 1-1, 3: 1 is set.
  • color stabilizer and activator such as triphenyl phosphate / di-sodium hydrogen phosphate.
  • the polycondensation takes place in a so-called finisher.
  • finisher 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.
  • the latter accounts for the increasing viscosity of the polyester with increasing reaction time.
  • 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.
  • 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.
  • 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.
  • 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.
  • the reaction mixture was transferred to a polycondensation reactor (as described, for example, in EP 0719582), and polycondensed at a temperature of 255 ° C.
  • 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).

Abstract

La présente invention concerne un procédé de fabrication en continu d'un polyester biodégradable à base d'acides dicarboxyliques aliphatiques ou aliphatiques et aromatiques et de composés aliphatiques dihydroxylés, un mélange des composés aliphatiques dihydroxylés, des acides dicarboxyliques aliphatiques et aromatiques et éventuellement d'autres comonomères (composant C) étant mélangé en une pâte sans ajouter de catalyseur ou, en variante, les esters liquides des acides carboxyliques, les composés dihydroxylés et éventuellement d'autres comonomères sont amenés sans addition de catalyseur, et dans lequel i) au cours d'une première étape, ce mélange est estérifié ou transestérifié en continu en même temps que la totalité ou qu'une partie d'un catalyseur au titane, ii) dans une deuxième étape, le produit de transestérification ou d'estérification obtenu en i) est pré-condensé dans un réacteur en tour et en s'écoulant en courants parallèles dans un évaporateur à film tombant, les vapeurs de réaction sont extraites in situ du mélange de réaction jusqu'à obtenir un indice de viscosité DIN 53728 de 20 à 80 cm3/g et iii), dans une troisième étape, le produit obtenu en ii) est polycondensé jusqu'à un indice de viscosité DIN 53728 de 100 à 220 cm3/g en continu.
EP09732629A 2008-04-15 2009-04-07 Procédé de fabrication en continu de polyesters biodégradables Withdrawn EP2268704A1 (fr)

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JP5675586B2 (ja) 2015-02-25
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JP2011516708A (ja) 2011-05-26
EP2628758B1 (fr) 2014-10-08
US20110034662A1 (en) 2011-02-10
WO2009127555A1 (fr) 2009-10-22
EP2628758A1 (fr) 2013-08-21

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