Isocyanate and bpa-free copolymer (urethane-carbonate)

Abstract

The present invention relates to a process for preparing a random copolymer (urethane-carbonate) comprising reacting a 6-membered bicyclic carbonate with a polyamine by a ring-opening polymerization reaction in the presence of a catalyst via catalytically controlled ring-opening polymerization (ROP) for carbonate unit formation. Furthermore, the present invention relates to a random copolymer (urethane-carbonate) obtainable by said process.

Description

Field of the Invention

[0001] The present invention belongs to the technical field of polymer synthesis, and more particularly, to the manufacture of isocyanate-free and BPA-free copolymers via ring-opening polymerization and to the copolymers thus obtained. Background of the Invention

[0003] Polyurethanes are widely used in foams, seals, high-performance coatings and adhesives. Due to their biodegradable and biocompatible characteristics, these polymers are also expected to find increasingly widespread applications in the biomedical field.

[0004] Although these polymers have good functional properties, their main drawback lies in the need to use highly toxic reagents, mainly phosgene and isocyanates, in their manufacturing processes. Currently, there is an increasing demand for polyurethanes and copolymers produced without the use of phosgene and isocyanates.

[0005] It is known that cyclic carbonates have attracted much attention in recent years as potential monomers for the production of polyurethanes, polycarbonates and copolymers via a phosgene-free and isocyanate-free route [1].

[0006] Polycarbonates have been widely used in various fields from automotive parts to electronic devices, and they are obtained from carbonates from aromatic or aliphatic dihydroxy compounds. The main polycarbonate materials are obtained from the polymerization of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) with toxic phosgene or diphenyl carbonate (which is derived from the reaction of phenol with phosgene), and the products require high purity and the absence of chlorinated impurities. However, the main raw material BPA exhibits estrogenic properties, and due to the widespread use of polycarbonates in food and beverage packaging, such as food cans, bottle caps, water supply pipes, and dental sealants and tooth coatings, a large number of studies have been conducted on the exposure and risk assessment of the release of BPA from polycarbonates.

[0007] Attempts have been made to develop routes for the production of isocyanate-free PUs and BPA-free PCs, and one way to bypass these toxic raw materials is to produce polymers by ring-opening polymerization (ROP) of cyclic carbonates [1,2,3].

[0008] A method starting from five-membered alkylene carbonates as cyclic carbonates is an option. However, due to thermodynamic properties, the ROP of five-membered cyclic carbonates is a slower reaction, and it is reported that the reaction is carried out in the presence of catalysts such as metal alkoxides, metal acetylacetonates and metal alkylates. The ROP reaction rate of six-membered cyclic carbonates is higher, however, such monomers are usually difficult to obtain commercially, and their production is not easy.

[0009] Therefore, there is a need to develop new manufacturing methods for the production of isocyanate-free and BPA-free polycarbonates. Summary of the Invention

[0011] Accordingly, the present invention preferably seeks to alleviate, mitigate or eliminate one or more of the above-mentioned deficiencies and disadvantages in the prior art, either alone or in any combination, and at least solve the above problems by providing a method for preparing a random copolymer (urethane - carbonate), the method comprising: in the presence of a catalyst, by heating a mixture of a six - membered bicyclic carbonate, a polyamine and a catalyst according to formula I, via catalytically controlled ring - opening polymerization (ROP) for carbonate unit formation, reacting the six - membered bicyclic carbonate with the polyamine by a ring - opening polymerization reaction to obtain a random copolymer (urethane - carbonate),

[0012] (I)

[0013] Wherein:

[0014] R is selected from the group consisting of: C1 - C20 carbonates, oxygen (ethers), C1 - C20 dialkyls, C1 - C20 alkyl ethers, C1 - C20 ketones, C1 - C20 esters;

[0015] R1 and R2 are each independently selected from the group consisting of: H, C1 - C20 alkyls, hydroxyl, C1 - C20 hydroxyalkyls, phenyl, C6 - C20 phenylalkyls, C3 - C20 alkyl carbonyls, C3 - C20 carbonylalkyls, C4 - C20 alkoxy carbonyls, C4 - C20 alkoxy carbonyl oxys, C2 - C20 carboxyls or their derivatives.

