WO2020234294A1 - Procédé continu de production d'un polyester aliphatique-aromatique - Google Patents

Procédé continu de production d'un polyester aliphatique-aromatique Download PDF

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WO2020234294A1
WO2020234294A1 PCT/EP2020/063963 EP2020063963W WO2020234294A1 WO 2020234294 A1 WO2020234294 A1 WO 2020234294A1 EP 2020063963 W EP2020063963 W EP 2020063963W WO 2020234294 A1 WO2020234294 A1 WO 2020234294A1
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aliphatic
polyester
acid
weight
aromatic
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PCT/EP2020/063963
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English (en)
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Timo Benjamin WITT
Jerome LOHMANN
Norbert Effen
Jens-Uwe Schierholz
Motonori Yamamoto
Andreas Kuenkel
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Basf Se
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    • 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
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/02—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor of the thin-film type
    • 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
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • 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
    • C08G63/88—Post-polymerisation treatment
    • C08G63/90—Purification; Drying
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00168—Controlling or regulating processes controlling the viscosity
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00189—Controlling or regulating processes controlling the stirring velocity
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00252—Formation of deposits other than coke

Definitions

  • a continuous process for producing an aliphatic-aromatic polyester constructed from aliphatic dicarboxylic acids, aromatic dicarboxylic acids and aliphatic diols comprising the stages of i) esterification, ii) polycondensation and optional ly iii) chain extension, wherei n during stage ii) in which the polycondenser functions as a degassing apparatus the crude polyester is degassed at a pressu re of 0.01 to 5 mbar in the presence of 0.01 % to 1 % by weight, preferably 0.02 to 0,2 % by weight based on the total weight of the crude polyester, introduced into the gas space of the degassing apparatus as an entraining agent.
  • EP-A 2623540 describes a process for pu rifying aliphatic polyesters such as polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA) or polybutylene succinate-co-sebacate (PBSSe) , in which cyclic byproducts are extracted by means of extraction with solvents.
  • PBS polybutylene succinate
  • PBSA polybutylene succinate-co-adipate
  • PBSSe polybutylene succinate-co-sebacate
  • the present invention accordingly has for its object to find an efficient and scaleable continuous process for purifying aliphatic-aromatic polyesters with reduced amount of cyclic ester oligomers, particularly cyclic ester monomers and dimers which have the highest relevance to obtain an approval for contact with foodstuffs according to EU 10/2011.
  • the inventors have surprisingly found a continuous process for producing an aliphatic-aromatic polyester constructed from aliphatic dicarboxylic acids, aromatic dicarboxylic acids and aliphatic diols com prising the stages of i) esterification, ii) polycondensation and optionally iii) chain extension, wherein du ring stage ii) in which the polycondenser functions as a degassing apparatus the crude polyester is degassed at a pressure of 0.01 to 5 m bar in the presence of 0.01 % to 1 % by weight, preferably 0.02 to 0,2 % by weight based on the total weight of the crude polyester, introduced into the gas space of the degassing apparatus as an entraining agent.
  • Biodegradable aliphatic-aromatic (semiaromatic) polyesters are described by way of example in WO-A 96/15173 and WO-A 2009/127556.
  • biodegradable polyesters are aliphatic-aromatic polyesters whose structure is as follows:
  • a diol component composed of: bl) at least equimolar amounts with respect to component A of a C 2 -C 12 alkanediol, or a mixture thereof, and
  • b2) from 0 to 2% by weight, based on the amount of polyester after stage ii (which corresponds to the amou nt used of components A and B minus the reaction vapors removed), of a compou nd comprising at least 3 fu nctional groups; and C) of from 0 to 10% by weight, preferably 0 % by weight based on the total amou nt of components A and B of a component selected from: cl) at least one dihydroxy compound comprising ether functions and having the formu la I HO-[(CH 2 ) n -0] m -H (I) where n is 2, 3 or 4 and m is a whole num ber from 2 to 250, c2) at least one hyd roxycarboxylic acid of the formula lla or l ib
  • the acid component A of the semiaromatic polyesters comprises from 40 to 60 mol%, of al and from 40 to 60 mol%, of a2.
  • the acid component A of the semiaromatic polyesters com prises more than 50 mol% of aliphatic dicarboxylic acid al) .
  • a feature of these polyesters is excel lent biodegradability.
  • Aliphatic acids and the corresponding derivatives al which may be used are general ly those having from 2 to 40 carbon atoms, preferably from 4 to 14 carbon atoms. They may be either linear or branched.
  • the cycloaliphatic dicarboxylic acids which may be used for the purposes of the present invention are general ly those having from 7 to 10 carbon atoms and in particular those having 8 carbon atoms. I n principle, however, it is also possible to use dicarboxylic acids having a larger nu mber of carbon atoms, for example having up to 30 carbon atoms.
  • 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 (e.g.
  • Empol ® 1061 from Cognis 1,3-cyclopentanedicarboxylic acid, 1,4- cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, maleic anhyd ride, and 2,5-norbornanedicarboxylic acid.
  • Ester-forming derivatives of the abovementioned ali phatic or cycloaliphatic dicarboxylic acids which may also be used and which may be mentioned are in particular the di-C j -Cg-alkylesters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl, di-tert-butyl, di-n-pentyl, diisopentyl or di-n-hexylesters. It is also possi ble to use anhydrides of the dicarboxylic acids.
  • dicarboxylic acids or their ester-forming derivatives may be used here individually or in the form of a mixtu re composed of two or more of these.
