FI102283B - Melt-processable polyester urethane and process for its preparation - Google Patents

Description

102283

Meltable polyester urethane and method for its preparation

The present invention relates to a melt processable polyester urethane according to the preamble of claim 1. Such a polymer contains polyester-derived units and diisocyanate-derived units.

The invention also relates to a prepolymer according to the preamble of claim 12, which is suitable for the production of a polyester urethane according to the invention, and to a process for the preparation of a melt-processable polyester urethane according to the preamble of claim 10. According to the process, the hydroxy acid monomers are first formed into a polyester prepolymer which is copolymerized with a monomer containing isocyanate groups to form a polyester urethane.

Numerous solutions for the preparation of biodegradable polymers from lactic acid condensation polymers and isocyanates are already known from the patent application. The isocyanate acts as a linking group through which the condensation polymer chains are joined by amide and urethane bonds to form polyester urethane.

20 Known manufacturing methods involve e.g. the disadvantage of not being able to significantly influence the molecular weight distribution of the polymer formed. ···, or the degree of crosslinking. However, these properties are important when it comes to poly- • · • · ·. ·. : for the machinability, mechanical properties and heat resistance of seams.

: Furthermore, there is a glass transition temperature of L-lactic acid-based polyester urethane, T8, which • · · ·: 1 £ j largely determines the maximum operating temperature of such an amorphous polymer, about 53 ° C, which is too low for some applications.

It is an object of the present invention to obviate the problems associated with the prior art; and to provide a completely new type of biodegradable polyester urethanes which are meltable • · ·: ‘30 and thus easily adaptable to the desired shape. Further invention: [·. the purpose is to provide polymers with sufficient glass transition temperatures ..,.: high for most practical applications.

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The solution according to the invention is based on the idea that a hydroxylic acid prepolymer which is hydroxyltenninated is used for the preparation of polyester urethane and said prepolymer is reacted with a diisocyanate to give a polymer in which the bonds between the prepolymer and the isocyanate are at least substantially ) are urethane bonds. Continuing the polymerization for at least some time after essentially all the free end groups have reacted with the diisocyanate, i.e. there are almost no free hydroxyl groups in the polymer and the isocyanate groups are mainly present only at the ends of the polymer chains, the polymer becomes at least to some extent. the mechanical properties also improve.

Long chain branching arises as a result of reactions between polymer chains, for example as a result of a reaction between a urethane bond and an isocyanate group at the end of the polymer chain.

To increase the glass transition temperature of polyester urethane, the polyester is prepared by copolymerizing hydroxy acid monomers with polyester chain stiffening components. The hydroxy acid monomers are typically aliphatic hydroxy acids, such as lactic acid, and the polyester chain stiffening components preferably consist of aromatic hydroxy acids.

The number average molecular weight, Mn, of the new polymer is at least 10,000 g / mol and | it has a weight average molecular weight, Mw, of more than 20,000 g / mol and a molecular weight distribution of more than 2. Preferably, the number average molecular weight is • · · V · 10,000 to 200,000 g / mol, particularly preferably about 15,000 to 100,000, the weight average has a molecular weight of 20,000 to 1,000,000, particularly preferably about 30,000 to 600,000, and a molecular weight distribution of 2 to 20, preferably 3 to 10. Its glass transition temperature is usually «·· * '·; ; above 53 ° C.

• · · ♦ · * ··· • · ·: ...: More specifically, the polymer according to the invention is characterized by:: 3D as set forth in the characterizing part of claim 1.

• · · ·

The polyester prepolymer according to the invention comprises structural units derived from lactic acid, aromatic 102283 3 hydroxy acid and organic diol, which are connected to one another in such a way that the end groups of the polyester at least mainly consist of hydroxyl groups. The number average molecular weight of the polyester is relatively low, typically 500 to 20,000, preferably about 1,000 to 8,000 g / mol. The prepolymer has a lactide content of less than 10% by weight and a free lactic acid content of less than 10% by weight.

More specifically, the polymer according to the invention is characterized by what is set out in the characterizing part of claim 12.

The method according to the invention is in turn characterized by what is set forth in the characterizing part of claim 14.

