Isocyanate-free and BPA-free copoly(urethane-carbonate)

Abstract

The present invention relates to a process for preparing random copoly(urethane-carbonate)s, which comprises reacting a six-membered dicyclic carbonate with a polyamine in the presence of a catalyst via a ring-opening polymerization (ROP) reaction to form carbonate units. The present invention also relates to the random copoly(urethane-carbonate)s obtained by this process.

Description

[Technical Field]

[0001] The present invention is in the field of polymer synthesis, and in particular in the field of the preparation of isocyanate-free and BPA-free copolymers by ring-opening polymerization and the resulting copolymers. [Background technology]

[0002] Polyurethanes are widely used in foams, seals, high-performance coatings, and adhesives. These polymers are also expected to be increasingly used in the biomedical field due to their biodegradable and biocompatible characteristics.

[0003] Despite their desirable functional characteristics, a major drawback of these polymers is that the processes for their production involve highly toxic reagents, primarily phosgene and isocyanates. Currently, there is a growing demand for polyurethanes and copolymers that are produced without the use of phosgene and isocyanates.

[0004] It is known that cyclic carbonates have recently been attracting attention as promising monomers for the production of polyurethanes, polycarbonates, and copolymers via phosgene- and isocyanate-free routes [1].

[0005] Polycarbonate, a material used in a wide range of applications from automotive parts to electronic devices, is derived from carbonates of aromatic or aliphatic dihydroxy compounds. The primary polycarbonate material is obtained from the polymerization of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) with toxic phosgene or diphenyl carbonate, derived from the reaction of phenol with phosgene. The product requires high purity without the presence of chlorinated impurities. However, the main raw material, BPA, exhibits estrogenic properties. The release of BPA from polycarbonate has been investigated in numerous studies for exposure and risk assessment due to its widespread use in food and beverage packaging, such as food cans, bottle caps, and water supply pipes, as well as dental sealants and coatings.

[0006] Attempts are being made to develop routes to make isocyanate-free PU and BPA-free PC, and one way to bypass these toxic raw materials is to produce the polymers by ring-opening polymerization (ROP) of cyclic carbonates [1, 2, 3].

[0007] Starting from a 5-membered alkylene carbonate as the cyclic carbonate is one option, but due to thermodynamic properties, the ROP of 5-membered cyclic carbonates is a slow reaction that has been reported to proceed in the presence of catalysts such as metal alkoxides, metal acetylacetonates, and metal alkyls. The ROP reaction rate of 6-membered cyclic carbonates is higher, however, such monomers are generally not commercially available, and their preparation remains challenging.

[0008] Therefore, there is a need to develop new manufacturing methods for producing isocyanate-free and BPA-free polycarbonates. [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] Pyo, SH, Persson, P., Mollaahmad, MA, Sorensen, K., Lundmark, S. and Hatti-Kaul, R., 2011. Pure and Applied Chemistry, 84(3), pp. 637-661 [Non-patent document 2] Wang, P., Park, JH, Sayed, M., Chang, TS, Moran, A., Chen, S. and Pyo, SH, 2018. Polymer chemistry, 9(27), pp. 3798-3807 [Non-patent document 3] Carre, C., Ecochard, Y., Caillol, S. and Averous, L., 2019. ChemSusChem, 12(15), pages 3410-3430. Summary of the Invention [Means for solving the problem]

[0010] Accordingly, the present invention seeks to mitigate, alleviate or eliminate one or more of the above-identified drawbacks and shortcomings in the art, singly or in any combination, or to solve at least the above-mentioned problems, by providing a process for preparing random copoly(urethane-carbonate) comprising reacting a 6-membered dicyclic carbonate with a polyamine via catalyst-controlled ring-opening polymerization to form carbonate units in the presence of a catalyst, preferably through a ring-opening polymerization (ROP) reaction by heating a mixture of a 6-membered dicyclic carbonate according to Formula I, a polyamine and a catalyst to obtain the random copoly(urethane-carbonate). [ka] During the ceremony, R is selected from the group consisting of C1-C20 carbonate, oxygen (ether), C1-C20 dialkyl, C1-C20 alkyl ether, C1-C20 ketone, and C1-C20 ester; R1 and R2 are each independently selected from the group consisting of H, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group, or a derivative thereof.

[0011] Also provided is a process wherein the six-membered dicyclic carbonate is a dicyclic carbonate according to formula II: [ka] R3 is selected from the group consisting of oxygen, C(O), OC(O), C(O)O, and OC(O)O; R4 and R5 are each independently a C1-C20 alkylene; R1 and R2 are each independently selected from the group consisting of H, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group, or a derivative thereof.

[0012] Further provided is a process wherein the molar ratio of polyamine to 6-membered dicyclic carbonate is 0.01:1 to 1:0.01, or 0.1:1 to 1:0.1, or 0.01:1, or 0.1:1, or 0.2:1 to 1:2, or 1:0.01, or 1:0.1, or 1:0.2 to 2:1, for example 0.25:1 to 1:0.25, or even more preferably 0.25:1 to 1:2 or 0.3:1 to 0.9:1.

[0013] Also provided is a process in which the six-membered dicyclic carbonate is ditrimethylolpropane dicyclic carbonate (DTMP-DC) or pentaerythritol dicarbonate (PE-DC), preferably in which the six-membered dicyclic carbonate is ditrimethylolpropane dicyclic carbonate (DTMP-DC).

[0014] Further, the process wherein the polyamine is selected from the group consisting of alkyl diamines, such as 1,6-hexamethylenediamine, 1,2-diethylenediamine and isophoronediamine, bio-based diamines, such as amine derivatives of dimerized fatty acids, and polymeric diamines, triamines and polyamines, such as block copolymers with a polyether backbone consisting of polyethylene glycol and polypropylene glycol with terminal amino functional groups.