  • succinic acid adipic acid, azelaic acid, sebacic acid, brassylic acid, or their respective ester-forming derivatives, or a mixtu re thereof. It is particularly preferable to use succi nic acid, adipic acid, or sebacic acid, or their respective ester-forming derivatives, or a mixtu re thereof. It is particularly preferable to use adipic acid or its ester-forming derivatives, for example its al kyl esters or a mixtu re of these. Sebacic acid or a mixtu re of sebacic acid with adipic acid is preferably used as aliphatic dicarboxylic acid.
  • Succinic acid, azelaic acid, sebacic acid, and brassylic acid have the additional advantage of being available in the form of renewable raw materials.
  • Aromatic dicarboxylic acids a2 which may be mentioned are general ly those having from 6 to 12 carbon atoms and preferably those having 8 carbon atoms.
  • terephthalic acid isophthalic acid, 2,6-naphthoic acid and 1,5-naphthoic acid, 2,5-furandicarboxylic acid, and also ester-forming derivatives of these.
  • di-C j -C 8 - alkylesters e.g.
  • dicarboxylic acids a2 are also suitable ester-forming derivatives.
  • aromatic dicarboxylic acids a2 having a greater number of carbon atoms, for example up to 20 carbon atoms.
  • aromatic dicarboxylic acids or ester-forming derivatives of these a2 may be used individually or as a mixture of two or more of these. It is particularly preferable to use terephthalic acid or its ester-forming derivatives, such as dimethyl terephthalate.
  • the compound used comprising sulfonate groups is usually one of the alkali metal or alkaline earth metal salts of a dicarboxylic acid comprising sulfonate groups or ester-forming derivatives thereof, preferably alkali metal salts of 5-sulfoisophthalic acid or a mixture of these, particularly preferably the sodium salt.
  • the acid component A comprises from 40 to 60 mol% of al, from 40 to 60 mol% of a2, and from 0 to 2 mol% of a3.
  • the diols B are generally selected from branched or linear alkanediols having from 2 to 12 carbon atoms, preferably from 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-ethyl -1,3- hexanedio I, 2,2-dimethyl -1,3 -propanediol, 2 -ethyl -2 -butyl -1,3- propanediol, 2-ethyl-2-isobutyl-l, 3-propanediol and 2,2,4-trimethyl-l,6-hexanediol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol or 2,2-dimethyl-l,3- propanediol (neopentyl glycol); cyclopentane
  • 1.4-butanediol and 1,3-propane-diol, in particular in combination with sebacic acid as component al).1,4-butanediol and 1,3-propanediol have the additional advantage of being obtainable in the form of a renewable raw material. It is also possible to use mixtures of different alkanediols.
  • the ratio of component bl (diol) to diacids A generally set in stages i) of the process is from 1.5 to 2.5 and preferably from 1.8 to 2.2.
  • the compounds b2) preferably comprise crosslinking agents comprising at least three functional groups. Particularly preferred compounds have from three to six hydroxy groups. Exam ples that may be mentioned are: tartaric acid, citric acid, malic acid; trimethylolpropane, trimethylolethane; pentaerythritol; polyethertriols, and glycerol, trimesic acid, trimel litic acid, trimel I itic anhyd ride, pyromel litic acid, and pyromel litic dianhyd ride. Preference is given to polyols, such as
  • the compounds b2 can act as branching agents or else as crosslinking agents. By using components b2, it is possible to construct biodegradable polyesters which are pseudoplastic.
  • the rheology of the melts improves; the biodegradable polyesters are easier to process, for example easier to d raw by melt-solidification processes to give foils.
  • the compounds b2 have a shear-thinning effect, and viscosity therefore decreases under load.
  • amou nts used of the com pounds b2 are preferably from 0.01 to 2% by weight, with preference from 0.05 to 1% by weight, with particular preference from 0.08 to 0.20% by weight, based on the total amount of polymer.
  • polyesters on which the polyester mixtu res of the invention are based can comprise further com ponents alongside com ponents A and B.
  • the component dl used com prises an isocyanate or a mixture of various isocyanates. It is possible to use aromatic or aliphatic diisocyanates. However, it is also possible to use isocyanates of higher functionality.
  • an aromatic diisocyanate dl is especial ly tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 2,2’-diiso- cyanate, diphenylmethane 2,4’-diisocyanate, diphenyl methane 4,4’-diisocyanate, naphthylene 1,5-diisocyanate, or xylylene diisocyanate.
  • diphenylmethane 2,2’-, 2,4’-, or 4,4' - diisocyanate as component dl.
  • diisocyanates are generally used in the form of a mixtu re.
  • An isocyanate d l that can also be used, having three rings, is tri(4-isocyanato- phenyO methane.
  • Polynuclear aromatic diisocyanates are produced by way of example during production of diisocyanates having one or two rings.
  • Com ponent dl can also comprise subordinate amounts of uretdione groups, for example up to 5% by weight, based on the total weight of component dl, for example for capping of the isocyanate grou ps.
  • an aliphatic diisocyanate dl is especially any of the linear or branched al kylene diisocyanates or cycloal kylene diisocyanates having from 2 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, exam ples being hexamethylene 1,6-diisocyanate, isophorone diisocyanate, or
  • diisocyanates dl are isophorone diisocyanate and especial ly hexamethylene 1,6- diisocyanate.
