WO2003029325A1 - Method for producing aliphatic polycarbonates - Google Patents

Method for producing aliphatic polycarbonates

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Publication number
WO2003029325A1
WO2003029325A1 PCT/EP2002/010406 EP0210406W WO03029325A1 WO 2003029325 A1 WO2003029325 A1 WO 2003029325A1 EP 0210406 W EP0210406 W EP 0210406W WO 03029325 A1 WO03029325 A1 WO 03029325A1
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WO
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Prior art keywords
catalyst
polycarbonates
example
reaction
reactor
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PCT/EP2002/010406
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German (de)
French (fr)
Inventor
Johannes Heinemann
Gerrit Luinstra
Edward Bohres
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Basf Aktiengesellschaft
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02Aliphatic polycarbonates
    • C08G64/0208Aliphatic polycarbonates saturated
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D317/00Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34Oxygen atoms
    • C07D317/36Alkylene carbonates; Substituted alkylene carbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18Block or graft polymers
    • C08G64/183Block or graft polymers containing polyether sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20General preparatory processes
    • C08G64/32General preparatory processes using carbon dioxide
    • C08G64/34General preparatory processes using carbon dioxide and cyclic ethers

Abstract

The invention relates to a method for producing high-molecular aliphatic polycarbonates having the following properties: the average molecular weight Mw ranges from 30,000 to 1,000,000, and; the content of cyclic carbonates and polyethers equals, in total, a maximum of 5 wt. %. Said polycarbonates are produced by polymerizing carbon dioxide with at least one epoxide while using at least one catalyst selected from the group consisting of zinc carboxylates and multi-metal cyanide compounds. The invention is characterized in that the catalyst is introduced in anhydrous form, and the catalyst is firstly brought into contact with at least a partial quantity of the carbon dioxide before the epoxide is added.

Description

A process for preparing aliphatic polycarbonates

description

The invention relates to a process for preparing high molecular weight aliphatic polycarbonates having the following properties

10 - the weight average molecular weight M w, determined by means of

Gel permeation chromatography using as eluent Hexafluo- roisopropanol and polymethyl methacrylate standards is 30,000 to 1,000,000,

15 - the content of cyclic carbonates and polyethers together is 5 wt .-% maximum,

by polymerization of carbon dioxide with at least one epoxide of the general formula 1 20

(1)

/ \ / \

25

in which the radicals R represent hydrogen, halogen, -N0, -CN, -COOR, or a hydrocarbon group having 1 to 30 20 carbon atoms which may be substituted, independently of one another,

using at least one catalyst selected from the group consisting of compounds of zinc carboxylates and multimetal cyanide.

35

The invention also aliphatic polycarbonates, obtainable by this process, as well as thermoplastic molding compositions containing these polycarbonates relates. Finally, the invention relates to the use of these thermoplastic molding compositions

40 for producing molded parts, sheets, films, coatings and fibers, and these molded parts, sheets, films, coatings and fibers from the thermoplastic molding compositions.

Copolymers of epoxides, such as ethylene oxide (abbreviated EO) or propylene oxide 5 (abbreviated to PO) and carbon dioxide (C0 2) and methods for their preparation are known. The copolymers are referred to as aliphatic polycarbonates or aliphatic polyether.

Usual catalysts for this polymerization are in particular organic zinc compounds such as Zinkcarboxy- translate, or cyanide with two or more metal atoms, for example, double metal cyanide complexes.

Thus, DE-A 197 37 547 describes a process for the preparation of polyalkylene carbonates by means of a catalyst which is prepared from zinc oxide or other inorganic zinc compounds and a mixture of two aliphatic or aromatic dicarboxylic acids. In this case, first, the epoxy and then metered into the reactor C0 2, that the catalyst comes into contact first with the epoxy before C0 2 is added.

The US-A 5,026,676 discloses a process for the copolymerization of C0 2 and epoxides in the presence of catalysts Zinkcarboxylat-, again first the epoxide and then the C0 2 are added to the reactor.

The ÜS-A 4,943,677 describes a similar process in which the zinc carboxylate catalyst placed in the reactor and is heated for several hours in the nitrogen stream before the epoxide and then the C0 2 are added.

In US-A 4,783,445, a corresponding method is disclosed in which a Zinkdicarbonsäureester is used as catalyst. Again, the epoxy is first added to the catalyst before C0 2 is pressed.

The US-A 5,041,469 describes the copolymerization of epoxide and C0 in methylene chloride of the solvent, epoxy, C0 2 and the zinc carboxylate catalyst are placed together.

The three WO-A documents 01/04178, 01/04179 and 01/04183 describe a process for the preparation of polyoxyalkylenes of epoxides in the presence of metal cyanide as a catalyst, whereby C0 can be used. In this case, the catalyst and epoxide are placed and allowed to stand to activate the catalyst. Thereafter, the reaction starts and it is further epoxide added.

EP-A 222 453 discloses a process for the preparation of polycarbonates from epoxides and C0 2 using a

Catalyst system of the double metal cyanide catalyst and a cocatalyst such as zinc sulfate. The polymerization is in- itiiert by a small part of the epoxide is contacted with the catalyst system. Only then is the remaining amount of epoxide and the C0 are simultaneously metered in, the copolymerization takes place (page 3, lines 53-57 and Examples).

In US-A 4,500,704 a process for the preparation of EP oxide C0 2 will be described copolymers can be used as catalysts in the Doppelmetallcyanidkom- complexes. Again, the Doppelmetallcyamidka- talysator is activated by being brought into contact for up to 45 min with the epoxide prior to the actual first copolymerization. Only then is C0 2 injected and copolymerized (col. 5, lines 46-50). According to Example 1, the resulting PO-C0 2 has copolymer has a number average molecular weight (molar mass) M n of 23,000.

The prior art methods have at least one of the following disadvantages:

The activity of the catalysts is insufficient, that is, per gram of catalyst used so few grams of polymer are produced, that the process is uneconomical.

The polymerization times are so long that the process is uneconomical with four to 84 hours.

The molecular weights of the polycarbonates obtained are so small that their own use, sheep s (in particular the mechanical properties) are at unacceptably low level. Ie the polycarbonates for the production of molding compounds and moldings hardly suitable.

In addition to the desired polycarbonates unwanted byproducts are formed, in particular epoxy homopolymers (ie polyethers) and cyclic (usually monomeric) carbonates. The by-products reduce the yield of polycarbonate and may have to be laboriously separated from the main product. They also impair the mechanical properties of the resulting polymer mixture considerably. So cyclic carbonates lower the glass transition temperature of the polycarbonate materially thwarted certain applications.

the possible reaction products Schematically the example of the reaction of propylene oxide and represent C0 as follows: alternating polycarbonate I

polyether II

polyether III

propylene carbonate IV

The indices n and k are integers greater than or equal 1 and enter the number of repeating units.

The polyether III and IV are the cyclic carbonates undesirable byproducts.

The polycarbonates I and II, the polyether are the desired end products and are collectively referred to herein as "Polycarbonate". "Polycarbonate" in the sense of the invention therefore includes both strictly alternating polycarbonates I and II, the polycarbonates ducks with Polyetherseg (polyether carbonate). It was the object to remedy the disadvantages. provide in particular, the object was to provide a process for the preparation of polycarbonates from epoxides and C0 in which the Katalysatoraktivtät (mass polymer obtained per unit mass of catalyst) is improved.