The prior art describes the preparation of low molecular weight biodegradable poly (L-lactic acid-co-D, L-mandelic acid) and poly (L-lactic acid-co-L-3-phenyl lactic acid) [Fukuzaki et al., Makromol . Chem. 190 (1989) 2407-2415]. Although the glass transition temperature of the copolymer increased with increasing monomer content of D, L-mandelic acid, the glass transition temperatures are quite modest with known polymers.

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Solutions are also known in which L-lactic acid and aromatic hydroxy acids have been copolymerized by direct copolycondensation. Due to the poor polycondensation ability of aromatic hydroxy acids, the molecular weights of the copolymers thus prepared are remarkably low. The glass transition temperatures are between 50 and 60 ° C.

In the present invention, it has surprisingly been found that by combining two essential .25 operations, namely the preparation of an e-prepolymer by copolymerization of aliphatic and aromatic hydroxy- • · «• · · acid monomers and coupling of a * ·: · * hydroxyl-terminated prepolyester with a diisocyanate '·; · 'A copolyester urethane with a high molecular weight (= good strength, -3 () cheese properties) and a sufficiently high glass transition temperature (usually> 60 ° C) can be obtained for practical applications.

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In addition, the polyester urethane (PEU) to be produced has quite advantageous properties: - The polymer is biodegradable (i.e. it degrades in the biological environment, typically by microorganisms) and is compostable.

- The mechanical properties of the polymer are even better than PLLA.

5 - As a plastic, it is of the polystyrene type, but stronger.

- The polymer is thermoplastic.

- The raw material costs are very close to the price of hydroxy acids, as the total yield of PEU from hydroxy acid is about 95 mol%, and the isocyanate used as the second main reactant is inexpensive.

10

The invention will now be examined in more detail by means of a detailed description and a few application examples. The attached figure shows the glass transition temperatures of lactic acid and mandelic acid copolymers as a function of the molar fraction of mandelic acid.

15

Preparation of Prepolymer Depending on the amount of starting materials, the polyester consists of 1 to 99.9, typically 50 to 99.9. **. % of aliphatic hydroxy acid monomers, 99.9% to 1%, typically 40% to 20%; 0.1% of aromatic hydroxy acid monomers and 10-0.1% of aliphatic diol monomer. Aliphatic hydroxy acid monomers are preferably L-lactic acid monomers, D-lactic acid monomers or mixtures thereof (e.g. so-called racemic monomers). Other examples of aliphatic hydroxy acid monomers are glycolic acid and α-hydroxyisobutanoic acid In the copolyester urethanes of the present invention, the aromatic group of the hydroxy acid forms a main group of the polyester after the copolyesteration or either of the polyester side chain. The first case is achieved by copolymerizing aliphatic hydroxy acids, e.g. with mandelic acid: or phenyl lactic acid, the phenyl or benzyl groups of the monomers of which cause a reduction in the mobility of the polymer chain after copolyesteration. and L-stereoisomers as well as my and racemic • - · · ta D, L-mandelic acid. The incorporation of a structure-stiffening aromatic group into the copolyester backbone is successful, e.g., by copolymerizing aliphatic / aliphatic hydroxy acid monomer (s) with para-hydroxy acid, e.g. with.

The preparation of the prepolymer, i.e. the copolymerization of aliphatic and aromatic hydroxy acid monomers by condensation polymerization, can be carried out in any apparatus suitable for esterification reactions. According to a preferred alternative, the polyesterification is carried out as a bulk polymerization in a melt, in which case the water formed as a condensation product can be removed by introducing a dry inert gas into the polymer melt while stirring. The removal of water can also be improved by using a vacuum, whereby the pressure of the reaction is calculated stepwise so that the boiling point of the polymer melt at that vacuum is not exceeded. The level of vacuum is limited by the boiling of the polymer, in which case in practice about 20 mbar is the lowest suitable pressure.

In the examples below, the polyester was prepared on a laboratory scale using a "Rotavapor" type apparatus for continuous dewatering.

Preferably, the polyesterification is carried out in the presence of a catalyst, in which case, according to a preferred embodiment, a catalyst suitable for the polymerization of polyurethane is also used. Such polyesterification catalysts are, for example, alkyl or titanium compounds of tin or titanium, such as Sn (II) octoate.