  • isocyanu rates are the aliphatic isocyanu rates that derive from al kylene diisocyanates or from cycloal kylene diisocyanates, where these have from 2 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, exam ples being isophorone diisocyanate or methylenebis(4-isocyanatocyclohexane).
  • al kylene diisocyanates can be either linear or branched compounds. Particu lar preference is given to isocyanurates based on n-hexamethylene diisocyanate, examples being cyclic trimers, pentamers, or higher oligomers of hexamethylene 1,6-diisocyanate.
  • amou nts generally used of com ponent dl are from 0 to 4% by weight, preferably from 0.1 to 2% by weight, particu larly preferably from 0.2 to 1.2% by weight, based on the total amount of polymer.
  • Suitable di- or oligofunctional peroxides are the fol lowing compou nds: benzoyl peroxide, 1 , 1 - bi s (tert- butyl peroxy) -3,3,5- trimethylcyclohexane, l,l-bis(tert-butyl peroxy) methylcyclododecane, n-butyl 4,4- bis(butylperoxy)valerate, dicumyl peroxide, tert-butyl peroxybenzoate, dibutyl peroxide, a , a -bis(tert-butylperoxy)diisopropyl benzene, 2 ,5 - di m ethy I -2 ,5-d i (tert- butylperoxy) hexane, 2,5-dimethyl-2,5-di(tert- butyl peroxy) hex-3-yne, and tert
  • amou nt used of component d2 is from 0 to 4% by weight, preferably from 0.1 to 2% by weight, and particularly preferably from 0.2 to 1% by weight, based on the biopolymer.
  • the component d3 used can comprise difunctional or oligofu nctional epoxides, such as: hydroquinone, diglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether.
  • difunctional or oligofu nctional epoxides such as: hydroquinone, diglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether.
  • epoxides comprise diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahyd rophthalate, dimethy Idiglycidyl phthalate, phenylene diglycidyl ether, ethylene diglycidyl ether, trimethylene diglycidyl ether, tetramethylene diglycidyl ether, hexamethylene diglycidyl ether, sorbitol diglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether,
  • a particularly suitable component d3 is a copolymer com prising epoxy grou ps and based on styrene, acrylic ester and/or methacrylic ester d3a.
  • the u nits bearing epoxy groups are preferably glycidyl (meth)acrylates.
  • Compounds that have proven advantageous are copolymers having a proportion of more than 20% by weight, particularly preferably more than 30% by weight, and with particular preference more than 50% by weight, of glycidyl methacrylate in the copolymer.
  • the epoxy equivalent weight (EEW) in these polymers is preferably from 150 to
  • the average molecu lar weight (weight average) MW of the polymers is preferably from 2000 to 25 000, in particu lar from 3000 to 8000.
  • (number average) M n of the polymers is preferably from 400 to 6000, in particular from 1000 to 4000.
  • the polydispersity (Q) is general ly from 1.5 to 5.
  • Copolymers of the abovementioned type com prising epoxy groups are marketed by way of example by BASF Resins B.V. with trademark Joncryl ® ADR.
  • Particularly suitable chain extenders are Joncryl ® ADR 4368, Joncryl ® ADR 4468, long-chain acrylates as described in EP Application No. 08166596.0, and Cardura ® E10 from Shell.
  • the amou nt of component d3 used, based on the biopolymer, is from 0 to 4% by weight, preferably from 0.1 to 2% by weight, and particularly preferably from 0.2 to 1% by weight.
  • Com ponent d3 can also be used as acid scavenger.
  • the concentration used of d3 is from 0.01 to 0.5% by weight, and that this is followed by chain extension usi ng component dl, d2 and/or d3a, the concentration of which added is preferably from 0.2 to 1.2% by weight.
  • biodegradable, aliphatic-aromatic polyester Particular preference is given to biodegradable, aliphatic-aromatic polyester:
  • polybutylene adipate coterephthalate which com prises, as component A: 45 to 55 mol% of adipic acid (component al) and 45 to 55 mol% of terephthalic acid (component a2) ) ; as diol component (component B) : 100 mol% 1,4-butanediol; as component b2) 0.03 to 2% by weight, based on the polyester, glycerol,
  • biodegrada ble a li phatic-aromatic polyester: polybutylene sebacate coterephthalate (PBSeT) which com prises, as component A: 45 to 55 mol% of sebacic acid (component al) and 45 to 55 mol% of terephthalic acid (component a2)) ; as diol component (component B): 100 mol% 1,4-butanediol; as component b2) 0.03 to 2% by weight, based on the polyester, glycerol, pentaerythritol, and trimethylol propane as com ponent dl) 0 to 2%, preferably 0.1 to 1 % by weight, based on the polyester, hexamethylene diisocyanate.
  • PBSeT polybutylene sebacate coterephthalate
  • the aliphatic-aromatic polyesters are generally random copolyesters, i.e. the aromatic and aliphatic diacid units are incorporated entirely randomly.
  • the distribution of the lengths of the individual blocks can be calculated by the method of B. Vol lmert, Grundriss der makromolekularen Chemie [Basic princi ples of macromolecular chemistry] . As described by Witt et al. in J. Environ. Pol.
  • the molar mass (Mn) of the aliphatic-aromatic polyesters, preferably polybutylene adipate coterephthalate is generally in the range from 1000 to 100 000 g/mol, in particular in the range from 9000 to 75 000 g/mol, preferably in the range from 20 000 to 50 000 g/mol, and their molar mass (Mw) is generally from 50 000 to 300 000 g/mol, preferably from 75 000 to 200 000 g/mol, and their Mw/Mn ratio is general ly from 1 to 6, preferably from 2 to 4.