Furthermore, the object, an economical process having shorter polymerization times, in particular times to provide up to four hours, existed.

Furthermore, the method should provide polycarbonates having higher molecular weight than the processes of the prior art. The polycarbonates obtainable according to the method should have better mechanical properties.

Finally, a method should be found in which fewer unwanted by-products. In particular, the content of disturbing polyether homopolymer III and in particular of cyclic carbonates IV should be significantly reduced.

Accordingly, the process defined at the outset. It is characterized in that the catalyst is used in anhydrous form, and by initially contacting the catalyst with at least a subset of the carbon dioxide into contact before adding the epoxy.

In addition, the aliphatic polycarbonates mentioned above, thermoplastic molding compositions, the use of the molding materials and the objects made therefrom have been found, as mentioned above.

Preferred embodiments of the invention are disclosed in the subclaims.

The weight average molecular weight M w of the polycarbonate is determined by gel permeation chromatography (GPC, also known as Size Exclusion Chromatography (SEC) indicated) by using hexafluoroisopropanol (HFIP) as eluent and calibration with polymethyl methacrylate (PMMA) standards. It can be as beispiels- work as follows: Detector: differential refractometer ERC 7510 from the company ERC;. Columns. HFIP gel guard column and HFIP gel linear separation column, both from the company Polymer Laboratories; Calibration with narrow distribution PMMA standards with molecular weights M 505-2740000 Fa. PSS. The polycarbonates prepared according to the process of this invention have a weight average molecular weight M w 30,000 to 1,000,000. Preferably at molecular weights M w of propylene oxide as the epoxide 200,000 to 500,000, and for ethylene oxide as the epoxide 30,000 to 300,000.

The content of the polycarbonates of cyclic carbonates, such as cyclic carbonate monomer IV, and polyethers, including polyether homopolymers III (see Fig. Prominent scheme) is zusammenge- no men most 5 wt .-%. Ie the sum of the by-products cyclic carbonates and polyether maximum of 5 percent by .-%.

The content of cyclic carbonates and polyethers can be determined in a known manner. Usually, this one uses the Kernresonanzspektrosopie (nuclear magnetic resonance, NMR), particularly the ^ H NMR. A X H-NMR spectrum of the method - the product polycarbonate displays by corresponding bands (peaks), whether cyclic carbonates and / or polyether are present in the polycarbonate. The amount thereof can be determined in a known manner by quantitative analysis of the spectra.

Among the starting materials of the process following to say:

Carbon dioxide C0 2 is inexpensive as a component of air and almost unlimited availability.

The epoxides used have the general formula 1

R 0 R

on. Therein, the radicals R independently represent hydrogen, halogen, nitro group -N0 2 group, cyano group -CN, an ester group -COOR or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted.

Such hydrocarbon groups are especially Cι_o -alkyl, C 2-20 -alkenyl, C 3 -C 20 cycloalkyl, C 6 _ 18 aryl, and C 7 _ 0 arylalkyl. And wherein two radicals R, when they are on different carbon atoms of the epoxy group

are to be bridged to each other and form a C_ o-cyclo alkylene group.

As the substituents with which the Cι_ 2 o-hydrocarbon group may be substituted, are in particular the following groups: halogen, cyano, nitro, thioalkyl, tertiary amino, alkoxy, aryloxy, arylalkyloxy, Carbonyldioxyalkyl, Carbonyldioxyaryl, Carbonyldioxyarylalkyl, alkoxycarbonyl, aryloxycarbonyl , Arylal- kyloxycarbonyl, alkylcarbonyl, arylcarbonyl, aryl alkyl, alkylsulfinyl, arylsulfinyl, arylalkylsulfinyl, alkylsulfonyl, arylsulfonyl and arylalkylsulphonyl.

Preferably used epoxy ethylene oxide, propylene oxide, butylene (1-butene oxide, BuO), cyclopentene oxide, cyclohexene oxide (CHO), cycloheptene oxide, 2, 3-Epoxypropylphenylether, epichlorohydrin, epibromohydrin, i-butene oxide (IBO) or acrylic oxides. Particular preference is given to using ethylene oxide (EO), propylene oxide (PO), butylene oxide, cyclopentene oxide, cyclohexene oxide or i-butene oxide. Very particularly preferably ethylene oxide and propylene oxide. It is understood that also mixtures of the aforementioned epoxides may be employed.

In the use of C0 2 and two or more epoxides polycarbonate terpolymers formed. If, in addition C0 2, the epoxides of ethylene oxide and cyclohexene oxide, so arise C0 / E0 / cyclohexene terpolymers example. As mixtures of two epoxides are for example are: EO and PO (there arises a C0 2 / Eθ / PO terpolymers mer), EO and Cyclenhexenoxid, PO and cyclohexene oxide, i-butene oxide, and EO or PO, butylene oxide, and EO or PO, etc.

The two or more epoxides may be added as a mixture or separately.

The amount ratio of C0 2: epoxide can be varied within wide limits. C0 usually used in excess, that is more than 1 mol per 1 mol of C0 epoxide.

The catalyst is selected from the group consisting of zinc carboxylates and multimetal cyanide compounds. Zinc carboxylates are zinc salts of carboxylic acids. Particularly suitable carboxylic acids are dicarboxylic acids, in particular aliphatic dicarboxylic acids. Especially suitable are adipic acid and glutaric acid. Accordingly, zinc adipate and zinc glutarate are particularly suitable zinc carboxylates.

The zinc carboxylates are used in a conventional manner from zinc compounds (inorganic such as zinc oxide, zinc hydroxide, zinc halide, or organic such as zinc acetate, zinc propionate), and produced the corresponding carboxylic acids the carboxylate group. Instead of the carboxylic acids can also carboxylic acid derivatives such as carboxylic or lower carboxylic acid esters such as acetates or propionates use. Corresponding manufacturing method of zinc carboxylates are described in the documents US-A 4,783,445 and DE-A 197 37 547, for example.

Multimetal cyanide compounds are complexes containing per formula unit at least two coordinated complex with cyanide ions metals, and possibly other ligands. In exactly two coor- dined with cyanide metals per formula unit is also called double - metal cyanide (DMC).

Suitable multimetal are known and described in the following A-documents: US 3,278,457, US 3,278,458, US 3,278,459, US 3,427,256, US 3,427,334, US 3,404,109, US

3,829,505, US 3,941,849, EP 283.148, EP 385.619, EP 654.302, EP 659.798, EP 665.254, EP 743.093, EP 755.716, US 4,843,054, US 4,877,906, US 5,158,922, US 5,426,081, US 5,470,813, US 5,482,908, US 5,498,583, US 5,523,386, US 5,525,565, US 5,545,601, JP 7,308,583, JP 6,248,068, JP 4,351,632 and US 5,545,601.

Multimetal cyanide complexes are also, for example, in the documents DD-A 148 957, EP-A 862 947, EP-A 654 302, EP-A 700 949, WO-A 97/40086, WO-A 98/16310, EP-A 222 453 , EP-A 90 444, EP-A 90 445, WO-A 01/04177, WO-A 01/04181, WO-A 01/04182, WO-A 01/03830, DE-A 199 53 546..

Particularly suitable multimetal cyanide catalysts are double - metallcyanidverbindungen, in particular those of the formula 2

M 1 a [M 2 (CN) b A c] d • f • h H n Mi g 2 0 • L • e k P (2)

The letters M, A, X, L and P represent atoms or Atomgrup- pen. CN and H 2 0 are cyanide and water. The superscripts 1 and 2 are used to distinguish between the different M. The deep-set indices a, t>, C / <ι, g, n are stoichiometric indices and the letters f, h, e and k are molar numbers.