«4 4 • • ·:. · * The rate of increase in the molecular weight of the polyester product depends on the polymerization temperature.

When the polymerization temperature rises above 210 ° C, the degradation of the polymer chains begins to limit the polymerization rate. The formation of a harmful by-product, the lactone, also increases • · ’· * · * significantly at temperatures above 220 ° C. For the above reasons, the temperature of the polyesterization is preferably raised stepwise at a temperature in the range of 140 to 200 ° C at a rate of 5 to 50 ° C per hour and in the range of 200 to 230 ° C at a rate of 0 to 30 ° C per hour.

«« 4 1: 30 According to a preferred alternative, the polyesterification starts from a temperature of about 160 ° C, which is gradually raised to 210 ° C. The pressure is correspondingly reduced stepwise between 240 and 20 mbar, and the condensation product is removed continuously with nitrogen. The standard process described above typically provides a polyester prepolymer having a number average molecular weight of about 2,000 to 8,000 g / mol (e.g., about 4,000 g / mol) and a polydispersity of about 1.5 to 2.5.

In the final stage of polyesterification, the low molecular weight fraction can, if desired, be removed from the reaction mixture by lowering the pressure, whereby the said fraction is distilled off.

Functionalization of Prepolymer Chainheads The isocyanate used as a coupling agent for polyurethanes reacts best with hydroxyl groups. Normally, when polymerizing hydroxy acid, one end group of the chain is a carboxylic acid and the other a hydroxyl. Coupling of such a prepolymer with diisocyanates has proven difficult and too much crosslinking a problem. According to the present invention, the problem is solved by preparing a prepolymer having hydroxyl groups at both ends of the polymer chain.

According to the invention, the hydroxyl-terminated prepolymer is obtained by adding

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A suitable amount of aliphatic diol as a starting material for the mixture of roxic acid monomers. Diolina: '. e.g. ethylene glycol or 1,4-butanediol can be used, but other diols can also be used

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20 1 .. 'to be considered. Preferably, the amount of aliphatic diol is 0.1 to 10 mol% of the amount of hydroxy acid * 'monomers and the hydroxyl and carboxyl of the copolymerizable monomers; : the molar ratio of the groups is greater than 1. 1,4-butanediol is used, e.g. about 1 to 5 mol%.

• · · • · · *

Characterization of the prepolymer 25 • «\ The resulting prepolymer is a brittle, colorless, transparent and amorphous material. By co-polymerizing 90 to 80% of the aliphatic hydroxy acid monomers and 10 to 20% of the almond • · · · · / acid, the glass transition temperature of the final polyester urethane is raised by about 5 to 7 ° C compared to the polyester ester of the aliphatic hydroxyester alone. . The aromatic side groups of mandelic acid raise the glass transition temperature by forming an ethereal barrier to the movement of the polymer chain and thus increasing the stiffness of the chain. Although the decrease in molecular weight has a decreasing effect on the glass transition temperature, the glass transition temperatures of the copolymers of lactic acid and mandelic acid clearly increase with increasing molar proportion of mandelic acid. The glass transition temperatures as a function of the molar fraction of mandelic acid are shown in the accompanying figure.

5 The molecular weights of the copolymers of lactic acid and p-hydroxybenzoic acid remain somewhat lower than those of the copolymers of lactic acid and mandelic acid. The products are still bright and hard. Although increasing the molar fraction of p-hydroxybenzoic acid from zero to 20 mol% reduces the molecular weight of the prepolymer by a quarter compared to the molecular weight of pure polylactic acid, the glass transition temperature of the prepolymer does not decrease.

Due to their low molecular weight, prepolymers containing p-hydroxybenzoic acid (or similar aromatic acids, e.g. p-acetoxybenzoic acid) can be converted to polyester urethanes with a fairly high glass transition temperature by a coupling reaction. This is because the smaller the prepolymer, the more urethane bonds are formed in the product and the urethane bonds increase the glass transition temperature just like aromatic hydroxy acids. By using low molecular weight prepolymers, the molecular weight distribution of the polyester urethane is expanded more rapidly in the copolymerization, and by continuing the polymerization, a higher molecular weight is achieved than, for example, with a pure milk-based prepolymer.