  • the melting point is in the range from 60 to 170° C, preferably i n the range from 80 to 150° C.
  • the MVR (melt volume rate) according to EN ISO 1133 (190° C, 2.16 kg weight) of the aliphatic-aromatic polyester is generally 0.1 to 6.0 cm 3 /10 min, preferably 0.5 to 5.0 cm 3 /10 min and particularly preferably 1.0 to 3 cm 3 /10 min.
  • the viscosity nu mber according to DIN 53728 of the ali phatic- aromatic polyesters are from 160 to 250 cm 3 /g, preferably from 170 to 220 cm 3 /g. The dimension for the viscosity numbers is always cm 3 /g.
  • the MVR (melt volume rate) according to EN ISO 1133 (190° C, 2.16 kg weight) of the aliphatic-aromatic polyester is general ly 2 to 100 cm 3 /10 min, preferably from 3 to 50 cm3/10 min, and particularly preferably from 5 to 20 cm 3 /10 min.
  • the viscosity number according to DIN 53728 of the aliphatic-aromatic polyesters are from 80 to 200 cm 3 /g, preferably from 100 to 150 cm 3 /g.
  • aliphatic-aromatic copolyesters which not only have high viscosity numbers but also have low acid number to DI N EN 12634.
  • polyhydroxyalkanoates aliphatic polyester such as Bionol le ® , cellulose, or polycaprolactone.
  • the shelf life of the polyesters or polyester mixtures improves accordingly.
  • the feature "biodegradable” is achieved by a substance or a su bstance mixtu re if this substance or the su bstance mixtu re exhibits, as defined in DIN EN 13432, a percentage degree of biodegradation of at east 90%.
  • Biodegradation generally leads to decomposition of the polyesters or polyester mixtu res in an appropriate and demonstrable period of time.
  • the degradation can take place by an enzymatic, hydrolytic, or oxidative route, and/or via exposu re to electromagnetic radiation, such as UV radiation, and can mostly be brought about predominantly via exposure to microorganisms, such as bacteria, yeasts, fungi, and algae.
  • Biodegradabi lity can be quantified by way of example by mixing polyester with com post and storing it for a particular period.
  • C0 2 -free air is passed through ripened com post du ring the composting process, and the compost is subjected to a defined temperature profile.
  • the biodegradability here is defined as a percentage degree of biodegradation by way of the ratio of the net amou nt of C0 2 released from the specimen (after subtraction of the amount of C0 2 released by the compost without specimen) to the maximum amou nt of C0 2 that can be released from the specimen (calculated from the carbon content of the specimen).
  • Biodegradable polyesters or biodegradable polyester mixtures general ly exhibit marked signs of degradation after just a few days of com posting, examples being fungal growth, cracking, and perforation.
  • EU Regulation 10/2011 specifies migration limits of substances in plastics materials that are in contact with food products.
  • Packaging materials made of non- pu rified aliphatic-aromatic polyesters such as polybutylene adipate terephthalate (PBAT) do not necessarily meet the requirements of this standard and are restricted in their application as food contact material.
  • PBAT polybutylene adipate terephthalate
  • the cyclic im purities in the polyester such as THF, cyclic monomers, dimers, trimers and tetramers can migrate out of the packaging material under the various test conditions.
  • the process according to the invention now provides aliphatic-aromatic polyesters which are distinctly depleted in cyclic impu rities and which achieve the threshold values required in EU Regulation 10/2011.
  • liquid esters of the dicarboxylic acids (com ponent A) and the dihyd roxyl com pound and optional ly fu rther comonomers are mixed in the abovementioned mixing ratios - preferably without addition of a catalyst - generally at a temperature of 40-200° C.
  • I n a fu rther alternative one or more dicarboxylic acids are esterified with the aliphatic diol to afford highly flowable polyester having a viscosity of 5 to 15 cm 3 /10 min and employed in the preliminary stage.
  • the excess diol component is general ly distilled off and after distil lative purification for example returned to the circuit.
  • I n stage i) either the total amount or a sub-amou nt - preferably 50 to 80 parts - of the catalyst are supplied.
  • Typical ly employed catalysts are zinc, aluminu m and especial ly titaniu m com pou nds.
  • I n addition, com pared to tin, antimony, cobalt and ead compounds often used in the prior art such as tin dioctanate, titanium catalysts such as tetrabutyl orthotitanate or tetra(isopropyl)orthotitanate have the advantage that residual amounts of the catalyst or descendent products of the catalyst remaining in the product have a lower toxicity. This fact is particu larly im portant in the case of the biodegradable polyesters, since they get directly into the environ ment, for example, in the form of composting bags or mu lch films.
  • stage i) A temperature of 180° C to 260° C, preferably 220° C to 250° C, and a pressure of 0.6 to 1.2 bar, preferably 0.8 to 1.1 bar, are simultaneously established in stage i).
  • Stage i) may be performed in a mixing apparatus such as a hydrocyclone for example. Typical residence times are 1 to 2 hours.
  • Stage i) (esterification and pre-condensation) is advantageously performed in a single reactor such as for example a tower reactor (see for example WO 03/042278 and WO 2009/127556), wherein the reactor com prises the internals suitable for the particular stage.
  • Reactors such as a shell and tube reactor, a tank cascade or a bubble colu mn and especial ly a downflow cascade optional ly comprising a degassing u nit have proven advantageous for the pre-condensation.