[0015] Additionally provided are random copoly(urethane-carbonates) obtainable by the process.

[0016] Furthermore, the FT-IR spectrum of the random copoly(urethane-carbonate) shows a peak at about 3200 cm -1 , for example, 3000-3400 cm -1 The hydroxyl peak is shown in.

[0017] Additionally, an article comprising the random copoly(urethane-carbonate) produced by blow molding, injection molding, or sheet extrusion.

[0018] Also, a film, fiber or pipe comprising a random copoly(urethane-carbonate).

[0019] Furthermore, the use of random copoly(urethane-carbonate) for the production of films, blow-molded or injection-molded articles, fibers or pipes. [Brief explanation of the drawings]

[0020] These and other aspects, features and advantages of the present invention will become apparent and elucidated from the following description of embodiments of the invention which refers to the accompanying drawings.

[0021] [Figure 1]Figure 1 shows an example of the reaction scheme for (A) the random polymerization process of the present invention for producing an isocyanate-free, BPA-free copoly(urethane-carbonate) from a specific molar ratio of a six-membered dicyclic carbonate and a polyamine, and (B) shows a comparison for producing a polyurethane with no carbonate units in the polymer. [Figure 2] FIG. 2 shows the formula for an example of an isocyanate-free, BPA-free copoly(urethane-carbonate) of the present invention. [Figure 3] FIG. 3 shows a table summarizing examples and comparisons of polymerizations of different ratios of ditrimethylolpropane dicyclic carbonate (DTMP-DC) and polyamine (Jeffamine® ED-600) (modifier: 1,4-butanediol, catalyst: 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)). [Figure 4] FIG. 4 shows the Shore D hardness of polyurethane (Comparative 1), polycarbonate (Comparative 2), and isocyanate-free, BPA-free copoly(urethane-carbonate) (Examples 1-7), with Comparative 1 and Examples 1 and 7 showing a Shore D hardness of less than 1. [Figure 5] FIG. 5 shows the FTIR spectra of (A) DTMP-DC, (B) polyamine (Jeffamine® ED-600), (C) polyurethane (Comparative 1), and (D) polycarbonate (Comparative 2). [Figure 6] FIG. 6 shows the FTIR spectra of (A) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 1), (B) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 2), (C) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 3), and (D) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 4). [Figure 7]FIG. 7 shows the FTIR spectra of (A) isocyanate-free, BPA-free copoly(urethane-carbonate) with 1 g of modifier (Example 5), (B) isocyanate-free, BPA-free copoly(urethane-carbonate) with 2 g of modifier (Example 6), and (C) isocyanate-free, BPA-free copoly(urethane-carbonate) with 3 g of modifier (Example 7). [Figure 8] FIG. 8 shows a photograph of an isocyanate-free, BPA-free copoly(urethane-carbonate) (Example 6) prepared in a molding machine from a 30 / 5 ratio of DTMP-DC and a diamine (Jeffamine® ED-600). [Figure 9] FIG. 9 shows an example of a reaction for the preparation of an isocyanate-free, BPA-free copoly(urethane-carbonate) from DTMP-DC and a diamine (Jeffamine® ED-600) with a randomly distributed 30 / 20 urethane unit / carbonate unit ratio. DETAILED DESCRIPTION OF THE INVENTION

[0022] The following description focuses on embodiments of the invention applicable to methods for producing isocyanate-free, BPA-free copoly(urethane-carbonate)s via controlled, base-catalyzed ring-opening polymerization of different ratios of dicyclic carbonates and polyamines (FIG. 1A shows a non-limiting example of such a reaction), and the resulting polymers containing both urethane and carbonate units in the molecule in a randomly ordered structure (FIG. 2 shows a non-limiting example of such a structure).

[0023] Attempts have been made to develop routes to make isocyanate-free PU and BPA-free PC. One way to bypass these toxic raw materials is to produce polymers by ring-opening polymerization (ROP) of cyclic carbonates [1, 2, 3]. Five-membered alkylene carbonates are considered less suitable for commercial use due to their thermodynamic properties during ROP. ROP of five-membered cyclic carbonates is a slow reaction that has been reported to proceed in the presence of catalysts such as metal alkoxides, metal acetylacetonates, and metal alkyls. This polymerization involves partial decarboxylation and loss of CO2, resulting in polymers containing both carbonate and ether linkages.

[0024] The reactivity of allylic and homoallylic five- and six-membered cyclic carbonates, 5-(2-propenyl)-1,3-dioxan-2-one and 4-(3-butenyl)-1,3-dioxolan-2-one, with hexylamine and benzylamine was compared. [4] The reaction rates of the six-membered cyclic carbonates at 30-70 °C were 29-62 times greater than those of the five-membered cyclic carbonates. Thus, six-membered cyclic carbonates appear to offer more opportunities for use in polymerization. Although six-membered cyclic carbonates are thermodynamically more favorable precursors, their preparation is not straightforward, and the monomers are not readily commercially available.

[0025] In the present invention, it has been discovered that dicyclic carbonates can be used to prepare isocyanate-free and BPA-free copoly(urethane-carbonate)s via ring-opening polymerization of dicyclic carbonates with polyamines in different ratios under catalytic control to form urethanes and carbonates (Example illustrated in Figure 1A). This is a mild, environmentally friendly process that does not use phosgene, other chlorinated materials, or bisphenols.

[0026] Cyclic carbonates were reacted with amine or diamine compounds in the absence or presence of a catalyst. Monocyclic carbonates can open their rings to form urethane bonds with amine compounds but may not polymerize, whereas monocyclic carbonates can be polymerized to PC with a catalyst. On the other hand, dicyclic carbonates can form both PU with polyamines and PC with a catalyst. Therefore, dicyclic carbonates can be reacted with polyamines in different ratios with or without heating by using a base catalyst.