[0016] There is also provided a method, wherein the six - membered bicyclic carbonate is a bicyclic carbonate according to formula II;

[0017] (II)

[0018] R3 is selected from the group consisting of oxygen, C(O), OC(O), C(O)O and OC(O)O;

[0019] R4 and R5 are each independently C1 - C20 alkylene groups;

[0020] R1 and R2 are each independently selected from the group consisting of: H, C1 - C20 alkyls, hydroxyl, C1 - C20 hydroxyalkyls, phenyl, C6 - C20 phenylalkyls, C3 - C20 alkyl carbonyls, C3 - C20 carbonylalkyls, C4 - C20 alkoxy carbonyls, C4 - C20 alkoxy carbonyl oxys, C2 - C20 carboxyls or their derivatives.

[0021] Further provided is a method in which the molar ratio of polyamine to the six-membered bicyclic 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 0.1:1, or 0.2:1 to 1:2, or from 1:0.01, or 1:0.1, or 1:0.2 to 2:1, such as from 0.25:1 to 1:0.25, or even more preferably from 0.25:1 to 1:2 or 0.3:1 to 0.9:1.

[0022] Also provided is a method in which the six-membered bicyclic carbonate is ditrimethylolpropane bicyclic carbonate (DTMP-DC) or pentaerythritol dicarbonate (PE-DC); preferably, the six-membered bicyclic carbonate is ditrimethylolpropane bicyclic carbonate (DTMP-DC).

[0023] Further, a method in which the polyamine is selected from the group consisting of: alkyl diamines such as 1,6-hexamethylenediamine, 1,2-diethylenediamine, and isophorone diamine; bio-based diamines such as amine derivatives of dimer fatty acids; and polymeric diamines, triamines, and polyamines such as block copolymers having a polyether framework composed of polyethylene glycol and polypropylene glycol and having terminal amino functional groups.

[0024] Further provided is a random copolymer (urethane-carbonate) obtainable by the method.

[0025] Further, for the random copolymer (urethane-carbonate), the FT-IR spectrum of the random copolymer (urethane-carbonate) shows a hydroxyl peak at about 3200 cm -1 , for example, between 3000 and 3400 cm -1 .

[0026] Further, an article comprising the random copolymer (urethane-carbonate), wherein the article is prepared by blow molding, injection molding, or sheet extrusion.

[0027] In addition, a film, fiber, or tube comprising the random copolymer (urethane-carbonate).

[0028] Further, the use of the random copolymer (urethane-carbonate) for producing a film, an article made by blow molding or injection molding, a fiber, or a tube. Brief Description of the Drawings

[0030] These and other aspects, features, and advantages achievable by the present invention will become apparent and clarified by the following description of the embodiments of the present invention with reference to the drawings, in which:

[0031] Figure 1Examples of reaction overviews are shown: (A) The random polymerization method of the present invention, which produces a copolymer (urethane-carbonate) without isocyanate and without BPA from a six-membered bicyclic carbonate and a polyamine in a certain molar ratio; (B) A comparative example showing the production of a polyurethane without carbonate units in the polymer;

[0032] Figure 2 The chemical formula of an example of the isocyanate-free and BPA-free copolymer (urethane-carbonate) of the present invention is shown;

[0033] Figure 3 A table summarizing the examples and comparisons of the polymerization of ditrimethylolpropane bicyclic carbonate (DTMP-DC) and polyamine (Jeffamine® ED-600) at different ratios is shown (modifier: 1,4-butanediol, catalyst: 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU));

[0034] Figure 4 The Shore D hardness of polyurethane (Comparative Example 1), polycarbonate (Comparative Example 2), and isocyanate-free and BPA-free copolymer (urethane-carbonate) (Examples 1-7) is shown. Comparative Example 1, and Examples 1 and 7 are both below 1 (Shore D hardness);