  • reaction temperatures of 230° C to 270° C, preferably 240° C to 260° C, and pressures at the begin ning of stage i) of 0.1 to 0.5 bar, preferably 0.2 to 0.4 bar, and at the end of stage i) of 5 to 100 mbar, preferably 5 to 20 mbar.
  • the acid nu mbers according to DI N EN 12634 at the end of stage i) are general ly 0.7 to 2 g KOH/g.
  • Reactors which have proven particu larly advantageous for the precondensation i) are the tower reactors described in detail in WO-A 03/042278 and WO 2009/127556 in which the product stream is passed cocurrently through a single or multistage fal ling-film evaporator, wherein the reaction vapors - i n particular water, THF, and, if dicarboxylic esters are used, alcohols - are drawn off at a plu rality of sites distributed over the reactor.
  • reaction vapours consisting essential ly of water and, if dicarboxylic esters are used, of alcohol, of excess diol and - if the diol 1,4-butanediol is used - byproduct THF are su bjected to distillative purification by customary processes and recycled into the process.
  • the precondensed polyester is optionally admixed with a deactivator for the catalyst.
  • Contemplated deactivators include in particular phosphorus compounds, either organophosphites such as phosphonous acid or phosphorous acid or inorganic phosphites such as sodium phosphite or sodium hypophosphite. The use of deactivators is particularly advisable when highly reactive titanium catalysts are em ployed.
  • the deactivators may be added in an amou nt of 0.001% to 0.1% by weight, preferably 0.01% to 0.05% by weight, based on the polymer amou nt after stage ii) .
  • a Ti/P ratio of 1.3-1.5 : 1 is preferred and 1.1- 1.3 : 1 especial ly preferred.
  • the polycondensation stage ii) is carried out in a so-cal led finisher.
  • Apparatuses that have proven particu larly suitable as finishers include in particu lar reactors such as a spinning-disc reactor or a cage reactor, as described in US 5779986 and EP 719582.
  • the latter reactor in particular accommodates the increasing viscosity of the polyester with increasi ng reaction time.
  • reaction temperatures of 220° C to 270° C, preferably 230° C to 250° C and pressures of 0.1 to 5 mbar, preferably 0.5 to 5 mbar.
  • I n order to l imit the average residence time of the polymer melt the conveying of the melt through the finisher may be adjusted for example via a higher speed of rotation of the disc or of the cage.
  • I n this stage typical molecular weights (M n) are 10 000 to 25 000 and molecular weights (Mw) are 35 000 to 70 000.
  • a finisher as described hereinabove (a spinning-disc reactor or a cage reactor) is provided with a means which allows introduction of the entraining agent into the gas space of the finisher.
  • a suitable entraining agent is an inert gas such as carbon dioxide, argon, methane, ethane, propane, butane, and preferably nitrogen.
  • the amou nt of the entraining agent is generally between 0.01 % and 2% by weight, preferably 0.02 % to 0.2% by weight, based on the polyester at the end of stage i) (crude polyester) . Greater amounts of entraining agent result i n an unacceptable im pairment of the vacuum established in the finisher. At a lower entraining agent concentration the crude polyester is insufficiently depleted in cyclic impurities such as THF and cyclic monomers, dimers, trimers and tetramers of the polyester.
  • the entraining agent is introduced i nto the gas space of the finisher. This has the advantage that a homogeneous polyester film is formed in the finisher and for example blister formation or foaming in the polyester fil m are avoided.
  • the finisher the polymer melt general ly forms an average fil m thickness of less than 5 mm, preferably less than 2 mm and especial ly preferably less than 1 m m.
  • the preferred chain-extended aliphatic-aromatic polyesters are produced as described in the literature or in the introduction (see optional stage iii).
  • I n the chain extension (stage iii) the polycondensed polyester is introduced into an extruder, a continuous kneader (List reactor) or a static mixer together with 0.01% to 4% by weight, preferably 0.1% to 2% by weight and especially preferably 0.5% to 1.2% by weight based on the polyester of a chain extender.
  • I nternals that may be employed include: in the case of a static mixer SMR, SMX, or SMXL elements or combinations thereof, for example from Sulzer Chemtech AG, Switzerland.
  • Examples of a List reactor include depending on the field of application a single screw DISCOTHERM B reactor or twin-screw CRP and ORP reactors.
  • Suitable extruders include single-screw or twin-screw extruders.
  • Suitable chain extenders include the above-described isocyanates or isocyanu rates dl, peroxides d2 and epoxides d3.
  • These diisocyanates are selected for example from the group consisting of tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, 4,4’- and 2,4’-diphenyl methane diisocyanate, naphthylene 1,5-diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and methylenebis(4-isocyanatocyclohexane). Hexamethylene diisocyanate is particularly preferred.
  • the chain extension reaction is carried out at reaction tem peratu res of 220° C to 270° C, preferably 230° C to 250° C, and at superatmospheric pressure or atmospheric pressu re depending on the system used. Residence times of 2 to 30 minutes, preferably 4 to 15 minutes, al low production of aliphatic-aromatic polyesters having a viscosity number according to DI N 53728 of 160 to 250 cm 3 /g and acid numbers according to DI N EN 12634 of preferably 0.5 to 1.2 mg KOH/g and especially preferably of 0.6 to 1.0 mg KOH/g.
  • the reactor in which the chain reaction is performed has the above-described internals which ensure thorough commixing of the product stream.