[0027] Here, a 1 / 1 ratio (equimolar ratio, dicyclic carbonate / polyamine) theoretically produces only PU, while a 1 / 0 ratio (no polyamine) theoretically produces only PU. Therefore, in the present invention, the ratio of polyamine to dicyclic carbonate is used to control the ratio of PU units to PC units in the copoly(urethane-carbonate).

[0028] Since random copoly(urethane-carbonate)s may contain free hydroxyl groups, the FT-IR spectrum of random copoly(urethane-carbonate)s may contain free hydroxyl groups at approximately 3200 cm -1 , for example, 3000-3400 cm -1 may show a hydroxyl peak.

[0029] It has been discovered that the random copolymers obtained from the reaction using both dicyclic carbonates and polyamines are novel materials with unique properties and structures, and that the ratio of PU to PC units in the manufacturing process can be used to control these properties.

[0030] To achieve the above object, a method for preparing the degradable random copoly(urethane-carbonate) is provided. The process involves polymerizing a six-membered dicyclic carbonate with a polyamine via catalyst-controlled ring-opening polymerization (ROP) to form carbonate units in the presence of a catalyst. The process may be a multi-step process. The process may include the steps of preparing a six-membered dicyclic carbonate, adding a polyamine and a catalyst, and heating the resulting mixture to obtain the random copoly(urethane-carbonate) through a polymerization reaction.

[0031] More specifically, it involves heating a mixture of a six-membered dicyclic carbonate according to Formula I, a polyamine, and a catalyst to obtain a random copoly(urethane-carbonate). [ka]

[0032] wherein R is selected from the group consisting of C1-C20 carbonate, oxygen (ether), C1-C20 dialkyl, C1-C20 alkyl ether, C1-C20 ketone, and C1-C20 ester; R1 and R2 are each independently selected from the group consisting of a direct bond, H, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group, or a derivative thereof.

[0033] The six-membered dicyclic carbonate may be a dicyclic carbonate according to formula II. [ka]

[0034] wherein R3 is selected from the group consisting of a direct bond, oxygen, C(O), OC(O), C(O)O, and OC(O)O; R4 and R5 are each independently a C1-C20 alkylene; R1 and R2 are each independently selected from the group consisting of none, H, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group, or a derivative thereof.

[0035] In this process, the six-membered dicyclic carbonate may be ditrimethylolpropane dicyclic carbonate (DTMP-DC), pentaerythritol dicarbonate (PE-DC), or a combination thereof. Both DTMP and PE are well-known commercial products, making the present invention readily accessible.

[0036] A mixture of six-membered dicyclic carbonates may be used in this process.

[0037] The polyamines of the process may be alkyl diamines such as 1,6-hexamethylenediamine, 1,2-diethylenediamine and isophoronediamine, bio-based diamines such as amine derivatives of dimerized fatty acids (dimeric diamines) and polymeric diamines, triamines and polyamines such as block copolymers with a polyether backbone consisting of polyethylene glycol and polypropylene glycol with terminal amino functional groups.

[0038] The polyamine may be a block copolymer having a polyether backbone consisting of polyethylene glycol and polypropylene glycol with terminal amino functional groups.

[0039] Such polyamines are also well known commercially available products, such as Priamine® and Jeffamine®, making the methods of the present invention readily available for practice and use. In one example of the present invention, the bio-based diamine is Priamine®.

[0040] A mixture of polyamines may be used in this process.

[0041] For the reaction to produce a random copolymer, the molar ratio of polyamine to dicyclic carbonate used is not limited, but is preferably 0.01:1 to 1:0.01, or 0.1:1 to 1:0.1, or 0.01:1, or 0.1:1, or 0.2:1 to 1:2, or 1:0.01, or 1:0.1, or 1:0.2 to 2:1, for example, 0.25:1 to 1:0.25, or even more preferably 0.25:1 to 1:2 or 0.3:1 to 0.9:1.

[0042] The polyamine to dicyclic carbonate used may be in a non-equivalent molar ratio, which promotes the formation of a random copolymer.

[0043] The ratio of polyamine to dicyclic carbonate may be expressed as a molar ratio of 0.01-0.99:1-1:0.99-0.01, for example 0.1-0.9:1-1:0.1-0.9, for example 0.2-0.8:1-1:0.8-0.2, or 0.3-0.8:1-1:0.8-0.3 (mol:mol).

[0044] It was found that polycarbonates made using the ROP of DTMP-DC without polyamine (see Comparative 2) achieve high Shore D hardnesses of over 90, whereas polyurethanes made using the ring-opening polymerization of an equimolar ratio of DTMP-DC and a diamine (Jeffamine® ED-600) achieve Shore D hardnesses of less than 1.

[0045] It was found that by decreasing the proportion of polyamine used, the Shore D hardness increased from less than 1 (Example 1) to 15.2 (Example 2), 28.6 (Example 3), 70.8 (Example 4), and 88.4 (Comparative 2, no polyamine used).

[0046] The preferred weight ratio of polyamine to dicyclic carbonate used is 0.1:1 to 1:0.1. Using the method of the present invention, this results in a strong and resilient copolymer material.

[0047] The mixture of dicyclic carbonate, the mixture of dicyclic carbonate and monocyclic carbonate, and the mixture of polyamine can be used for polymerization, respectively.In one embodiment of the present invention, the dicyclic carbonate is used in the method of the present invention.In another embodiment, the mixture of dicyclic carbonate and monocyclic carbonate is used.

[0048] The polymerization temperature is selected according to the different monomers and initiators and the required requirements. The polymerization temperature may be 0°C or higher, for example, 30°C or higher, 60°C or higher, for example, 100°C or higher, 140°C or higher, or 180°C or higher.

[0049] By having a polymerization temperature of at least 80°C, for example 80-180°C, the resulting material becomes strong and elastic, as shown by the compound properties of the copolymers of Examples 1-8, which have a polymerization temperature of 95°C.