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As a side reaction in the polymerization of hydroxy acids, the corresponding cyclic esters, i.e., lactones, are formed. Thus, in the condensation polymerization of lactic acid, L-lactide is easily formed. In the standard polymerization process, less than 1% of the starting material is sublimed in the condensation product • ··: collection vessels, but ‘1 H-NMR analyzes show that some L-lactide remains in the product. Typically, however, the lactide content is less than • · · 25 '' 'than 10% by weight (e.g. about 3-5%) and the free lactic acid content is likewise less than * · * * 10% by weight. The polyester contains 0 to about 0.5% by weight of polyesterification catalyst.

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The molecular weights of the prepolymer have been measured by the GPC method compared to polystyrene standards: unless otherwise indicated. In some examples, the molecular weights of the prepolymers have also been measured by 13 C-NMR to determine the concentrations of the end groups.

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By appropriately changing the conditions of polyesterification and functionalization, a number average molecular weight of the prepolymer of between 500 and 20,000 can be obtained; preferably it is about 1,000 to 8,000 g / mol. Low molecular weight is preferred for the production of polyester urethane.

5

Manufacture of polyester urethane

Polyester urethane is prepared by interconnecting the polymer chains of a prepolymer with coupling agents that react in a folder of functional groups at the ends of the chains. According to the invention, a relatively high molecular weight, biodegradable polyester urethane can be prepared from OH-terminated prepolymer and diisocyanate with relatively short polymerization times. Most preferably, the coupling reaction, hereinafter also referred to as copolymerization, is performed as a bulk polymerization in the molten state. As the diisocyanate, an aliphatic diisocyanate such as 1,6-hexamethylene di-15 isocyanate is usually used. If it is desired to further increase the glass transition temperature of the resulting polyester urethane at about 5-7 ° C, an alicyclic diisocyanate, e.g. 3-isocyanate methyl-3,5,5-trimethylisocyclohexylate, is used instead of an aliphatic isocyanate (e.g. Unlike hexamethylene diisocyanate, isophorone diisocyanate does not increase polydispersity, which is apparently due to the fact that the isocyanate group 20 'cannot react as easily with urethane bonds, so that the molecular weight distribution does not widen.

• · · | The reaction can be carried out in the presence of a catalyst. Preferred catalysts include tin octoate, dibutyltin dilaurate, dibutyltin diacetate and tertiary amines such as 1,4-diaza (2,2,2) bicyclooctane. The amount of catalyst is up to 2% of the total weight of the reaction mixture.

• t · · | In the copolymerization, the molar ratio between the isocyanate groups of the diisocyanate and the hydroxyl groups of the polyester is typically 0.5 to 1.5, e.g. 0.7 to 1.2, preferably about 1.

The molar ratio between the isocyanate groups and the hydroxyl groups of the polyester may also be greater than 1, preferably about 1.2 to 1.5, if it is desired to obtain at least a partially crosslinked product. The crosslinked product is also obtained by continuing the polymerization for a sufficient time.

The copolymerization is carried out at a temperature of about 130 to 240 ° C, preferably 150 to 220 ° C, and the copolymerization is continued until the resulting copolyester urethane is at least substantially free of free isocyanate groups. Preferably, the copolymerization is continued until the molecular weight distribution of the resulting copolyester urethane, expressed as suhte ^, / Μ ,, is at least 2. By raising the polymerization temperature, the reaction between the end groups of the prepolymers and the diisocyanate can be improved and the glass transition temperature can be raised. This is particularly evident for isophorone diisocyanate.

10

Properties of the polymer

The polymer produced has a number average molecular weight, Mn, of typically 15,000 to 100,000 g / mol, a weight average molecular weight, Mw, of 30,000 to 600,000 g / mol, and a molecular weight distribution of 2 to 12, preferably about 3 to 8.

The polymer is substantially free of free isocyanate groups (i.e. the diisocyanate compounds are completely or at least 99% reacted) and the content of free hydroxy, acid monomers and lactides is at most 3% by weight of the polymer.

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20 ·

Despite the fact that some of the copolymers of lactic acid and mandelic acid are crosslinked, I <«:; : all the polymers prepared according to the invention are melt-processable, the viscosity of the polymer melt being between 10 and 5,000 Pa s, preferably between 50 and 2,000 Pa s, measured with a capillary rheometer at a temperature of 200 ° C at a shear rate of 200 l / s. In some cases, polyester urethanes are long chain branched.