In the general formula 2 '

M 1 is at least one metal ion selected from the group comprising Zn 2+, Fe 2+, Fe 3+, Co 2+, Co 3+, Ni 2+, Mn 2+, Sn +, Pb 2+, Mo +, Mo6 + , A13 +, v +, V5 +, Sr 2+, W 4+, W 6+, Cr 2+, Cr 3+, Cd 2+, La 3+, Ce 3+, Ce 4+, Eu 3+, Mg 2+, Ti 3+, Ti 4+, Ag +, Rh 2+, Ru +, Ru 3+,

M 2 is at least one metal ion selected from the group comprising Fe 2+, Fe 3+, Co 2+, Co 3+, Mn 2+, Mn 3+, V +, V 5+, Cr 2+, Cr 3+, Rh 3+, Ru +, Ir3 +

wherein M 1 and M 2 may be identical or different,

A is at least one anion selected from the group consisting of halide, hydroxide, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, phosphate, dihydrogen Phosphorylation at, hydrogen phosphate,

X is at least one anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, hydrogen carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate,

wherein A and X may be the same or different,

L at least one water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, sulfides, amines, ligands having pyridin nitrogen, phosphides, phosphites, phosphanes , phosphonates, phosphates,

P alkylenglykolsorbitanester, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, at least one organic additive selected from the group consisting of polyethers, polyesters, polycarbonates, poly , polyalkylmethacrylates, Polyvinylmethether, polyvinyl - nylethylether, polyvinyl acetate, polyvinyl alcohol, poly-N-vi- pyrrolidone, poly (N-vinylpyrrolodon-co-acrylic acid), polyvinyl - nylmethylketon, poly (4-vinyl phenol), poly (acrylic acid-co-sty - rol), oxazoline polymers, polyalkylenimines, maleic acid, ma- leinsäureanhydridcopolymer, hydroxyethyl cellulose, Polyace- ended, coside ionic surfactants and surface-active compounds, bile acids and salts, esters and amides of the bile acid, carboxylic acid esters, polyhydric alcohols, Gly,

wherein a, b, d, g and n are integers or fractions greater than zero, and

wherein c, f, h, e and k are integers or fractions greater than or equal to zero, and

wherein a, b, c, d, g and n are selected such that the electrical neutrality of the cyanide compound M 1 [M 2 (CN) A] and the compound M x X is ensured.

As carboxylate groups A and X formate, acetate and propionate are preferred.

The multimetal may be crystalline or amorphous. For k equal to zero, the multimetal generally are crystalline or predominantly crystalline. For k greater than zero, they are usually crystalline, partially crystalline or amorphous WE ~ sentliehen.

The primary particles of the multimetal cyanide compounds preferably have a crystalline structure and a content of platelet-shaped particles of more than 30 wt .-%, based on the total weight of the multimetal cyanide compound, to. The platelet shape of the particles results in that the proportion of of catalytic active surface, based on the total surface to-take and thus the mass-specific activity increases.

The term "primary particles" of individual crystallite is understood as, for example, on the Rasterelektronenmikroskopieauf - took can be seen. These primary particles can then glomerates to Ag, assemble the so-called secondary particles.

By the term "platelet-like" is meant that the length and width of the primary particles is at least three times greater than the thickness of these particles.

The term "crystalline structure" is meant that the solid state not only short-range order, such as an array of, for example 6 carbon atoms, there is a metal atom around, but also a long-range order, that can be an im- mer recurring unit, also called a unit cell, define, from which leaves the entire solid build. Is a solid crystalline, this manifests itself among others in the X-ray diffraction. In X-ray diffraction can be seen in the case of a crystalline substance "sharp" reflections whose intensity that is at least three times, are clearly greater than that of the substrate.

Instead of plate-like primary particles can also be eg rod-elle-like, cube-shaped or spherical.

Preferred multimetal included:

as M 1 is at least one metal ion selected from the group comprising Zn 2+, Fe 2+, Fe 3+,

when M 2 is at least one metal ion selected from the group consisting of Co 2+, Fe 2+, Fe 3+,

as cyanide anion A,

as X is at least one anion selected from the group contained - tend formate, acetate, propionate,

L as at least one water-miscible ligand selected from the group comprising tert-butanol, dimethyl ether Monoethylengly- (Gly e)

P as polyether.

Particularly preferred are multimetal cyanide compounds of the above formula 2 in which k and s are greater than zero. These compounds contain the multimetal cyanide, at least one ligand L and at least one organic additive P.

Also particularly preferred are multimetal cyanide compounds of the above formula 2 in which k is zero and, optionally, e is equal to zero. These compounds contain no organic additive P. and optionally no ligand L.

Very particularly preferred multimetal with k and e is equal to zero, where X is selected from the group corresponds holding formate, acetate and propionate. These compounds contain no organic additive and no P ligand L. details are WO-A 99/16775 refer. management form in this training crystalline double metal are preferred; and double metal cyanide catalysts, which are crystalline and platelet-shaped (see WO-A 00/74845). Moreover, are particularly preferred multimetal cyanide of the formula 2, in which, e, and f k are nonzero. This means that these compounds contain the metal salt M ^ - g X n, a ligand L and organic additives P. ' See WO 98/06312. 5

The preparation of multimetal cyanide compounds is described for example in WO-A 00/74843, WO-A 00/74844, WO-A 00/74845, EP-A 862 947, WO-A 99/16775, WO-A 98/06312 and US -A 5 158 922. Usually, combined an aqueous solution of the metal salt

1.0 M i gX n with an aqueous solution of Cyanometallats H a M 2 (CN) b A c, where H is hydrogen, alkali metal, alkaline earth metal or ammonium. The metal salt solution and / or the Cyanometallatlösung may contain the water-miscible ligand L and / or the organic additive P. After the merging the solu-

15 solutions are added, if necessary, added ligand L and / or P additive. In catalyst production, it is advantageous to stir intense, eg with high-speed stirrers. The precipitate which is separated in the usual manner and optionally dried.

20 The starting material cyanometallate H a M 2 (CN) b A c H is hydrogen (so-called. Cyanometalic acids) can be prepared, for example kalicyanometallaten via acidic ion exchangers from the corresponding alkali metal or alkaline earth metal, see for example WO-A 99 / 16,775th

25 As in the older, unpublished DE application Az. described 10009568.2, you can first create an inactive catalyst phase and then converting them by recrystallization converted into an active phase.

30 Further details of the production process of the multimetal found by the expert in the writings of the three preceding paragraphs.

Very particularly preferably used as Multimetallcyanidver- 35 bond is a compound which is obtainable by reaction of aqueous hexacyanocobaltic acid H 3 [Co (CN) g] with aqueous Zinkace- tat solution. This reaction can make, for example, under the conditions indicated in the examples and conditions, see for example the local Herstellungsvorschrif. 0

For the inventive method for preparing high molecular weight aliphatic polycarbonates by polymerizing C0 with at least one epoxide following to say (the reaction conditions mentioned below apply equally to 5 Zinkcarboxylat- and multimetal cyanide catalysts, unless stated otherwise): According to the invention the catalyst used in anhydrous form. This means that the catalyst - apart from the chemically bound water (for example, h mol of water of crystallization in the above general formula 2) - does not contain water or only un- significant traces of water, in particular not adhering to the surface or physically trapped in voids of water.