[0050] In one example, the polymerization temperature is at least 80°C, for example, 80 to 180°C.

[0051] The polymerization reaction time is 1 minute to 24 hours, for example, 20 minutes to 3 hours, for example, 30 minutes to 2 hours, for example, 1 hour. In Examples 1 to 8, the duration of the polymerization reaction was 1 hour.

[0052] Preferably, the preparation method includes a melting step in which the six-membered dicyclic carbonate is melted prior to the addition of the polyamine and catalyst.

[0053] Alternatively, the melting step is carried out after the addition of the polyamine and / or catalyst.

[0054] The melting temperature is selected mainly according to the melting point of the 6-membered dicyclic carbonate. The melting temperature in the melting step may be 0°C or higher, for example, 30°C or higher, for example, 60°C or higher, for example, 100°C or higher, 140°C or higher, or 180°C or higher.

[0055] Preferably, the melting temperature is at least the melting point of the six-membered dicyclic carbonate.

[0056] In Examples 1 to 8, the melting temperature for the cocarbonate DTMP-DC was 105° C. The melting temperature may be slightly higher than the melting point of the six-membered dicyclic carbonate, for example, 5° C., 10° C., 15° C., 20° C., or 50° C. higher than the melting point of the six-membered dicyclic carbonate.

[0057] The duration of the melting step may be 0 to 60 minutes depending on the amount of material, but is preferably 1 to 30 minutes, for example 5 minutes. In Examples 1 to 8, the melting step lasted 5 minutes.

[0058] One advantage of melting the 6-membered bicyclic carbonate is that the 6-membered bicyclic carbonate, which is often in solid form, mixes much more efficiently with the polyamine and catalyst (which is often in liquid form) when melted.This is particularly beneficial when the reaction occurs in a solvent-free environment.By carrying out the reaction in a solvent-free environment, the reaction becomes a mild and environmentally friendly process.

[0059] Therefore, the method does not require the use of a solvent.

[0060] The reaction and application may be carried out in solution, and any organic solvent may be used, although it is not essential for the reaction. However, preferred solvents are alcohols (e.g., methanol, ethanol, and propanol), (cyclic) ethers (e.g., diethyl ether and THF), ketones (e.g., acetone, ethyl methyl ketone), toluene, acetonitrile, halogenated alkanes (dichloromethane and chloroform), dimethylformamide, and pyridine, or mixtures thereof or mixtures containing the above solvents. The use of a solvent may be beneficial for homogenization, polymerization, and application.

[0061] The catalyst may be a heterogeneous catalyst or a homogeneous catalyst.

[0062] The catalyst may be an inorganic catalyst, an organometallic catalyst, or an organic catalyst.

[0063] Inorganic and organometallic catalysts can be selected from a variety of potential systems based on metal centers such as sodium, potassium, zinc, magnesium, calcium, tin, titanium, cesium, or rare earth metals with appropriate ancillary ligands.

[0064] Although metal-based catalysts have high catalytic efficiency, they may result in metal contamination in the product, which may affect the application of polymers in the biomedical field. Therefore, it may be beneficial to use organic catalysts.

[0065] Organocatalysts that can be used to direct the ROP of dicyclic carbonates include commercially available amines (e.g., 4-N,N-dimethylaminopyridine), guanidines (e.g., 1,5,7-triazabicyclo-[4.4.0]dec-5-ene), phosphazenes (e.g., 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine), amidines (e.g., 1,8-diazabicycloundec-7-ene), tertiary amines (e.g., dimethylethanolamine), N-heterocyclic carbenes, and bifunctional thiourea-tertiary amine catalysts.

[0066] In Examples 1-8, the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). In one example, the organic catalyst is an amidine catalyst. In a further example, the organic catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0067] The weight ratio of the catalyst to the dicyclic carbonate used is not limited. Preferably, the weight ratio of the catalyst to the dicyclic carbonate used is 0.000001:1 to 1:1, for example, 0.000001:1, or 0.00001:1, for example, 0.0001:1, or 0.001:1, or 0.01:1, or 0.1:1 to 1:1, preferably 0.0001 to 1:1 (weight:weight). It has been found that if the amount of initiator is too small, the polymerization reaction crosslinks in a short time to form a gel, while if the amount of inhibitor is too large, the crosslinking becomes inhomogeneous.

[0068] Therefore, in one preferred example, the weight ratio of the catalyst to the dicyclic carbonate used is 0.001 to 10% by weight, for example 0.01 to 1% by weight.

[0069] The organic catalyst can be used in the presence of an alcohol. Alcohols such as benzyl alcohol, 1,3-propanediol, glycerol, and 1-propanol, which act as coinitiators, chain transfer agents, and modifiers, can be used with the catalyst. These agents can control the properties and ensure proper mixing of the monomers in the process. The weight ratio of the alcohol to the dicyclic carbonate used is not limited, but is preferably 0.01 to 100% by weight, such as 0.01%, 0.1%, 1%, 10%, and 100% by weight, and even more preferably 0.1 to 30% by weight.

[0070] The process may also include the addition of a denaturing agent.

[0071] It has been found that modifiers can play a role in controlling properties and properly mixing the monomers in the process, and therefore material properties such as the Shore D hardness of the copolymer can be further modified with modifiers.

[0072] The denaturant may be an alcohol such as benzyl alcohol, 1,3-propanediol, glycerol and / or 1-propanol. The denaturant may be 1,4-butanediol.

[0073] The weight ratio of the modifier to the dicyclic carbonate used is not limited, but is preferably 0.0001:1 to 1:1 (weight:weight), for example, 0.0001:1, or 0.001:1, or 0.01:1, or 0.1:1 to 1:1, or preferably 0.001:1 to 0.3:1 (weight:weight).