Polyester urethanes with 1,6-hexamethylene diisocyanate as coupling agent | • f * tia, the tensile modulus is about 1.8 to 2.2 GPa, the maximum stress is about 43 to 50 MPa and the maximum elongation is about 1.5-5%. There is no significant difference in the tensile strength values of polyester urethanes made from poly (L-lactic acid) and copolymers of L-lactic acid and mandelic acid 30 **: (LLA / MA), although the number average molecular weights of the copolymers of mandelic acid are lower. However, the weight average molecular weights are close to each other and the incorporation of 102283 10 aromatic ring stiffens (LLA / MA) copolymers, which contributes to compensating for the decreasing molecular weight so that no clear differences in tensile strength measurements are observed.

From the DSC curves of the prepolymer and the final polymer, it can be seen that both polymers are amorphous. Compared to polyester urethane consisting of aliphatic hydroxy acid pomonomers alone, copolymerization with stiffening components results in a higher product with a Tg of more than 10 ° C, up to 12 ° C, i.e. about 60-65 ° C.

10

Despite its good machining properties, the polyester urethane according to the invention is hydrolytically degradable in a biological environment.

The results show that the final coupled polyester urethane (PEU) is of the type 15 quite strong and rigid, but also relatively brittle. However, the polymer is clearly tougher than glass-clear polystyrene. The properties are very close to the poly-L-lactide made by the ring-opening method, even slightly better at least: for these control samples.

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20, Blending, filling and reinforcing polyester urethanes I t

The new polyester urethane can be melt blended with other melt-processable polymers (e.g., thermoplastics) to modify the properties of either the new polyester urethane or another polymer, depending on the blend ratios. Polymers to be melt blended with polyester urethane • · · 25 '/ can be e.g. polyesters or polyolefins, thereby affecting, for example, the biodegradability properties of the polymer blend. The heat resistance of polyester urethanes can be improved, for example, by melt blending polyethylene terephthalate (PET).

4 · 30 V: New polyester urethane can also be filled or reinforced with fillers or reinforcements, which can, for example, increase the heat resistance of the polyester urethane, improve its mechanical properties or reduce the price. Suitable fillers are, for example, chalk and talc.

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For example, cellulose fibers or hemp can be used as reinforcements.

Applications of polyester urethanes 5 Due to the long chain branching of the polymer, the new polyester urethanes are particularly well suited for coating paper or paperboard, which today uses LD polyethylene with long chain branches, largely for coating technical reasons.

The new polyester urethanes have a wide range of applications. Thus, rapeseed-10 extruded pieces and thermoformed and blow-molded packages and bottles can be made from them.

The polymer can be used as a coating for sacks, bags and films made of paper or cardboard. They can be used to produce blown or flat films, which in turn can be used to make packages, bags and sacks. Polymers can also be used in the manufacture of fibers and nonwoven products and can be used to produce expanded plastic products, foams and foams suitable, for example, for filling packaging. Finally, they are also suitable as a coating or matrix for controlled release fertilizers and drugs.

i The unique properties of the new polyester-20s, which combine biodegradability and good mechanical properties, can be exploited in all the above applications.

··· 9 1 1 · '1 The following examples illustrate the invention in more detail: · 25

Example 1 Preparation of a hydroxyl-terminated prepolymer A 2-liter rotary evaporator was used as the reactor. The reactor was weighed with 450 g of L-lactic acid, 76 g of DL-mandelic acid (corresponding to 10 mol% mandelic acid), 9.9 g of 1,4-butanediol and 0.29 g of stannous octoate, which nitrogen was then introduced and an absolute pressure of 240 mbar was drawn in. The reaction vessel was partially immersed in an oil bath. The temperature of the oil bath was raised at a rate of 20 ° C / h to 200 ° C and further to 5 ° C / h to 210 ° C, where it was kept until the end of the polymerization. The pressure was reduced every hour in the following steps: 240 (start) - 160 - 130 - 95 - 80 - 65 - 50 - 40 mbar, where it was held until the end of the polymerization. Nitrogen bubbling was continued throughout the polymerization and the water formed in reaction 5 was recovered as it formed. The total polymerization time was 8 hours.