  • Chain extension reaction Due to the marked viscosity increase during the chain extension reaction it may be advantageous to run the chain extension reaction in the reactor only until the chain extender has fully reacted at least with one functional unit. Chain formation may be completed for example in a separate stirred tank or in a tube without internals. This makes it possible to avoid blockages and wall deposits.
  • the aliphatic-aromatic polyesters obtainable by the process according to the invention such as for example PBAT or PBSeT are suitable for numerous applications such as injection molded products, thermoforming products, foams and particularly films.
  • the aliphatic-aromatic polyesters are often employed in mixtures with further biopolymers such as polylactic acid, polyhydroxyalkanoates, biodegradable aliphatic-aromatic polyesters, starch, mineral fillers or other additives such as for example lubricants, nucleating agents, plasticizers or pigments.
  • the process according to the invention makes it possible to achieve a distinct depletion of cyclic impurities.
  • the residual THF content of the aliphatic polyester may generally be reduced to two third or preferably a half and especially preferably to less than a quarter of the original THF content.
  • the purified aliphatic-aromatic polyester generally has a residual THF content of less than 300 ppm, preferably less than 200 ppm and especially preferably less than 100 ppm.
  • the cyclic oligomers content of the aliphatic-aromatic polyester can also be distinctly reduced.
  • the process according to the invention generally reduces the content of dimeric ester cycles (comprising the 3 cyclic dimers: Cyclic 2AA 2BDO is the cyclic dimer polyester containing two adipic acid units and two 1,4-butanediol units; Cyclic AA TPA 2BDO is the cyclic dimer polyester containing adipic acid, terephthalic acid and two 1,4-butanediol units and Cyclic 2TPA 2BDO is the cyclic dimer polyester containing two terephthalic acid units and two 1,4- butanediol units) by more than 20%, preferably more than 30% and in particular more than 40%.
  • PBAT monomeric ester cycle
  • the disruptive cyclic ester dimers in PBAT may general ly be reduced to less than 1200 ppm, preferably from 500 to 1100 ppm and especially preferably from 700 to 1000 ppm based on the weight of PBAT.
  • the efficient depletion of the cyclic ester (monomers and) dimers in the process according to the invention makes it possible to obtain approval for contact with foodstuffs according to EU 10/2011.
  • the total amou nt of cyclic ester oligomers (monomer, dimers, trimers, tetramers and pentamers) is reduced by the process according to the invention below 3800 ppm, preferably below 3600 ppm, based on the weight of PBAT.
  • Cyclic SeA BDO is the cyclic monomer containing sebacic acid and 1,4-butanediol
  • dimeric ester cycles comprising the 3 cyclic dimers: Cyclic 2SeA 2BDO is the cyclic dimer polyester containing two sebacic acid u nits and two 1,4-butanediol units; Cyclic SeA TPA 2BDO is the cyclic dimer polyester containing sebacic acid, terephthalic acid and two 1,4-butanediol u nits and Cyclic 2TPA 2BDO is the cyclic dimer polyester containing two terephthalic acid u nits and two 1,4-butanediol units) by more than 20%, preferably more than 30% and in particular more than 40%.
  • the disruptive cyclic ester monomer and dimers in PBSeT may generally be reduced to less than 1300 ppm, preferably from 500 to 1100 ppm and especially preferably from 700 to 1000 ppm based on the weight of PBSeT.
  • the efficient depletion of the cyclic ester monomers and dimers in the process according to the invention makes it possible to obtain approval for contact with foodstuffs according to EU 10/2011.
  • the total amount of cyclic ester oligomers (monomer, dimers, trimers, tetramers and pentamers) is reduced by the process according to the invention below 4200 ppm, preferably below 3800 ppm, based on the weight of PBSeT.
  • Viscosity num bers were determined according to DI N 53728 Part 3, January 3, 1985.
  • the melt of volume rate was determined according to ISO 1133. Test conditions of 190° C, 2.16 kg were used. The melting time was 4 minutes.
  • the MVR describes the rate of extrusion of a molten plastics molding com position through an extrusion die of defined length and defined diameter under the above-described conditions: temperature, loading and piston position. The volume extruded in a defined time in the barrel of an extrusion plastometer is determi ned.
  • oligomers were characterized by liquid chromatography/high resolution mass spectrometry (LC-HRMS) - this method had the advantage in com parison to gas chromatography coupled with mass spectroscopy (GC-MS) that the higher cyclic oligomers (> 600 Daltons) were reproducibly measured.
  • LC-HRMS liquid chromatography/high resolution mass spectrometry
  • GC-MS mass spectroscopy
  • the dissolved and diluted polymer extracts were analyzed by LC-H RMS using a Thermo Scientific Ultimate 3000 H PLC system equipped with a XBridge BEH (C18) column (particle size 2.5 pm, 150 x 2.1 mm) as stationary phase.
  • the mobile phase consisted of water with 0.1% formic acid (A) and methanol with 0.1% formic acid (B).
  • the gradient started at 40% B and was held for 1 min, then raised to 100% B in 12 min, held at 100% B for 6 min and final ly equilibrated at 40% B for 5 min.
  • the total ru ntime of the gradient program was 24 min.
  • the flow rate was 0.35 m L/min, the colu mn temperature was 40 ° C.
  • the LC systems was coupled to a heated electrospray ionisation source of a high resolution mass spectrometer Q Exactive Plus Orbitrap from Thermo Scientific.