[0035] Figure 5 The FTIR spectra of (A) DTMP-DC, (B) polyamine (Jeffamine® ED-600), (C) polyurethane (Comparative Example 1), and (D) polycarbonate (Comparative Example 2) are shown;

[0036] Figure 6 The FTIR spectra of (A) isocyanate-free and BPA-free copolymer (urethane-carbonate) (Example 1), (B) isocyanate-free and BPA-free copolymer (urethane-carbonate) (Example 2), (C) isocyanate-free and BPA-free copolymer (urethane-carbonate) (Example 3), and (D) isocyanate-free and BPA-free copolymer (urethane-carbonate) (Example 4) are shown;

[0037] Figure 7 The FTIR spectra of (A) isocyanate-free and BPA-free copolymer (urethane-carbonate) with 1 g of modifier (Example 5), (B) isocyanate-free and BPA-free copolymer (urethane-carbonate) with 2 g of modifier (Example 6), and (C) isocyanate-free and BPA-free copolymer (urethane-carbonate) with 3 g of modifier (Example 7) are shown;

[0038] Figure 8Pictures of the isocyanate- and BPA-free copoly(carbamate-carbonate) prepared from DTMP-DC and diamine (Jeffamine® ED-600) at a ratio of 30 / 5 in a mold are shown (Example 6); and

[0039] Figure 9 Examples of the reaction for producing an isocyanate- and BPA-free copoly(carbamate-carbonate) in a random distribution manner from DTMP-DC and diamine (Jeffamine® ED-600) at a ratio of 30 / 20 urethane units / carbonate units are shown. Detailed Description

[0040] The following description pertains to one embodiment of the present invention, which is applicable to a method for manufacturing an isocyanate- and BPA-free copoly(carbamate-carbonate) by ring-opening polymerization of a bicyclic carbonate and a polyamine at different ratios controlled by an alkali catalyst ( Figure 1 A shows a non-limiting example of this reaction). Further, the resulting polymer contains both urethane units and carbonate units in the molecule and has a random structure ( Figure 2 A non-limiting example of this structure is illustrated).

[0041] Attempts have been made to develop routes for preparing isocyanate-free PUs and BPA-free PCs, and one way to bypass these toxic raw materials is to produce polymers by ring-opening polymerization (ROP) of cyclic carbonates [1,2,3]. Due to the thermodynamic properties of ROP, the commercial application prospects of five-membered alkylene carbonates have been considered limited. The ROP of five-membered cyclic carbonates is a slow reaction, and it has been reported that the reaction is carried out in the presence of catalysts such as metal alkoxides, metal acetylacetonates, and metal alkylates. The polymerization involves partial decarboxylation and loss of CO2, and thus the resulting polymer contains both carbonate bonds and ether bonds.

[0042] The reactivity of allyl- and homoallyl-substituted five- and six-membered cyclic carbonates, 5-(2-propenyl)-1,3-dioxan-2-one and 4-(3-butenyl)-1,3-dioxolane-2-one, with hexylamine and benzylamine was compared [4]. The reaction rate of six-membered cyclic carbonates at 30 - 70 °C was 29 to 62 times higher than that of five-membered cyclic carbonates at 30 - 70 °C. Therefore, six-membered cyclic carbonates seem to offer more opportunities for applications in polymerization. Although six-membered cyclic carbonates are more thermodynamically suitable precursors, their production is not simple, and the monomers are not easily commercially available.

[0043] In the present invention, it has been found that bicyclic carbonates can be used to produce isocyanate-free and BPA-free copoly(urethane-carbonate) under catalytic control for urethane and carbonate formation by ring-opening polymerization with polyamines at different bicyclic carbonate and polyamine ratios (Examples are set forth in Figure 1 A). This is a mild and environmentally friendly method that does not require the use of phosgene, other chlorides, and bisphenol.