In a preferred embodiment, therefore you do in yields of anhydrous before use. Particularly preferably, this in which one heats the catalyst before the start of the polymerization in an inert gas or in a vacuum to anhydrous happens. Usually used as an inert gas nitrogen, argon or other customary inert gases. The temperature to which the catalyst is heated, usually is 80 to 130 ° C. The duration of heating is usually 20 to 300 min. Typical values ​​are for 2 hours at 120 ° C for Zinkcarboxylat- and 4 hours at 130 ° C for multimetal cyanide catalysts.

One can provide for example the catalyst in the polymerization reactor, in an inert gas make anhydrous (annealing), and - possibly after cooling, - in the same reactor to make the polymerization, ie, make anhydrous the catalyst and polymerization can be performed in a simple manner in the same vessel.

However, it can also render the catalyst anhydrous by heating in a vacuum or other suitable drying methods.

In a preferred embodiment of the water-free catalyst is then dissolved in an inert reaction medium or dis- persed (suspended or emulsified), before polymerization is begun. The dissolving or dispersing can be carried out with stirring.

As the inert reaction medium all substances are suitable which do not adversely affect the catalyst activity, in particular aromatic hydrocarbons such as toluene, xylenes, benzene, also aliphatic hydrocarbons such as hexane, cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, isobutyl chloride. Also, ethers such as diethyl ether are suitable, furthermore tetrahydrofuran, diethylene glycol dimethyl ether (Dig lyme), dioxane, and nitro compounds such as nitromethane. Preference is given to using toluene. The inert medium can be, for example, as such or preferably with a gas stream into the polymerization reactor ken hineindrük-, it being possible to use an inert gas such as nitrogen or the reaction partners C0 2 as a gas.

Preference is given to defining the first catalyst into the reactor before, makes it anhydrous by heating in a stream of inert gas can cool down and presses stirring the inert reaction medium with the gas in the reactor.

Based on the catalyst solution or dispersion (the total of the catalyst and reaction medium) the catalyst concentration is preferably 0.01 to 20, in particular 0.1 to 10 wt .-%. Based on the sum of epoxide and inert Reationsmedium loading carrying the catalyst concentration is preferably 0.01 to 10, particularly preferably 0.1 to 1 wt .-%.

In another, likewise preferred embodiment, one works without an inert reaction medium.

According to the invention the catalyst is contacted first with at least a subset of C0 into contact before adding the epoxy. Here, "with at least a subset of" in that before adding the epoxide, either adding a partial amount of the C0 2 amount used overall, or already the C0 2 -Gesamtmenge.

Preferably is added to only a subset of the C0 2 and more preferably this portion is 20 to 80, in particular 55 to 65 wt .-% of the total amount of C0.

Usually adds the C0 2 as a gas added and the C0 2 amount is - set via the C0 gas pressure - depending on the temperature. At room temperature (23 ° C) in the reactor of the C0 2 pressure prior to the addition of the epoxide is (hereinafter called C0-form), corresponding to the preferred C0 2 -Teilmenge, when using the zinc carboxylate catalysts 5 to 70, particularly 10 to 30 bar, and when using the catalysts Multimetallcya- nid 5 to 70, especially 10 to 50 bar. Typical values for the C0 2 -Vordruck are 15 bar and 50 bar for Zinkcarboxylat- catalysts for multimetal cyanide catalysts, in each case at 23 ° C.

All pressure data are absolute pressures. The C0 2 may be discontinuously set -Vordruck at once or divided into several steps, or continuously over a certain period of time th linear or exponential following a linear or stepwise gradient can be adjusted. When choosing the C0-admission pressure, the pressure rise in the reactor due to the subsequent heating of the reactor to be observed on the reactor temperature. The C0 2 -Vordruck (eg at 23 ° C) should be selected so that the 'desired C0 2 -Enddruck in Reaction - temperature (eg 80 ° C) is not exceeded.

The contacting of the catalyst with C0 generally takes place at temperatures of 20 to 80 ° C, preferably 20 to 40 ° C instead. Particularly preferably carried out at room temperature (23 ° C). The duration of contacting of the catalyst and C0 2 is dependent on the reactor volume and is usually 30 sec to 120 min.

In general, the catalyst or the solution or dispersion of the catalyst in the inert reaction medium is stirred during the contacting with the C0.

Only after the catalyst was contacted with C0 2, the epoxide is added to the reactor. The epoxide is usually pressed as such or, preferably, with a small amount of inert gas or C0 2 in the reactor.

The addition of the epoxide is carried out usually under stirring, and may at once (in particular at a small reactor volume), or continuously over a period of at least generally from 1 to 100, preferably 10 to 40 carried min, the addition may be constant, or a gradient can follow the example, linear, exponential, or stepwise may be ascending or descending.

The temperature during the addition of the epoxide is generally at 20 to 100, preferably 20 to 70 ° C. In particular, one can a) either the epoxide at low temperature (eg room temperature add 23 ° C) and then the reactor (the reaction temperature T R, for example, 80 ° C set), or b) Setting vice versa until the reactor to the reaction temperature T R and then add the epoxide. Variant a) is preferred.

The reactor is therefore before or - preferably - brought to the addition of the epoxide to the reaction temperature T R. The reaction onstemperatur are customarily to a 30 to 180, in particular 50 to 130 ° C. This is usually done by He ¬ warming of the reactor while stirring. The reaction temperature is usually from 40 to 120, preferably 60 to 90 ° C. Typical values ​​are 80 ° C for Zinkcarboxylat- and 65 to 80 ° C for Multimetallcya- nid catalysts. After reaching the reaction temperature is added, preferably while stirring, the remaining amount of the C0 2 into the reactor, if not already the C0 -Gesamtmenge was supplied when contacting the catalyst with C0 2 (see above). Customarily as presents to the C0 2 amount again over the C0 2 gas pressure one. Preferably is as long as added C0, C0 until the pressure (hereinafter referred to as C0-end pressure) using Zinkcarboxylat- catalysts 1 to 200, preferably 10 to 100 bar and using multimetal cyanide catalysts 20 to 200, preferably 80 to 100 bar, is. Typical values for the C0 2 -Enddruck 20 to 100 bar and 100 bar for Zinkcarboxylat- for multimetal tallcyanid catalysts.

All pressure data are absolute pressures. In this process - step added C0 2 amount (C0 2 -Enddruck) naturally depends also on the C0 2 -Teilmenge that had been previously added. From said C0 2 -printing and reaction temperatures shows that the C0 in the reactor in the supercritical state (ie, liquid) may be present. In particular, in C0 2 -Enddrucken about 74 bar and reaction temperatures T above 31 ° C, the R C0 2 is present in the supercritical state. In contrast to conventional chemical reactions in supercritical C0 2 but the C0 2 in the present method, not only the reaction medium, but at the same time the feedstock (reactant) and the reaction medium.

The C0-end pressure can be adjusted discontinuously at a time or continuously as described for the C0 2 -Vordruck.

-After reaching the C0-end pressure can maintain this dose by demand of the spent C0 2, if necessary. If no C0 replenished, so usually falls to the C0 2 pressure during the reaction by consumption of C0 second This approach is also possible.