  • the positive ionization mode was used for identification as wel l as quantification.
  • the following instrumental parameters were used: spray voltage 4 kV, capillary tem peratu re 320 ° C, sheath gas flow rate 30.00, aux gas flow rate 6.00, S- lens RF level 55.00, probe heater temperature 250.00 ° C.
  • Identified oligomers were semi-quantified using external calibration. Due to the lack of standard substances two references were chosen as standard analogues.
  • cyclic PET trimer (3,6,13,16,23,26-hexaoxatetracyclo[26.2.2.28,
  • hexatriaconta-1 (30) , 8,10,18,20,28,31,33,35- non aene-2,7, 12, 17,22,27- hexone; CAS No. 7441-32-9; obtained from Santa Cruz Biotechnology (Heidel berg, Germany)
  • oligomers consisting of adi pic acid, terephthalic acid, and butanediol, dibutyl adipate (CAS No. 105-99-7) was used as internal reference.
  • the stock solutions were prepared in dichloromethane and acetonitrile, dilutions were freshly prepared in a mixture of ACN/water (1/1, v/v).
  • a semi-aromatic aliphatic copolyester was produced by physically mixing 19 kg/h of terephthalic acid (TPA), 19 kg/h of adipic acid (AA) , 32 kg/h of 1,4-butanediol (BDO), and 0.05 kg/h of glycerol at 35° C.
  • TPA terephthalic acid
  • AA adipic acid
  • BDO 1,4-butanediol
  • glycerol e.g. designed in the shape of a hydrocyclone as described by way of exam ple in WO 03/042278 Al.
  • the resulting esterification product and additional 0.012 kg of TBOT/h were transferred to a second stage reactor for further polycondensation by removal of the majority of excessive 1,4-butanediol.
  • This reactor was designed as a downflow cascade (as described by way of exam ple in WO 03/042278 Al) and operated at a temperature rising from 250 to 260° C, with a residence time of 2 h, and at a pressure falling from 300 m bar to 10 m bar. After this stage, the VN of the resulting polyester was 47 cm 3 /g.
  • Phosphorous acid (0.01 kg/h) was added to the polyester and the mixtu re was transferred to a polycondensation reactor (as described by way of exam ple in EP 0719582).
  • the reaction mixtu re was polycondensed at a temperatu re of 245° C and at a pressu re of 1 mbar to remove the residual excess of 1,4-butanediol by distillation.
  • the VN of the resultant polyester was 95 cm 3 /g and its acid num ber (AN) was 0.6 mg KOPI/g and the polyester was transferred to a static mixer for the finishing stage.
  • a semi-aromatic aliphatic copolyester was produced by physically mixing 19 kg/h of terephthalic acid (TPA), 19 kg/h of adipic acid (AA) , 32 kg/h of 1,4-butanediol (BDO), and 0.05 kg/h of glycerol at 35° C.
  • TPA terephthalic acid
  • AA adipic acid
  • BDO 1,4-butanediol
  • glycerol e.g. designed in the shape of a hydrocyclone as described by way of exam ple in WO 03/042278 Al.
  • the resulting esterification product and additional 0.012 kg of TBOT/h were transferred to a second stage reactor for further polycondensation by removal of the majority of excessive 1,4-butanediol.
  • This reactor was designed as a downflow cascade (as described by way of exam ple in WO 03/042278 Al) and operated at a temperature rising from 250 to 260° C, with a residence time of 2 h, and at a pressure falling from 300 m bar to 10 m bar. After this stage, the VN of the resulting polyester was 44 cm 3 /g.
  • Phosphorous acid (0.01 kg/h) was added to the polyester and the mixtu re was transferred to a polycondensation reactor (as described by way of exam ple in EP 0719582) . Additional ly, a constant stream of nitrogen (0.06 kg/h) was flushed through the reactor (corresponds to 0.09 % nitrogen related to the PBAT
  • the reaction mixture was polycondensed at a temperature of 245° C and at a pressure of 2 m bar to remove the residual excess of 1,4-butanediol and the formed cyclic oligomers by distil lation. After 45 minutes, the VN of the resultant polyester was 101 cm 3 /g and its acid number (AN) was 0.6 mg KOH/g and the polyester was transferred to a static mixer for the finishing stage.
  • AN acid number

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Abstract

L'invention concerne un procédé continu de production d'un polyester aliphatique-aromatique construit à partir d'acides dicarboxyliques aliphatiques, d'acides dicarboxyliques aromatiques et de diols aliphatiques comprenant les étapes i) d'estérification, ii) de polycondensation et éventuellement iii) d'extension de chaîne, pendant l'étape ii) le polycondenseur fonctionnant comme un appareil de dégazage, le polyester brut étant dégazé à une pression de 0,01 à 5 mbar en présence de 0,01 % à 1 % en poids, de préférence de 0,02 à 0,2 % en poids par rapport au poids total du polyester brut, introduit dans l'espace gazeux de l'appareil de dégazage en tant qu'agent d'entraînement.