[0044] Cyclic carbonates react with amine or diamine compounds in the presence or absence of a catalyst. Monocyclic carbonates can react with amine compounds to form urethane bonds but cannot polymerize, while they can be polymerized into PC under the action of a catalyst. At the same time, bicyclic carbonates can both generate PU with polyamines and generate PC under the action of a catalyst. Therefore, by using a base catalyst, bicyclic carbonates react with polyamines at different ratios, with or without heating.

[0045] Here, a ratio of 1 / 1 (bicyclic carbonate / polyamine, equimolar ratio) theoretically produces only PU, and a ratio of 1 / 0 (without polyamine) theoretically produces only PU. Therefore, in the present invention, the ratio of polyamine to bicyclic carbonate is used to control the ratio of PU units and PC units in the copoly(urethane-carbonate).

[0046] Since the random copoly(urethane-carbonate) can contain free hydroxyl groups, the FT-IR spectrum of the random copoly(urethane-carbonate) shows a hydroxyl peak at about 3200 cm -1 −1, for example, between 3000 and 3400 cm -1 −1.

[0047] It has been found that the random copolymers produced by the reaction of both bicyclic carbonates and polyamines are new materials with unique properties and structures, and their properties can be controlled by the ratio of PU units and PC units in the production method.

[0048] To achieve the above object, a method for preparing a degradable random copoly(urethane-carbonate). The method includes polymerizing a six-membered bicyclic carbonate with a polyamine via catalytically controlled ring-opening polymerization (ROP) for carbonate unit formation in the presence of a catalyst. The method can be a multi-stage method. The method can include the following steps: providing a six-membered bicyclic carbonate, adding a polyamine and a catalyst, and heating the resulting mixture to obtain a random copoly(urethane-carbonate) by a polymerization reaction.

[0049] More specifically, it includes heating a mixture of a 6-membered bicyclic carbonate, a polyamine, and a catalyst according to Formula I to obtain a random copoly(urethane-carbonate):

[0050] (I)

[0051] Herein, R is selected from the group consisting of: C1-C20 carbonates, oxygen (ethers), C1-C20 dialkyls, C1-C20 alkyl ethers, C1-C20 ketones, C1-C20 esters;

[0052] R1 and R2 are each independently selected from the group consisting of: a direct bond, H, C1-C20 alkyl, hydroxy, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl or their derivatives.

[0053] The 6-membered bicyclic carbonate may also be a bicyclic carbonate according to formula II:

[0054] (II)

[0055] Herein, R3 is selected from the group consisting of a direct bond, oxygen, C(O), OC(O), C(O)O and OC(O)O;

[0056] R4 and R5 are each independently C1-C20 alkylene;

[0057] R1 and R2 are each independently selected from the group consisting of: none, H, C1-C20 alkyl, hydroxy, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl or their derivatives.

[0058] In the method, the six-membered bicyclic carbonate may be ditrimethylolpropane bicyclic carbonate (DTMP-DC), pentaerythritol dicarbonate (PE-DC) or a combination thereof. Both DTMO and PE are well-known commercial products, making the present invention easy to apply.

[0059] In the method, a mixture of more than one type of 6-membered bicyclic carbonate may be used.

[0060] The polyamine of the method may be: an alkylenediamine, such as 1,6-hexamethylenediamine, 1,2-diethylenediamine and isophoronediamine; a bio-based diamine, such as an amine derivative of dimer fatty acid (dimer diamine); and a polymeric diamine, triamine and polyamine, such as a block copolymer having a polyether framework composed of polyethylene glycol and polypropylene glycol and having terminal amino functional groups.

[0061] The polyamine can be a block copolymer having a polyether framework composed of polyethylene glycol and polypropylene glycol and having a terminal amino functional group.

[0062] Such polyamines are also well-known commercial products, such as Priamine® and Jeffamine®, making the method of the present invention easy to implement and use. In one embodiment of the present invention, the bio-based diamine is Priamine®.