Typically, the time to complete the polymerization is 60 to 500 min, preferably 120 to 300 min. A typical value for this post-reaction time is 3 to 4 hours. Usually you hold it, the reaction temperature constant; However, they can also be raised or lowered depending on the progress of the reaction.

The Mengenverhäl used in the process nit C0 2: Epoxy depend in known manner on the desired properties of the polymer. Typically, the amount ratio (weight ratio) Total amount of C0 2: total amount of epoxide 1: 1 to 2: 1. In a preferred embodiment, taking all the above process steps to the exclusion of water before: not only the catalyst but also the inert reaction medium which C0 2 as well as the epoxide are water-free or made free from water in the usual manner.

After decay of the polymerization reaction, the reactor content was worked up to the polycarbonate. This is done in a known manner. As a rule, allowed to cool down the reactor with stirring len, provides pressure equalization with the environment forth (venting the reactor) and the polycarbonate polymer precipitates by adding the reactor contents into a suitable precipitating medium.

Usually used as the precipitating medium alcohols such as methanol, ethanol, propanol, or ketones such as acetone. Methanol is preferred. It is advantageous to acidify the precipitation medium with hydrochloric acid or other suitable acid to pH 0 to 5.5.

The precipitated polymer can be isolated as usual, be dried by filtration, and dried in vacuo for example.

In some cases, a part of the polycarbonate reaction product is also dissolved in the precipitation medium or dispersed, for example in acidified methanol. This polycarbonate may be isolated in customary manner by removing the precipitating agent. For example, one can distill off the methanol under reduced pressure, for example in a rotary evaporator.

From the foregoing, the procedure according to the invention Rens, a preferred method results in that essentially comprises the following process steps:

1. Anhydrous make the catalyst

2. presenting the anhydrous catalyst into a polymerization onsreaktor

3. Optional addition of an inert reaction medium

4. Addition of carbon dioxide

5. Add the epoxide

6. heating the reactor to the reaction temperature 7. Optional add of additional carbon dioxide

8. After decay of the polymerization reaction work-up of the reactor contents to the polycarbonate,

may be reversed wherein the steps 5 and 6 (first heating, then epoxy addition). As mentioned earlier, one can make the catalyst by heating under anhydrous inert gas in the reactor, which coincide steps 1 and 2. FIG.

The inventive method provides advantages over the processes of the prior art, the following advantages:

i) The quantities of catalyst required are considerably lower, ie more grams per gram of catalyst Polymer be generated. This ER höht the process economics.

ii) The polymerization time is 1 to 10 preferably 2 to 5 hours, typically about 3 to 4 hours considerably shorter, which greatly improves the economics of the process.

iii) The weight average molecular weights M w of the resulting polycarbonates are significantly higher than in the prior art of 30,000 to 1,000,000. Of polycarbonates with these molecular weights to molding materials or molded parts, sheets, films and fibers having good properties can, produce particularly good mechanical properties.

iv) By selecting suitable reaction conditions, the polymerization reaction can be controlled so that little or even no undesirable by-products. In particular, the emergence of disturbing polyether homopolymers (III specified at the beginning in the reaction scheme), and the interfering cyclic carbonates IV considerably reduced or omitted completely. III and IV increase the reduced or lack of by-products, the yield of polycarbonate and improve the economics of the process. The absence of the by-products also saves a complicated separation from the main product. This improves the efficiency significantly.

v) Further, improve by the low or non-detectable level of interfering by-products, the mechanical and other properties of the polycarbonates and the moldings produced therefrom.

In particular, can be personalized with the inventive process

producing polycarbonates, which contain no or only insignificant amounts of cyclic carbonates and no or only insignificant amounts of polyether.

By selecting suitable reaction conditions can be in

Setting process product polycarbonate, the ratio of alternating polycarbonate polyether I to II. The polycarbonates obtainable by the process of this invention, in a preferred embodiment, at least 50, preferably at least 70, in particular 75 to 95% carbonate linkages in the polymer chain.

A high proportion of carbonate linkages represent a small proportion of polyether in the polymer chain. Pure alternating polycarbonate I has 100% carbonate linkages. A high proportion of carbonate linkages in the process product by means DEM that the process product of the alternating polycarbonate comes close I. If the proportion of carbonate linkages low, so the process product is close to the polyether II.

To the reaction conditions, which I the polymerization reaction in the ratio main products and II / by-products III and IV, and in particular with respect to the proportion of carbonate linkages in the main product I or II, and thus control the (mechanical and other) properties, are in particular the catalyst, but also the amount of epoxide and C0 2, the C0-form and -Enddruck, and the temperature control of the reaction.

Thus, for example, provide for PO as epoxy zinc carboxylate catalysts predominantly polycarbonates having> 90% carbonate linkages. You ha-ben high modulus and low elongation at break and are tough and resistant. Such tough-resistant polycarbonates are suitable for example for the production of moldings.

Multimetal cyanide catalysts, however, arise with PO more polycarbonates having 70 to 90% carbonate linkages. They have low modulus and high elongation at break and are flexible. Such flexible polycarbonates are suitable for example for the production of sheets and films.

The former tough-resistant polycarbonates are similar in modulus and elongation polyesters such as polybutylene terephthalate (eg Ultradur of BASF), the latter flexible polycarbonates are similar with respect to modulus of elasticity and elongation at break aromatic-aliphatic copolyesters (such as Ecoflex of BASF) or polyethylenes such as LLDPE (linear low density polyethylene) or LDPE (low density polyethylene).

In particular, the polycarbonates of the invention, provided they have been prepared using a zinc carboxylate catalyst, a modulus of about 500 MPa, determined in the tensile test at 23 ° C on cylindrical extrudates of 2.5 mm diameter at 25 mm gauge length, 10 mm gauge length standard way, 50 mm / min tensile speed and 10 kN tensile force.

In addition, the erfindüngsgemäßen polycarbonates, provided they have been produced using a multimetal cyanide catalyst, an elongation at break over 500%, determined in a tensile test at 23 ° C on cylindrical extrudates of 2.5 mm diameter at 25 mm gauge length, 10 mm gauge length standard way 50 mm / min tensile speed and 10 kN tensile force.

The details of the preparation of the cylindrical strands, and for the measurement of E-modulus and elongation at break are as follows: the polycarbonates are dried at 60 to 80 ° C for 4 to 12 hours in vacuo. There are 4 to 5 g of the material in a melting - where flow capillary rheometer (for example, type MP-D of Göttfert Fa.). After 3 to 4 min pre-heating the strands with 2.16 kg load at 150 ° C through the nozzle of the rheometer are extruded (cylindrical die of 2 mm diameter) and allowed to cool in air. Tensile test: the approximately 50 mm long strands of 2.5 mm diameter to be examined at a tensile force of 10 kN and a tensile speed of 50 mm / min, wherein the clamping length 25 mm and the measuring length standard route is (distance between clamping jaws) 10 mm. The measurement is carried out according to DIN 53455-3.

These polycarbonates are also the subject of the invention.

The choice of catalyst accordingly determines substantially the property profile of the polycarbonates.

The inventive method permits the production of poly carbonate molding compounds with tailored, variable within wide limits properties, particularly customized and variable mechanical properties.

The polycarbonates of the invention, produced in particular with ethylene oxide polycarbonates, are characterized by good Bioabbaubar- ness, that is, they are degraded relatively rapidly by microorganisms in the soil, sunlight, hydrolysis or more of these mechanisms.