The number average molecular weight of the obtained polymer as determined by GPC equipment was 3700 g / mol compared to polystyrene standards and the polydispersity was 2.1. DSC-ana-10 lysis showed that the glass transition temperature of the polymer was 44 ° C and no melting peak was observed, so the polymer was completely amorphous.

Example 2 Preparation of hydroxyl-terminated prepolymer

The polymerization was carried out as in Example 1, but the amounts of substances were 450 g: L-lactic acid, 190 g of DL-mandelic acid (corresponding to 20 mol% of mandelic acid), 12 g of 1,4-butanediol and 0.33 g of stannous octoate , and the polymerization time was 10 hours.

The number average molecular weight of the obtained polymer as determined by GPC equipment was 4200 g / mol compared to polystyrene standards and the polydispersity was 2.2. DSC analysis showed that the glass transition temperature of the polymer was 52 ° C and no melting peak was observed.

«L« ···· ’Example 3 | · *: ** Preparation of hydroxyl-terminated prepolymer • * $ 30 Under the conditions of Example 1, L-lactic acid (LLA) and hydroxybenzoic acid or acetoxybenzoic acid, respectively, were copolymerized with butanediol. Table 1 shows the number average molecular weights and glass transition temperatures of the copolymers.

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Table 1. Number average molecular weights and glass transition temperatures of poly (L-lactic acid-co-p-hydroxybenzoic acid) and poly (L-lactic acid-po-co-4-acetoxybenzoic acid) 5 LLA LLA / hydroxybenzoic acid LLA / acetoxybenzoic acid

Molecular weight Glass transition Molecular weight Glass transition M „(g / mol) temperature (° C) Mn (g / mol) temperature (° C) 1.00 4700 35 0.95 2700 35 2000 42 0.90 2000 33 1400 37 10 0 , 85 1600 32 1100 40 0.80 1200 34 750 36

Usually, for low molecular weight polymers, the glass transition temperature is highly dependent on the molecular weight. As the molecular weight decreases, the proportion of end groups increases, which increases the free volume and the mobility of the chains, whereby the glass transition temperature decreases. It is clear from Table 1 that the copolymerization of LLA with p-hydroxy and p-acetoxy / benzoic acid, respectively, prevents a decrease in the glass transition temperature even when the molecular weight decreases. kee.

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20 • ♦ ·:. . Example 4 • · · - Preparation of polyester urethane from polyester containing 10 mol% mandelic acid. cross · «·· 25

A 300 ml glass reactor equipped with a paddle stirrer was used as the reactor. Reactor • «·; *. 40 g of the prepolymer prepared in Example 1 were weighed. After purging with argon (15 min), the reactor was lowered into an oil bath set at 150 ° C. After melting of the prepolymer (30 min), the mixer was started and after 15 min 4.2 g of 1,6-hexamethylene diisocyanate (iIncq: <1: 1) was added. After the addition, the temperature of the oil bath was raised to 180 ° C. The polymerization was continued as the stirrer torque increased, however, as long as the polymer did not contain isocyanate groups (detected by FTIR spectrophotometer), in this polymerization 110 min.

5

The final polyester urethane obtained had a number average molecular weight of 16,000 g / mol, a weight average of 116,000 g / mol and a polydispersity of 8.0. The glass transition temperature of the amorphous polymer was 58 ° C by DSC analysis and the maximum peak of the tanö curve of the DMTA analysis (dynamic-mechanical thermal analysis) at 61 ° C and the maximum of the loss-10 du peak at 55 ° C.

Example 5

Preparation of polyester urethane from a prepolymer containing 20 mol% mandelic acid

The coupling polymerization was carried out in the same manner as in Example 4, but as the prepolymer, the prepolymer of Example 2 containing 20 mol% of D, L-mandelic acid was used. Poly-: ’, the immersion time was 150 min.

20.