[0074] For example, the use of 1,4-butanediol can form ester units in the polymer chain or at the end groups. In Examples 5-7, 1,4-butanediol was used as the modifier. Shore D hardness measurements showed that as the amount of modifier increased, the hardness decreased in the following order: 70.8 (Example 4, 0 g modifier), 45.2 (Example 5, 1 mL modifier), 12.6 (Example 6, 2 mL modifier), and <1 (Example 7, 3 g modifier) ​​(Figure 4).

[0075] In one example of the present invention, the molar ratio of polyamine to dicyclic carbonate used is 30 to 91 wt %, the 6-membered dicyclic carbonate is ditrimethylolpropane dicyclic carbonate (DTMP-DC), the polyamine is a block copolymer having a polyether backbone consisting of polyethylene glycol and polypropylene glycol with terminal amino functional groups, the catalyst may be the organic catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and the process also includes the addition of a modifier, 1,4-butanediol.

[0076] The reaction was carried out under atmospheric pressure (1 atmosphere), but may be carried out under higher or lower pressures, for example higher pressures may be used to allow for higher temperatures in the presence of solvents.

[0077] The polymerization can be carried out by molding, casting, coating, film blowing and extrusion.

[0078] Thus, in the present invention, random copoly(urethane-carbonate)s may be obtained using the inventive method described above.

[0079] The structure of the random copoly(urethane-carbonate) in the examples was confirmed by FT-IR spectra, as seen in Figures 5-7, which show, among other things, the presence of free hydroxyl groups.

[0080] As can be seen, the FT-IR spectrum of the random copoly(urethane-carbonate) of the present invention has a peak at about 3200 cm -1 The hydroxyl peak is shown in.

[0081] In a random copolymer, the monomer residues are randomly located in the polymer molecule (rather than in a linear arrangement of blocks as in a block copolymer).

[0082] The resulting isocyanate-free and BPA-free copoly(urethane-carbonate) can be seen in Figure 8, which shows a copoly(urethane-carbonate) (according to Example 6) prepared in a molding machine from DTMP-DC and a diamine (Jeffamine® ED-600) in a 30 / 5 ratio.

[0083] As can be seen from Figure 4, the copolymers of the present invention achieve properties that differ from those of a polycarbonate made using the ROP of DTMP-DC without a polyamine (Comparative 2) or a polyurethane made using the ring-opening polymerization of an equimolar ratio of DTMP-DC and a diamine (Jeffamine® ED-600).

[0084] The Shore D hardness of the copolycarbonate (Comparative 2) prepared using the ROP of DTMP-DC without polyamine was close to 90 (88.4), whereas the Shore D hardness of the polyurethane prepared using the ring-opening polymerization of an equimolar ratio of DTMP-DC and a diamine (Jeffamine® ED-600) was <1.

[0085] For the copolymers of the present invention, the Shore D hardness is in the range of >1 to 85, for example, 1 to 80 or 5 to 75. As the proportion of polyamine decreases, the Shore D hardness <1 (Example 1) increases to 15.2 (Example 2), 28.6 (Example 3), 70.8 (Example 4), and 88.4 (Comparative 2, no polyamine used).

[0086] In the examples where a modifier was used, the Shore D hardness could be reduced by increasing the amount of modifier. The Shore D hardness results showed that as the amount of modifier increased, the hardness decreased in the following order: 70.8 (Example 4, 0 g modifier), 45.2 (Example 5, 1 mL modifier), 12.6 (Example 6, 2 mL modifier), and <1 (Example 7, 3 g modifier) ​​(Figure 4).

[0087] In one embodiment of the present invention, the Shore D hardness is in the range of 1-85, for example, in the range of 1-80.

[0088] Thus, the method of the present invention results in a strong, resilient random copolymer, which, because of its randomness, is easily obtainable over a wide range of melting points and seal initiation temperatures (SIT), and also achieves good radiation resistance.

[0089] Furthermore, the glass transition temperature (Tg) is >50°C.

[0090] Thus, random copoly(urethane-carbonates) are suitable for many applications, such as articles made by blow molding, injection molding, or sheet extrusion. Such articles may be films, fibers, or pipes.

[0091] The present invention therefore also relates to the use of random copoly(urethane-carbonates) for the production of films, blown or injection molded articles, fibers or pipes.

[0092] According to certain non-limiting embodiments, the resulting isocyanate-free, BPA-free random copoly(urethane-carbonate) was found to have Formula III: [ka] During the ceremony, R is selected from the group consisting of oxygen (ether), C1-C20 alkyl ether, C1-C20 alkyl, C3-C20 ketone, C3-C20 ester, and C1-C20 carbonate; R1, R2, and R3 are independently selected from the group consisting of none, H, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, C6-C20 phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group, or a derivative thereof; n is at least 1, and for each n, x is 1 to 100,000 and y is 1 to 100,000.

[0093] In such copolymers, the ratio of x to y in the random copoly(urethane-carbonate) is 1:99 to 99:1, or 1:66 to 66:1, or 30:40 to 30:5 (mol / mol). [Example]

[0094] Comparisons and Examples The present invention will now be described in more detail with reference to the following examples, which should not, however, be construed as limiting the scope of the invention.

[0095] The reaction and formation were monitored by FT-IR analysis using a Nicolet-iS5 (Thermo Scientific, USA). The Shore D hardness of the resulting materials was measured at room temperature using a digital hardness durometer (BGD 935 / D, Biuged Laboratory Instruments). The results were averaged from five tests performed on several zones of the sample.

[0096] The number average molecular weights of the polymers in the following examples are determined by gel permeation chromatography (GPC) using tetrahydrofuran as the solvent and polystyrene standards of known average molecular weight. GPC is a type of size exclusion chromatography (SEC) that separates analytes based on size, typically in an organic solvent. This technique is often used to analyze polymers.