Accordingly, the invention also provides the polycarbonates obtainable by the novel process, in particular those having at least 50, especially at least 70% carbonate linkages in the polymer chain, and those with good biodegradability. Furthermore, thermoplastic molding compositions are the subject of the invention that contain the aforementioned polycarbonates. Other ingredients of these molding compositions may be polymers such as polyesters such as polybutylene terephthalate, Pblyethylen, as well as biodegradable polymers. Exemplary (eg Ecoflex from BASF), polymers based on lactic acid (polylactide) or starch (starch polymers), polyanhydrides, polyhydroxybutyrate, Polyethylengglykole, polyvinyl alcohols, polyvinyl acetates, cellulose and Stärkeace- be for the latter aromatic-aliphatic rule copolyester did called.

They are known in the art and such. As described in the following documents, which is why further details are unnecessary:

M. Vert et al. , Biodegradable Polymers and Plastics (Second Inter- national Scientific Workshop on Biodegradable Polymers and Plastics), Royal Society of Chemistry, Cambridge, 1992, Special Publication 109;

Y. Doi et al. , Biodegradable Plastics and Polymers (Proceedings of the Third International Scientific Workshop on Biodegradable Plastics and Polymers, Osaka), Elsevier, Amsterdam, 1994, Studies in Polymer Science, 12;

GJ Griffin, Chemistry and Technology of Biodegradable Polymers, Blackie, London 1994th

The thermoplastic molding compositions may also contain conventional additives and processing aids. Such additives and processing aids are lubricants and mold release - medium, colorants such as pigments and dyes, flame retardants, antioxidants, light stabilizers, fibrous and pulverulent fillers and ärkungsmittel verse and antistatic agents in the usual amounts of these agents.

The molding compositions of the invention may by known mixing processes, for example by melting in an extruder, Banbury mixer. Kneader, roll mill or calender, at temperatures of 150 to 300 ° C. However, the components can also be mixed without melting "cold" and the powder or granules composed of mixture is melted and homogenized until during processing '.

The molding compositions to moldings of all kinds, including sheets, films, coatings and fabrics and fibers can, len manufacturer-. The preparation of the sheets may be effected by extrusion, rolling, calendering and other well-known to the skilled worker. The molding compositions according to the invention are thereby formed by heating and / or friction alone or by addition of plasticizing or other additives, to a workable film or a sheet (plate). The processing of three-dimensional moldings of all kinds such as by injection molding.

As coatings, for example coatings of surfaces of paper, wood, plastic, metal or glass are also suitable.

Another object of the present invention is thus the use of the thermoplastic molding compositions for producing moldings, sheets, films, coatings and fibers. Furthermore, the available through use of the thermoplastic molding compositions body sheets, films, coatings and fibers subject matter of the present invention.

Examples

1. Input materials

There were used the following catalysts:

Zn (Glu): zinc glutarate prepared as follows:

In a 1 1 four-necked flask provided with Rührknochen, heating bath and a Wasserauskreiseinrichtung, 35 g of grated zinc oxide were placed in 250 ml of absolute toluene. After addition of 52 g of glutaric acid was heated ER at 55 ° C with stirring for 2 hours. The mixture was then heated to boiling, the reaction water was distilled off azeotropically under reflux until no further water passed over. The toluene was distilled off and the residue is dried at 80 ° C under high vacuum.

DMC: DMC compound prepared as follows:

Equipped with a pitched-blade turbine, dip tube for dosing, pH electrode, Leitfähigkeitmeßzelle and scattered light probe in a stirred tank with a volume of 800 1, 370 kg of aqueous hexacyanocobaltic acid were H 3 [Co (CN) 6] (cobalt content 9 g / l ) and heated with stirring to 50 ° C. Then, with stirring (stirring power of 1 W / 1) 209.5 kg aqueous zinc acetate dihydrate solution (zinc content of 2.7 wt .-%), which was also heated to 50 ° C, were added within 50 min. Subsequently, the wur- 8 kg Pluronic ® PE 6200 (this is a EO-PO block copolymer with 20 wt.% EO and an average molecular weight of about 2000 to 5000, available from BASF) and 10.7 kg of water with stirring. Then 67.5 kg of aqueous zinc acetate dihydrate were Lό- solution (zinc content: 2.7 wt .-%) while stirring (stirring power: 1W / 1) at 50 ° C were metered in over 20 min. The suspension was at 55 ° C while stirring until the pH value of 3.7 to 2.7 had fallen and remained constant. The precipitation suspension obtained in this way was then filtered using a filter press and washed in the filter press with 400 1 water. The wet cake was dried in a circulating air open at 60 ° C to constant weight.

As monomers commercial grades from BASF were used without further purification:

C0: carbon dioxide EO: ethylene oxide PO: propylene oxide

The inert reaction medium toluene was dried over sodium.

2. Experimental procedure for the polymerization

a) Water make the catalyst

The catalyst (type and quantity see Tables) was placed in a re aktor. There was a 300 ml autoclave made of stainless steel, equipped with a mechanical stirrer, or for the SCA le-up experiments (tables 3A and 3B) a 3.5 1 autoclave used with mechanical stirrer nischm. After sealing the reactor 2 gas was purged with N, N-heated with current at 130 ° C and held for 4 hours at these conditions. Then allowed to cool to room temperature.

b) Polymerization

The inert reaction medium toluene (amount see Table) was pressed with C0 2 gas into the reactor. Thereafter, at room temperature (23 ° C) was pressed into the reactor as long as C0, to the value specified in the Ta ¬ bark C0 2 -Vordruck was reached. The duration of this bringing into contact of the catalyst with C0 2 was, depending on C0 2 CAS -before- RAS pressure and reactor volume 1 to 120 min. Thereafter the epoxide was (type and quantity see Tables) pressed with C0 gas into the reactor and then the reactor is heated to the reaction temperature indicated in the tables T R. Temperature T R while pressed C0 2 into the reactor until the specified in the tables C0 -Enddruck was reached - was then at the reaction. The reactor was maintained for a certain time at the reaction temperature T R (time duration see tables), with no C0 2 was replenished. Then allowed to cool to room temperature.

c) work-up

The reactor was vented and the reactor contents was dissolved in 1 1 of methanol containing 5 ml of conc. Hydrochloric acid (37 wt%) was acidified poured. It fell from a polymer, which was filtered and dried overnight at 60 ° C in vacuo. In some examples (denoted in the tables by suffix R) was further concentrated, the obtained when filtering off methanol liquid phase on a rotary evaporator to dryness. a polymer-containing residue was obtained.

3. measurements

To clarify, whether the polymer obtained a mixture (blend) of alternating polycarbonate (I in the above-mentioned scheme) and polyether homopolymer III or a random Polyethercarbo- nat copolymer II, 300 from were recorded on a NMR spectrometer AMX. Bruker 1 H and 13 C NMR spectra of pure alternating polycarbonate I, of pure polyether homopolymer and III of the polymer obtained and compared. It was found that the precipitated polymer was a polyether carbonate copolymer and not a blend.

The precipitated polymer, and the polymer recovered from the methanol liquid phase in the case of R-examples were molecular weights, glass transition and melting temperatures, as well as to the proportion of carbonate linkages, and by-products (cyclic carbonates and polyether), examined.

The indicated in the tables molecular weights of the polymers (weight average M w and number average M n) were determined by gel permeation chromatography (GPC). The details were as follows:

Eluent: hexafluoroisopropanol (HFIP)

Flow rate: 0.5 ml / min GPC system: 150 C ALC / GPC by Waters Fa.