The final polyester urethane obtained had a number average molecular weight of 23,000 g / mol, a weight average of 120,000 g / mol and a polydispersity of 6.7. Amorphous poly- | · ♦ ** * the glass transition temperature of the mere was 60 ° C by DSC analysis and the maximum peak of the tanö plot of the DMTA analysis (dynamic, f mechanical thermal analysis) at 64 ° C and the maximum of the loss * * 25 'IL dull peak at 57 ° C .

• '* r · · ·· ♦ Table 2 summarizes the results of Examples 4 and 5. For comparison, polyester urethane made of poly (L-lactic acid) is used.

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Example 6

Preparation of polyester urethane from isophorone diisocyanate

The coupling polymerization was carried out in the same manner as in Example 4, but 5.6 g of 3-isocyanate methyl 3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) was used as isocyanate 5. The polymerization time was 220 min.

The final polyester urethane obtained had a number average molecular weight of 13,500 g / mol, a weight average of 25,300 g / mol and a polydispersity of 1.9. The glass transition temperature of the amorphous poly-10 polymer was 63 ° C by DSC analysis.

Example 7

Preparation of polyester urethane from isophorone diisocyanate 15

The coupling polymerization was carried out in the same manner as in Example 5, but 5.6 g of isophorone diisocyanate was used as the isocyanate. The polymerization time was 210 min.

The final polyester urethane obtained had a number average molecular weight of 10,200 20 g / mol, a weight average of 18,300 g / mol and a polydispersity of 1.8. The glass transition temperature of the amorphous polymer was 65 ° C by DSC analysis.

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Example 8 t • · «25 'Preparation of polyester urethane • <· • <»

The coupling polymerization was carried out in the same manner as in Example 4 using coupling times Isophoronide isocyanate, but the temperature was raised to 200 ° C after the addition of isocyanate. The polymerization time was 220 min.

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The final polyester urethane obtained had a number average molecular weight of 19,600 g / mol, a weight average of 36,000 g / mol and a polydispersity of 1.8. The glass transition temperature of the amorphous polymer 102283 was 65 ° C by DSC analysis.

Table 4 summarizes the main results of Examples 6-8, which have been compared with those obtained with poly (L-lactic acid) -based polyester urethane.

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Claims (30)