[0097] Comparison 1. - Isocyanate-free PU formation from DTMP-DC and diamine (Jeffamine® ED-600) Ring-opening polymerization of DTMP-DC with an equimolar ratio of polyamine produced PU. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, followed by the addition of 18 g (equimolar, 30 mmol) of preheated Jeffamin ED-600. These were then premixed with 0.25 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 min, the polymerization was continued and completed after 1 h at 95 °C. The structure was confirmed by FT-IR (Figure 5C), and the Shore D hardness was measured to be <1 (Figure 4).

[0098] Comparison 2.- BPA-free PC production from DTMP-DC Ring-opening polymerization of DTMP-DC without polyamine yielded PC. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, followed by the addition of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 min, polymerization was continued and completed after 1 h at 95 °C. The structure was confirmed by FT-IR (Figure 5D), and the Shore D hardness was measured to be 88.4 (Figure 4).

[0099] Figure 5. FTIR spectra of (A) DTMP-DC, (B) polyamine (Jeffamine® ED-600), (C) polyurethane (Comparative 1), and (D) polycarbonate (Comparative 2).

[0100] Example 1. - Formation of Isocyanate-Free and BPA-Free Copoly(urethane-carbonate) from DTMP-DC and Diamine (Jeffamine® ED-600) in a 30 / 40 Ratio (Table 1) The use of an excess molar ratio of polyamine to DTMP-DC allows for the production of shorter-chain, isocyanate-free, BPA-free copoly(urethane-carbonate)s through catalysis, since there are not enough carbonate groups to react with the amine end groups. However, some carbonate units may still be formed through the catalyst. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, followed by the addition of 24 g (40 mmol) of preheated Jeffamin ED-600 mixed with 0.3 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 min, the polymerization was continued and completed after 1 h at 95 °C. The structure was confirmed by FT-IR (Figure 6A), and the Shore D hardness was measured to be <1 (Figure 4).

[0101] Example 2. - Formation of Isocyanate-Free and BPA-Free Copoly(urethane-carbonate) from Randomly Distributed 30 / 20 Urethane Unit / Carbonate Unit Ratio DTMP-DC and Diamine (Jeffamine® ED-600) (Table 1 and Figure 9) The use of a lower molar ratio of polyamine to DTMP-DC can produce isocyanate-free, BPA-free copoly(urethane-carbonate) through catalysis. The amine groups react with the cyclic carbonate groups, which also polymerize to form carbonates through the catalyst. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, followed by the addition of 12 g (20 mmol) of preheated Jeffamin ED-600 mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 min, the polymerization was continued and completed after 1 h at 95 °C. The structure was confirmed by FT-IR (Figure 6B), and the Shore D hardness was measured to be 15.2 (Figure 4).

[0102] Example 3. - Formation of Isocyanate-Free and BPA-Free Copoly(urethane-carbonate) from DTMP-DC and Diamine (Jeffamine® ED-600) in a 30 / 10 Ratio (Table 1) The use of a lower molar ratio of polyamine to DTMP-DC can produce isocyanate-free, BPA-free copoly(urethane-carbonate) through catalysis. The amine groups react with the cyclic carbonate groups, which also polymerize to form carbonates through the catalyst. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, followed by the addition of 6 g (10 mmol) of preheated Jeffamin ED-600 mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 min, the polymerization was continued and completed after 1 h at 95 °C. The structure was confirmed by FT-IR (Figure 6C), and the Shore D hardness was measured to be 28.6 (Figure 4).

[0103] Example 4. - Formation of Isocyanate-Free and BPA-Free Copoly(urethane-carbonate) from DTMP-DC and Diamine (Jeffamine® ED-600) in a 30 / 5 Ratio (Table 1) The use of a lower molar ratio of polyamine to DTMP-DC can produce isocyanate-free, BPA-free copoly(urethane-carbonate) through catalysis. The amine groups react with the cyclic carbonate groups, which also polymerize to form carbonates through the catalyst. Reducing the polyamine ratio used may increase the number of carbonate units in the polymer chain. 9.1 g (30 mmol) of DTMP-DC was melted at 110 °C in a 50 mL reaction vessel, followed by the addition of 3 g (5 mmol) of preheated Jeffamin ED-600 mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 min, the polymerization was continued and completed after 1 h at 95 °C. The structure was confirmed by FT-IR (Figure 6D), and the Shore D hardness was measured to be 70.8 (Figure 4). As the proportion of polyamine used decreased, the Shore D hardness increased from <1 (Example 1) to 15.2 (Example 2), 28.6 (Example 3), 70.8 (Example 4), and 88.4 (Comparative 2, no polyamine used).

[0104] Figure 6. FTIR spectra of (A) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 1), (B) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 2), (C) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 3), and (D) isocyanate-free and BPA-free copoly(urethane-carbonate) (Example 4).

[0105] Examples 5-7 - Formation of isocyanate-free and BPA-free copoly(urethane-carbonate) from DTMP-DC and diamine (Jeffamine® ED-600) in a 30 / 5 ratio using modifier (1 g, 2 g, and 3 g, respectively, of 1,4-butanediol) (Table 1) Additionally, the polymer can be further modified with a modifier. Modifiers can control properties and ensure proper mixing of the monomers in the process. For example, the use of 1,4-butanediol can form ester units in the polymer chain or as end groups. From Example 4 above, 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, followed by the addition of 1 g of 1,4-butanediol mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C and 3 g (5 mmol) of preheated Jeffamin ED-600. After 5 minutes, the polymerization was continued and completed after 1 hour at 95 °C. This process was also carried out using 2 g and 3 g of 1,4-butanediol, respectively. The structure was confirmed by FT-IR (Figure 5). Additionally, the Shore D hardness results showed that as the amount of modifier increased, the hardness decreased in the following order: 70.8 (Example 4, 0 g modifier), 45.2 (Example 5, 1 mL modifier), 12.6 (Example 6, 2 mL modifier), and <1 (Example 7, 3 g modifier) ​​(Figure 4).