Detector: differential refractometer ERC 7510 from the company ERC

Column: HFIP gel guard column and HFIP gel linear separation column, both from the company Polymer Laboratories.

Calibration: with narrowly distributed polymethyl methacrylate standards with molecular weights M 505-2740000 from PSS.

Temperature: 42 ° C. The indicated in the tables glass transition temperatures T g and T m melting temperatures were determined by differential scanning calorimetry (DSC) according to DIN 53,765th The details were as follows: heating from room temperature to 180 ° C, cooling to -100 ° C, heating to 180 ° C, rate of each 20 K / min, determining in the second run.

The data given in the tables to the proportion carbonate linkages in the polymer and to the presence of by-products (cy- clische carbonates and polyether) were, based on ^ -H-NMR spectra of the precipitated polymer determined. These were X H-NMR spectra of the polymer on a ^ H-NMR spectrometer AMX 300 of Messrs. Bruker, and analyzed qualitatively and quantitatively.

4. results

The following tables summarize the results. The tables labeled A contain the reaction conditions (see above experimental protocol) and the tables indicated by B show the results.

Where:

Time: Duration of Nachreagierenlassens

M w: weight average molecular weight M w M n: number average molecular weight M n

T g: glass transition temperature of the polycarbonate

T m: melting temperature of the polycarbonate

Percentage CV: percentage of carbonate linkages in the polymer

By-products "no" at a content of cyclic carbonates and polyethers of together are smaller or equal to 5 wt .-%, "yes" at a level greater than 5 wt .-%, each based on the polymer

-: not determined

V: for comparison

R: Analysis of the residue from the methanol liquid phase.

Table 1A: C0 / PO copolymer, variation of C0 2 pressure and temperature conditions

^ It was homopolymerized only PO (without C0 2).

2) The catalyst was not rendered anhydrous by heating.

3) The catalyst was made anhydrous by heating outside the reactor and then introduced into the reactor.5) Example 10 was repeated to check reproducibility.

Table IB: CO 2 / P0 Copolyrrter, variation of C0 2 pressure and temperature results

J) was homopolymerized only PO (no. C0 2). 2) The catalyst was not rendered anhydrous by heating.

3) The catalyst was made anhydrous by heating outside the reactor and then introduced into the reactor.

4) There was the polymer-like residue analyzed remaining in Example 8 after the precipitation of the polymer in the liquid phase and was isolated by removal of the methanol.5) Example 10 was repeated to check reproducibility.

Example 2C shows that the process according to the invention with a non-water-free catalyst did not work. It shows that it is erfindungswesentlic to use the catalyst in anhydrous form.

Examples 3 to 8V illustrate the effect of varying the C0 2 -Enddrucks. When C0 -Enddrucken 150-50 bar (Examples 3 to 6) were obtained polycarbonates with molecular weights M w 200,000, containing the most 5 wt .-% undesired by-products (sum of cyclic carbonates and polyethers). In contrast, in C0 -Enddrucken of 20 bar was obtained (Examples 7V to 8RV) polycarbonates having molecular weights M w to about 110,000, containing more than 5 wt .-% by-products.

The example illustrates the pair 4/5 varying the amount of catalyst.

The examples 9V and 10 illustrate the effect of varying the reaction temperature T R. At temperatures of 50 ° C (example 9 V) was obtained polycarbonates containing more than 5 wt .-% unwanted 'by-products. On the other hand showed temperatures of 65 ° C (Example 10) polycarbonates with most 5 wt .-% by-products.

The example pair 10 / 10a illustrates the good reproducibility of the method of the invention: the measured values ​​are in good agreement. This is also true for the scale-up to larger amounts of product, see the following tables 3A and 3B.

In Examples 11 to 15 was not DMC, but zinc glutarate used as catalyst. To give polycarbonates having mole masses M w with the polycarbonates produced by DMC were comparable. The proportion of carbonate linkages was higher than the polycarbonates via DMC with 88 to 97%.

The C0 final pressure was varied in Examples 11 to 15 from 20 to 100 bar, thus different molecular weights and proportions of carbonate linkages resulted. Table 2A: CO 2 / P0 copolymer, variation of amount of PO and amount of catalyst, conditions

6) Example 16 is identical to example 4 listed in Tables 1 A and IB, and has been here for better comparability again.

Table 2B: C0 2 / PO copolymer, variation of amount of PO and amount of catalyst, results

6) Example 16 is identical to Example 4 from Tables 1A and IB and was performed again here for better comparability.

Examples 16 to 19 show that a reduction of the amount of catalyst and an increase in the epoxide (PO) amount results in polycarbonates with high Molmas'sen M w.

The following tables 3A and B illustrate a scale-up of the method to larger quantities. There was used a volume autoclave with 3.5 1 instead of 300 ml.

Table 3A: C0 2 / PO copolymer, scale-up to larger quantities, conditions

7) Example 20 is identical to Example 4 from Tables 1A and IB and was performed again here for better comparability.

Table 3B: C0 / PO copolymer, scale-up to larger quantities, results

7) Example 20 is identical to Example 4 from Tables 1 A and IB, and was listed again here for better comparability.

Examples 20 to 23 demonstrate that a scale-up by a factor of 10 (Examples 20 and 21), or by a factor of 15 (Examples 20 and 22) or by a factor of 21 (Examples 20 and 23) was able to: example 20 24 ml of PO were used in example 21, 240 ml of PO, in example 22, 360 ml of PO and PO in example 23, 500 ml. The property profile of the polycarbonates obtained were similar.

The inventive method is therefore also flexible in terms of used or obtained amounts of fabric.

In the above Tables 1 to 3 propylene oxide was used as the epoxide. The following tables 4A and 4B summarize the results for ethylene oxide / C0 2 copolymers together.

Table 4A: C0 2 / EO copolymer, variation of C0 2 pressure and temperature conditions

Table 4B: C0 / EO copolymer variation of C0 -pressure and temperature conditions

Examples 24 to 26 show for EO as the epoxide the influence of the variation of C0-end pressure and reaction temperature T R. When C0 2 -Enddrucken of 100 to '20 bar and temperatures of 50 to 80 ° C according to the invention polycarbonates with molecular weights M w were obtained from at least 30,000.

For some selected polymers, the mechanical properties were studied. Subsequently, the results are zusammenge- provides.

5. Mechanical Properties

The mechanical properties of the polycarbonates of Example 10 (copolymer of C0 and PO with the DMC catalyst) and Example 12 (copolymer of C0 and PO with Zn (Glu) catalyst) were determined and compared with those of other polymers. These other polymers were ültradur® B 4520, a polybutylene terephthalate PBT (polyester) from BASF and Ecoflex, an aromatic-aliphatic bio- degradable copolyester from BASF.

To this was as follows from the polymer strands prepared: the polycarbonates were dried at 60 to 80 ° C for 4 to 12 hours in vacuo. There were placed in a melt 4 to 5 g of the material - given flow capillary rheometer (model MP-D of Göttfert Fa.). After 3 to 4 min pre-heating the strands with 2.16 kg load at 150 ° C through the nozzle of the rheometer were extruded (cylindrical die of 2 mm diameter) and allowed to cool in air.