PCT/EP2020/063963 2019-05-22 2020-05-19 Procédé continu de production d'un polyester aliphatique-aromatique WO2020234294A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831518A (zh) * 2021-11-15 2021-12-24 中核华纬工程设计研究有限公司 一种小分子酚改性pbat的方法
CN114621424A (zh) * 2022-01-07 2022-06-14 浙江恒逸石化研究院有限公司 一种含衣康酸的脂肪族-芳香族线性共聚酯的制备方法
IT202100030725A1 (it) * 2021-12-06 2023-06-06 Novamont Spa Poliesteri alifatico-aromatici con un controllato contenuto di oligomeri ciclici residui misti
EP4279528A1 (fr) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Composition de résine de polyester biodégradable

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465819A (en) * 1980-03-10 1984-08-14 Occidental Chemical Corporation Semi or fully continuous process for polyester of bisphenol and dicarboxylic acid by transesterification polymerization and product thereof
US5373029A (en) * 1992-07-13 1994-12-13 Bayer Aktiengesellschaft Process for the production of low-fog flexible polyester polyurethane foams and their use in vehicles
WO1996015173A1 (fr) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP0719582A2 (fr) 1994-12-30 1996-07-03 Karl Fischer Industrieanlagen Gmbh Réacteur pour substances à écoulement facile et substances à viscosité élevée
DE19528539A1 (de) * 1995-08-03 1997-02-06 Basf Ag Verfahren zur Herstelung von Polyesterolen mit einem verminderten Gehalt an flüchtigen Verbindungen
WO2003042278A1 (fr) 2001-11-12 2003-05-22 Inventa-Fischer Gmbh & Co. Kg Procede de production continue de polyester macromoleculaire et dispositif pour mettre en oeuvre celui-ci
US20070116615A1 (en) * 2003-10-31 2007-05-24 Uhde Inventa-Fischer Gmbh & Co. Kg Tower reactor and use thereof for the continuous production of high molecular weight polyesters
WO2009127555A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de fabrication en continu de polyesters biodégradables
WO2009127556A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de production en continu de polyesters biodégradables
EP2623540A1 (fr) 2010-09-27 2013-08-07 Mitsubishi Chemical Corporation Procédé de production de polyester
WO2019096918A1 (fr) * 2017-11-20 2019-05-23 Basf Se Procédé continu de production d'un polyester aliphatique
WO2019096920A1 (fr) * 2017-11-20 2019-05-23 Basf Se Procédé de purification d'un polyester aliphatique

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465819A (en) * 1980-03-10 1984-08-14 Occidental Chemical Corporation Semi or fully continuous process for polyester of bisphenol and dicarboxylic acid by transesterification polymerization and product thereof
US5373029A (en) * 1992-07-13 1994-12-13 Bayer Aktiengesellschaft Process for the production of low-fog flexible polyester polyurethane foams and their use in vehicles
WO1996015173A1 (fr) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP0719582A2 (fr) 1994-12-30 1996-07-03 Karl Fischer Industrieanlagen Gmbh Réacteur pour substances à écoulement facile et substances à viscosité élevée
US5779986A (en) 1994-12-30 1998-07-14 Karl Fischer Industrieanlagen Gmbh Reactor device for free-flowing and higher-viscosity media
DE19528539A1 (de) * 1995-08-03 1997-02-06 Basf Ag Verfahren zur Herstelung von Polyesterolen mit einem verminderten Gehalt an flüchtigen Verbindungen
WO2003042278A1 (fr) 2001-11-12 2003-05-22 Inventa-Fischer Gmbh & Co. Kg Procede de production continue de polyester macromoleculaire et dispositif pour mettre en oeuvre celui-ci
US20050163679A1 (en) * 2001-11-12 2005-07-28 Eike Schulz Van Endert Method for the continuous production of high-molecular polyester and device for carrying out the method
US20070116615A1 (en) * 2003-10-31 2007-05-24 Uhde Inventa-Fischer Gmbh & Co. Kg Tower reactor and use thereof for the continuous production of high molecular weight polyesters
WO2009127555A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de fabrication en continu de polyesters biodégradables
WO2009127556A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de production en continu de polyesters biodégradables
EP2623540A1 (fr) 2010-09-27 2013-08-07 Mitsubishi Chemical Corporation Procédé de production de polyester
WO2019096918A1 (fr) * 2017-11-20 2019-05-23 Basf Se Procédé continu de production d'un polyester aliphatique
WO2019096920A1 (fr) * 2017-11-20 2019-05-23 Basf Se Procédé de purification d'un polyester aliphatique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 7441-32-9
WITT ET AL., J. ENVIRON. POL. DEGRADATION, vol. 4, no. 1, 1996, pages 9

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113831518A (zh) * 2021-11-15 2021-12-24 中核华纬工程设计研究有限公司 一种小分子酚改性pbat的方法
IT202100030725A1 (it) * 2021-12-06 2023-06-06 Novamont Spa Poliesteri alifatico-aromatici con un controllato contenuto di oligomeri ciclici residui misti
WO2023104757A1 (fr) * 2021-12-06 2023-06-15 Novamont S.P.A. Polyesters aliphatiques-aromatiques à teneur contrôlée en oligomères cycliques résiduels mixtes
CN114621424A (zh) * 2022-01-07 2022-06-14 浙江恒逸石化研究院有限公司 一种含衣康酸的脂肪族-芳香族线性共聚酯的制备方法
CN114621424B (zh) * 2022-01-07 2023-06-13 浙江恒逸石化研究院有限公司 一种含衣康酸的脂肪族-芳香族线性共聚酯的制备方法
EP4279528A1 (fr) * 2022-05-21 2023-11-22 Ecovance Co. Ltd Composition de résine de polyester biodégradable
US11898031B2 (en) 2022-05-21 2024-02-13 Ecovance Co. Ltd. Biodegradable polyester resin composition and biodegradable polyester molded article including the same

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