1. Fusible polyester urethane containing structural units derived from a polyester and structural units derived from a diisocyanate, characterized in that the polyester consists of aliphatic and aromatic hydroxy acid monomers and diol monomers, the bonds between the structural units, which are derived from the polyester, 10 urethane bonds, the number average of the molar mass of the polymer, Mn, is at least 10,000 g / mol, the weight average of the molar mass, Mw, is over 20,000 g / mol and the molar mass distribution expressed by the ratio Mw / Mn is above 2, and the polymer is essentially free from free isocyanate groups. 15 Polyester urethane according to claim 1, characterized in that the number average number of its molar mass is 10,000 - 200,000 g / mol, preferably about 15,000 - 100,000, the weight average of its molar mass is 20,000 - 1,000,000, preferably about 30,000 - 600,000 and its molar mass distribution is 2-20. 20 Polyester urethane according to claim 1 or 2, characterized by reduced molar mass; the distribution is 3 - 10. • · · • · • · «« * 4. Polyester urethane according to claim 1, characterized in that the polyester comprises 5 to 1 - 99.9% of aliphatic hydroxy acid monomers, to 1 - 99.9% of aromatic hydroxy acid monomers and to 10 - 0.1% of a diol monomer. 5. Polyester urethane according to claim 1, characterized in that the polyester comprises: "to 50 - 99.9% of aliphatic hydroxy acid monomers, to 40 to 0.1% of aromatic". 1 / SO hydroxy acid monomers and to 10 - 0.1% of an aliphatic diol monomer. Γ:. * ·. Polyester urethane according to any of the preceding claims, characterized in that the aliphatic hydroxy acid monomers consist of L-lactic acid monomers, D-lactic acid monomers or mixtures thereof. Polyester urethane according to any of the preceding claims, characterized in that the aromatic hydroxy acid monomers consist of L or D-mandelic acid, p-hydroxybenzoic acid or mixtures thereof. Polyester urethane according to any of the preceding claims, characterized in that the aliphatic diol monomers consist of an ethylene glycol or a 1,4-butanediol. 10 Polyester urethane according to any of the preceding claims, characterized in that it is long chain branched. Polyester urethane according to any one of the preceding claims, characterized in that it is hydrolytically degradable. Polyester urethane according to any one of the preceding claims, characterized in that the viscosity of the polymer melt is between 10 - 5,000 Pa s, preferably 50 - 2,000 Pa s, measured by a capillarometer at a temperature of 200 ° C at a cutting speed of 20 200 l / s. • · t 12. Polyester for use in the production of melt-processable polyester urethane, characterized in that it comprises structural units derived from a lactic acid, an aromatic hydroxy acid as well as a diol, which adhere to each other in such a way that; - its lactide content is below 10% by weight and the content of free lactic acid is below 10% by weight. Polyester according to claim 12, characterized in that the aromatic hydroxy acid units consist of L or D-mandelic acid, p-hydroxybenzoic acid or mixtures thereof. 5 A process for preparing a polyester urethane according to claim 1, wherein the process of starting a hydroxy acid monomer is first formed a lower molecular weight polyester prepolymer, and the prepolymer is copolymerized with a monomer containing 10 isocyanate groups to form a polyester urethane of aliphatic and aromatic hydroxy acid monomers, the hydroxy acid monomer is copolymerized with an aliphatic diol to provide the polyester prepolymer with hydroxyl end groups, the hydroxy terminated polyester prepolymer is copolymerized with a diisocyanate, and the copolymerization is continued until the polyester obtained is free of the polyester residue. 20 15. A process according to claim 14, characterized in that the amount of the aliphatic diol is from 0.1 to 10% of the amount of the hydroxy acid monomer and the molar ratio of the hydroxyl and carboxyl groups of the monomers intended for copolymerization is over 1. • · t • 1 # • <·· '1 25 Process according to Claim 14 or 15, characterized in that the molar ratio between the isocyanate groups of the diisocyanate and the hydroxyl groups of the polyester is 0.5 -1.5. 4 · · * · 1 f 1 • I Process according to any of claims 14-16, characterized in that the hydroxy terminated polyester is copolymerized with a diisocyanate at a temperature of about 130-220 ° C, preferably 150-190 ° C. • · · «·« • I · • · 4 102283 27 18. Method according to claim 14, characterized in that the copolymerization is carried out as pulp polymerization in the molten state. Process according to any one of claims 14-18, characterized in that as S diisocyanate is used a diisocyanate, preferably an aliphatic or alicyclic diisocyanate, such as 1,6-hexamethylene diisocyanate, isofron diisocyanate or methyl bis-4-cyclohexyl isocyanate. 20. A process according to claim 14, characterized in that the polymerization of the polyester is carried out as a pulp polymerization in a molten state, wherein the polymerization temperature is gradually increased at a temperature between 140 and 200 ° C at a rate of 5-50 ° C / h and at temperature between 200 and 230 ° C at a rate of 0 - 30 ° C / h. 15 21. Process according to claim 14, characterized in that the polyester is produced in the presence of a catalyst, a catalyst suitable for polymerization of a polyurethane suitable for use as a catalyst. 22. A process according to claim 21, characterized in that as: polyesteration catalyst, alkyl or alkoxy compounds of tin or titanium are used, such as Sn (II) octoate. • · • · · • · · | ·; ν Polymer blend, characterized in that it contains a polymer according to claim 1 mixed with thermoplastic, such as polyolefin or polyester. 1.25 • I l · • · The polyester urethane of claim 1 or the polymer blend of claim 23. . ·. mixed with fillers or stabilizers. 1 ··· Use of a polymer according to claim 1, for the manufacture of molded ... 30 pieces, as well as heat-formed and mold-blown packages, bags, bags and bottles. «« »102283 Use of a polymer according to claim 1 for coating paper or cardboard. Use of a polymer according to claim 1 for coating bags, strips and sheets made of paper or cardboard. Use of a polymer according to claim 1, for the production of fibers and nonwoven fabrics. Use of a polymer according to claim 1 as coating or matrix in controlled nascent fertilizers or drugs. Use of a polymer according to claim 1, for the production of polymer foam pieces used in packaging. 15 • · • · ♦ ♦ · ♦ ··· ♦ ··· • · · • · «♦ · · • c. • «· •» »♦ · · 1 2 3 · · 2 • · · 3