The measurement was performed in a tensile test at 23 ° C, and as follows: the 50 mm long strands of 2.5 mm diameter were examined at a tensile force of 10 kN, said clamping length (distance between clamping jaws) 25 mm and the measuring length standard way was 10 mm. To facilitate comparison, tensile tests were performed at two different train speeds, namely 5 mm / min and 50 mm / min, see examples 28a and 28b. The measurement was performed according to DIN 53455-3.

Table 5 summarizes the results. Table 5: Mechanical properties of polycarbonates in comparison

Comparing the examples, the polycarbonate produced using DMC 27 and 28a, as shown in Example 10 (here, Example 27) a significantly lower modulus of elasticity and a much higher elongation at break than the prepared using Zn (Glu) polycarbonate of Example 12 (in this example 28a). The polycarbonate via DMC catalyst was therefore flexible and the polycarbonate via Zn (Glu) catalyst was tough-solid.

Comparing Examples 28b and VI, as the polycarbonate via Zn (Glu) catalyst shows a modulus of elasticity that is close to the PBT Ultradur.

Comparing Examples 27 and V2, so the polycarbonate shows via DMC-catalyst, an E-modulus and elongation at break, which are close to the polyester Ecoflex®.

Accordingly, the method of the invention allows the preparation of polycarbonates with interesting and tailored property profiles.

Claims

Patentansprüche1. A process for preparing high molecular weight aliphatic polycarbonates with following Eigenschaftendas weight average molecular weight Mw, determined by gel permeation chromatography using hexafluoroisopropanol as eluent and polymethyl acrylate standards, is 30,000 to 1,000,000, the content of cyclic carbonates and polyethers together is a maximum of 5 wt .-%, with at least one epoxide of the general formula 1 wherein R is hydrogen, halogen, -N0, -CN, -COOR or a hydrocarbon group having 1 to 20 carbon atoms which may be independently substituted by polymerization of carbon dioxide , are provided, using at least one catalyst selected from the group consisting of zinc carboxylates and multimetal cyanide compounds, characterized in that the catalyst is used in anhydrous form, and that the catalyst first with at least br a subset of the carbon dioxide in contact ingt before adding the epoxy .2. A method according to claim 1, characterized in that makes the catalyst free of water by heating to it before the beginning of polymerization or Inertgasström in vacuo to freedom from water. 3. The method according to claims 1 to 2, characterized in that verwendet.4 as epoxide ethylene oxide, propylene oxide, butene oxide, cyclopentene oxide, cyclohexene oxide, i-butene oxide, acrylic oxides or mixtures thereof. A method according to claims 1 to 3, characterized in that as zinc carboxylates verwendet.5 zinc glutarate, zinc adipate, or mixtures thereof. according to claims 1 to 4, characterized in that there is used as multimetal cyanide compounds of the general formula 2, M1a [M (CN) bAc] d • f MlgXn • h H20 • e L • k P (2) in which method: M1 at least one metal ion selected from the group consisting of Zn2 +, Fe +, Fe3 +, Co2 +, Co3 +, Ni2 +, Mn2 +, Sn2 +, Mo4 +, Mo6 +, Al3 +, V4 +, V5 +, sr2 +, W +, W6 +, Cr2 +, Cr3 +, Cd +, Pd2 +, a3 +, Ce3 +, Ce +, Eu3 +, Mg2 +, Ti3 +, Ti4 +, Ag +, Rh +, Ru2 +, Ru3 +, M2 is at least one metal ion selected from the group consisting of Fe2 +, Fe3 +, Co +, Co3 +, Mn2 +, Mn3 +, V +, V5 +, Cr +, Cr3 +, Rh3 +, Ru3 +, Ir3 +, and M1 and M2 may be the same or different, a is at least one anion selected from the group contained - tend halide, hydroxide, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, cyanide, thiocyanate, isocyanate , cyanate, carboxylate, oxalate, nitrate, nitrosyl, phosphate, dihydrogen phosphate, hydrogen phosphate, X is at least one anion selected from the group consisting of halide, Hydrox yd, sulfate, carbonate, hydrogencarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, where A and X may be identical or different, L is at least one water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones , fabrics ether, polyether, ester, polyester, polycarbonate, urea, amides, nitriles, sulfides, amines, ligands having Py ridin-nitrogen, phosphides, phosphites, phosphanes, phosphonates, phosphates, P, at least one organic additive selected from the group containing glykolglycidylether, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene, Polyvinylmethether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrroli - don, poly (N-vinylpyrrolodon-co-acrylic acid), polyvinyl ethyl ketone, poly (4-vinyl phenol), Pol y (acrylic acid-co-Sty rol), oxazoline polymers, polyalkylenimines, maleic acid, maleic anhydride, hydroxyethyl cellulose, polyvinyl lyacetete, nonionic surfactants and surface-active compounds, bile acids and salts, esters and amides of the bile acid Carbonsäureester polyhydric alcohols, glycosides, wherein a , b, d, g and n are whole or fractional numbers greater than zero, and wherein c, f, h, e and k are integers or fractions greater than or equal to zero, and wherein a, b, c, d, g and n are selected such are such that the electrical neutrality of the cyanide compound MX [M (CN) A] and the compound M ^ -X ist.6 ensured. Process according to claims 1 to 5, characterized in that there is used as Multimetallcyanidverbmdung a compound which is obtainable by reacting sung.7 aqueous hexacyanocobaltic acid H3 [Co (CN) 6] with aqueous zinc acetate solu-. Process according to claims 1 to 6, characterized in that it essentially comprises the following process steps:
1. Anhydrous make the catalyst
2. presenting the anhydrous catalyst in a polymethyl risationsreaktor
3. Optional addition of an inert reaction medium
4. Addition of carbon dioxide
5. Add the epoxide
6. heating the reactor to the reaction temperature
7. Optional addition of further carbon dioxide
8. After decay of the polymerization reaction work-up of the reactor contents to the polycarbonate,
5 wherein the steps may be reversed. 5 and 6
8. Aliphatic polycarbonates, obtainable by the process according to claims 1 to. 7
10 9. Aliphatic polycarbonates according to claim 8, characterized in that they contain at least 70% carbonate linkages in the polymer chain.
10. Aliphatic polycarbonates according to claims 8 to 9, 15 denotes overall by good biodegradability.
11. Aliphatic polycarbonates according to claims 8 to 10, which are made using a zinc carboxylate catalyst, characterized by an E modulus above 500 MPa,
20 determined in a tensile test at 23 ° C on cylindrical extrudates of 2.5 mm diameter at 25 mm gauge length, 10 mm gauge length standard way, 50 mm / min tensile speed and 10 kN tensile force.
12. Aliphatic polycarbonates according to claims 8 to 10, which represents 25 using a multimetal cyanide catalyst manufactured are characterized by an elongation at break over 500, as determined in a tensile test at 23 ° C on cylindrical extrudates of 2.5 mm diameter at 25 mm gauge length, 10 mm gauge length standard way, 50 mm / min pulling speed, and 10 to 30 kN tensile force.
13. Thermoplastic molding compounds containing aliphatic polycarbonates according to claims 8 to 12th
35 14. Use of the thermoplastic molding compositions according to claim 13 for the production of moldings, foils, films, and fibers Beschichtun ¬ gen.
15. moldings, sheets, films, coatings and fibers from the 40 thermoplastic molding compositions according to claim 13,
45
PCT/EP2002/010406 2001-09-27 2002-09-17 Method for producing aliphatic polycarbonates WO2003029325A1 (en)

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