[0106] Figure 7. FTIR spectra of (A) isocyanate-free, BPA-free copoly(urethane-carbonate) with 1 g of modifier (Example 5), (B) isocyanate-free, BPA-free copoly(urethane-carbonate) with 2 g of modifier (Example 6), and (C) isocyanate-free, BPA-free copoly(urethane-carbonate) with 3 g of modifier (Example 7).

[0107] Example 8. - In situ molding and preparation of isocyanate-free and BPA-free copoly(urethane-carbonate) from DTMP-DC and diamine (Jeffamine® ED-600) in a 30 / 5 ratio (Table 1) For Example 4, polymerization can be carried out in a molding machine. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, followed by the addition of 3 g (5 mmol) of preheated Jeffamin ED-600 mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, polymerization was continued and completed after 1 hour at 95 °C in a molding machine (Figure 8).

[0108] Figure 8. Photograph of isocyanate-free, BPA-free copoly(urethane-carbonate) (Example 6) prepared in a molding machine from DTMP-DC and diamine (Jeffamine® ED-600) in a 30 / 5 ratio.

[0109] Although the present invention has been described above with reference to specific embodiments, it is not intended that the invention be limited to the specific form set forth herein. Rather, the present invention is limited only by the appended claims, and embodiments other than the specific embodiments described above are equally possible within the scope of these appended claims, for example, embodiments different from those described above.

[0110] In the claims, the term "comprises" does not exclude the presence of other elements or steps. Furthermore, individually listed means, elements or method steps may be implemented in a plurality of means, elements or method steps. In addition, although individual features may be included in different claims, these may be advantageously combined where possible, and their inclusion in different claims does not imply that a combination of features is not feasible and / or advantageous. In addition, singular references do not exclude plural references. The terms "a," "an," "first," "second," etc. do not exclude plural references. Reference signs in the claims are provided merely as a clarifying example and shall not be construed as limiting the scope of the claims in any way.

[0111] References [1]Pyo, S. H., Persson, P., Mollaahmad, M. A., Sorensen, K., Lundmark, S., & Hatti-Kaul, R. (2011). Cyclic carbonates as monomers for phosgene- and isocyanate-free polyurethanes and polycarbonates. Pure and Applied Chemistry, 84(3), 637 - 661 pages. [2]Wang, P., Park, J. H., Sayed, M., Chang, T. S., Moran, A., Chen, S., & Pyo, S. H. (2018). Sustainable synthesis and characterization of a bisphenol A-free polycarbonate from a six-membered dicyclic carbonate. Polymer chemistry, 9(27), 3798 - 3807 pages. [3]Carre, C., Ecochard, Y., Caillol, S., & Averous, L. (2019). From the synthesis of biobased cyclic carbonate to polyhydroxyurethanes: A promising route towards renewable NonIsocyanate Polyurethanes. ChemSusChem, 12(15), 3410 - 3430 pages. [4]Tomita H., Sanda F., Endo T., Reactivity comparison of five- and six-membered cyclic carbonates with amines: Basic evaluation for synthesis of poly(hydroxyurethane), J.Polym.Sci. Part A:Polym.Chem. 2001:39:162 - 168.

Claims

1. 1. A method for preparing a random copoly(urethane-carbonate) comprising reacting a six-membered bicyclic carbonate according to formula I with a polyamine via a ring-opening polymerization (ROP) reaction by heating a mixture of the six-membered bicyclic carbonate according to formula I, a polyamine, and a catalyst in the presence of a catalyst to form carbonate units, thereby obtaining the random copoly(urethane-carbonate), 【Chemistry 1】 During the ceremony, R is selected from the group consisting of C1-C20 carbonate, oxygen (ether), C1-C20 dialkyl, C1-C20 alkyl ether, C1-C20 ketone, C1-C20 ester; R １ and R ２ are each independently selected from the group consisting of H, C1 to C20 alkyl, hydroxyl, C1 to C20 hydroxyalkyl, phenyl, C6 to C20 phenylalkyl, C3 to C20 alkylcarbonyl, C3 to C20 carbonylalkyl, C4 to C20 alkoxycarbonyl, C4 to C20 alkoxycarbonyloxy, C2 to C20 carboxyl group, or a derivative thereof.

2. wherein the six-membered bicyclic carbonate is a bicyclic carbonate according to formula II: 【Chemistry 2】 R ３ is selected from the group consisting of oxygen, C(O), OC(O), C(O)O, and OC(O)O; R ４ and R ５ are each independently a C1 to C20 alkylene; R １ and R ２ are each independently selected from the group consisting of H, C1 to C20 alkyl, hydroxyl, C1 to C20 hydroxyalkyl, phenyl, C6 to C20 phenylalkyl, C3 to C20 alkylcarbonyl, C3 to C20 carbonylalkyl, C4 to C20 alkoxycarbonyl, C4 to C20 alkoxycarbonyloxy, C2 to C20 carboxyl group, or derivatives thereof; The method of claim 1.

3. 3. A method according to claim 1 or claim 2, wherein the molar ratio of polyamine to 6-membered dicyclic carbonate is from 0.01:1 to 1:0.01, or from 0.1:1 to 1:0.1, or from 0.01:1, or from 0.1:1, or from 0.2:1 to 1:2, or from 1:0.01, or from 1:0.1, or from 1:0.2 to 2:1, for example from 0.25:1 to 1:0.25, or even more preferably from 0.25:1 to 1:2 or from 0.3:1 to 0.9:

1.

4. 4. A process according to any one of claims 1 to 3, wherein the weight ratio of catalyst to 6-membered dicyclic carbonate is from 0.000001:1 to 1:1, for example 0.000001:1, or 0.00001:1, for example 0.0001:1, or 0.001:1, or 0.01:1, or 0.1:1 to 1:1, preferably 0.0001 to 1:1 (wt:wt).

5. The method according to any one of claims 1 to 4, wherein the 6-membered dicyclic carbonate is ditrimethylolpropane dicyclic carbonate (DTMP-DC) or pentaerythritol dicarbonate (PE-DC), preferably the 6-membered dicyclic carbonate is ditrimethylolpropane dicyclic carbonate (DTMP-DC).

6. 6. The method of claim 1, wherein a mixture of six-membered dicyclic carbonates is used.

7. 7. The method of any one of claims 1 to 6, wherein the polyamine is selected from the group consisting of alkyl diamines, such as 1,6-hexamethylenediamine, 1,2-diethylenediamine and isophoronediamine, bio-based diamines, such as amine derivatives of dimerized fatty acids, and polymeric diamines, triamines and polyamines, such as block copolymers with a polyether backbone consisting of polyethylene glycol and polypropylene glycol with terminal amino functional groups.

8. 8. The method of claim 7, wherein the polyamine is a block copolymer having a polyether backbone consisting of polyethylene glycol and polypropylene glycol with terminal amino functional groups.

9. 9. The method according to claim 1, wherein a mixture of polyamines is used.

10. 10. The method of claim 1, wherein the catalyst is an inorganic catalyst, an organometallic catalyst, or an organic catalyst.

11. The inorganic and organometallic catalysts are selected from the group comprising potential systems based on metal centers such as sodium, potassium, zinc, magnesium, calcium, tin, titanium, cesium or rare earth metals with suitable ancillary ligands; and / or The organic catalyst is selected from the group consisting of amines (4-N,N-dimethylaminopyridine), guanidines (1,5,7-triazabicyclo-[4.4.0]dec-5-ene), phosphazenes (2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine), amidines (1,8-diazabicycloundec-7-ene), tertiary amines (dimethylethanolamine), N-heterocyclic carbenes, and bifunctional thiourea-tertiary amine catalysts.

11. The method according to any one of claims 1 to 10.

12. 12. The method of claim 11, wherein the catalyst is the organic catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

13. 13. The method of any one of claims 1 to 12, wherein the polymerization temperature is 30°C or higher, 60°C or higher, 100°C or higher, 140°C or higher, or 180°C or higher.

14. The method of any one of claims 1 to 13, wherein the polymerization reaction time is from 1 minute to 24 hours, such as from 20 minutes to 3 hours, for example from 30 minutes to 2 hours.

15. 15. The method of any one of claims 1 to 14, also comprising the addition of a modifier.

16. 16. The method of claim 15, wherein the weight ratio of modifier to dicyclic carbonate is from 0.0001:1 to 1:1 (wt:wt), for example from 0.0001:1, or from 0.001:1, or from 0.01:1, or from 0.1:1 to 1:1, or preferably from 0.001:1 to 0.3:1 (wt:wt).

17. The method according to claim 15 or claim 16, wherein the denaturing agent is an alcohol such as benzyl alcohol, 1,3-propanediol, glycerol and / or 1-propanol.

18. The method according to claim 15 or claim 16, wherein the denaturing agent is 1,4-butanediol.

19. the molar ratio of polyamine to dicyclic carbonate used is from 0.3:1 to 0.9:1; the six-membered dicyclic carbonate is ditrimethylolpropane dicyclic carbonate (DTMP-DC); The polyamine is a block copolymer having a polyether backbone composed of polyethylene glycol and polypropylene glycol having terminal amino functional groups, the catalyst is the organic catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); The method also includes adding a modifier, the modifier being 1,4-butanediol.

19. The method of any one of claims 1 to 18.

20. 20. The method of any one of claims 1 to 19, further comprising a melting step in which the 6-membered dicyclic carbonate is melted, preferably said melting step occurring before the addition of the polyamine and catalyst.

21. 19. The method of claim 18, wherein the melting temperature of the melting step is 30°C or higher, such as 60°C or higher, 100°C or higher, 140°C or higher, or 180°C or higher.

22. 22. The method of claim 20 or claim 21, wherein the melting temperature of the melting step is at least as high as the melting point of the six-membered dicyclic carbonate.

23. 23. The method of any one of claims 1 to 22, wherein the reaction is solvent-free.

24. 24. The method of any one of claims 1 to 23, wherein the reaction is carried out in a solution, the solution comprising an organic solvent, the organic solvent being selected from an alcohol, a cyclic ether, a ketone, toluene, acetonitrile, a halogenated alkane, dimethylformamide, and pyridine, or a mixture thereof.

25. the alcohol is selected from methanol, ethanol and propanol; the cyclic ether is selected from diethyl ether and THF; the ketone is selected from acetone and ethyl methyl ketone, and / or The halogenated alkane is selected from dichloromethane and chloroform.

25. The method of claim 24.

26. 26. The method of any one of claims 1 to 25, wherein the polymerization is carried out by molding, casting, coating, film blowing and extrusion.

27. A random copoly(urethane-carbonate) obtainable by the method of any one of claims 1 to 26.

28. The random copoly(urethane-carbonate) of claim 27, having a Shore D hardness of less than 85, for example in the range of 1 to 80.

29. The FT-IR spectrum of the random copoly(urethane-carbonate) is at about 3200 cm －１ 29. The random copoly(urethane-carbonate) of claim 27 or claim 28, which exhibits a hydroxyl peak at

30. The random copoly(urethane-carbonate) of any one of claims 27 to 29, which is isocyanate-free and BPA-free.

31. An article comprising the random copoly(urethane-carbonate) of any one of claims 27 to 30, wherein the article is made by blow molding, injection molding, or sheet extrusion.

32. Use of the random copoly(urethane-carbonate) according to any one of claims 27 to 31 for the manufacture of films, blown or injection moulded articles, fibres or pipes.

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