[0063] In the method, a mixture of more than one type of polyamine can be used.

[0064] For the reaction to obtain a random copolymer, the molar ratio of the polyamine to the bicyclic carbonate used is not restrictive, but is preferably from 0.01:1 to 1:0.01, or from 0.1:1 to 1:0.1, or from 0.01:1, or 0.1:1, or 0.2:1 to 1:2, or from 1:0.01, or 1:0.1, or 1:0.2 to 2:1, such as from 0.25:1 to 1:0.25, or even more preferably from 0.25:1 to 1:2 or 0.3:1 to 0.9:1.

[0065] The polyamine and the bicyclic carbonate used can be in a non-equimolar ratio. This is to promote the formation of a random copolymer.

[0066] The ratio of the polyamine to the bicyclic carbonate can be expressed as a molar ratio (mol:mol) of 0.01-0.99:1 to 1:0.99-0.01, such as 0.1-0.9:1 to 1:0.1-0.9, such as 0.2-0.8:1 to 1:0.8-0.2 or 0.3-0.8:1 to 1:0.8-0.3.

[0067] It was found that the polycarbonate obtained by ROP of DTMP-DC in the absence of polyamine (see Comparative Example 2) had a high Shore D hardness of >90, while the polyurethane obtained by the ring-opening polymerization of DTMP-DC and diamine (Jeffamine® ED-600) in an equimolar ratio had a Shore D hardness of <1.

[0068] By reducing the ratio of the polyamine used, it was found that the Shore D hardness increased from <1 (Example 1) to 15.2 (Example 2), to 28.6 (Example 3), to 70.8 (Example 4), and to 88.4 (Comparative Example 2, without using polyamine).

[0069] The preferred weight ratio of the polyamine to the bicyclic carbonate used is between 0.1:1 and 1:0.1. By using the method of the present invention, a copolymer material with high strength and resilience is obtained.

[0070] Mixtures of bicyclic carbonates, mixtures of bicyclic carbonates and monocyclic carbonates, and mixtures of polyamines can be used for polymerization respectively. In one embodiment of the present invention, a bicyclic carbonate is used in the method of the present invention. In a further embodiment, a mixture of a bicyclic carbonate and a monocyclic carbonate is used.

[0071] The polymerization temperature is selected according to different monomers and initiators and the required requirements. The polymerization temperature can be above 0 °C, such as above 30 °C, above 60 °C, such as above 100 °C, above 140 °C or above 180 °C.

[0072] By making the polymerization temperature at least 80 °C, such as 80 to 180 °C, the resulting material will be high in strength and good in elasticity, as shown by the compound properties of the copolymers in Examples 1 to 8, where the polymerization temperature is 95 degrees.

[0073] In one instance, the polymerization temperature is at least 80 °C, such as 80 to 180 °C.

[0074] The polymerization reaction time is from 1 minute to 24 hours, such as 20 minutes to 3 hours, such as 30 minutes to 2 hours, such as 1 hour. In Examples 1 - 8, the polymerization reaction time lasts for 1 hour.

[0075] Preferably, the preparation method includes a melting step, in which a 6-membered bicyclic carbonate is melted before the addition of polyamine and catalyst.

[0076] Alternatively, the melting step is carried out after the addition of polyamine and / or catalyst.

[0077] The melting temperature is mainly selected according to the melting point of the 6-membered bicyclic carbonate. The melting temperature of the melting step can be above 0 °C, such as above 30 °C, such as above 60 °C, such as above 100 °C, above 140 °C or above 180 °C.

[0078] Preferably, the melting temperature is at least the melting point of the 6-membered bicyclic carbonate.

[0079] In Examples 1 to 8, the melting temperature for the bicyclic carbonate (co-carbonate) DTMP-DC is 105 °C. The melting temperature can also be slightly higher than the melting point of the 6-membered bicyclic carbonate, such as 5, 10, 15, 20 or 50 degrees higher than the melting point of the 6-membered bicyclic carbonate.

[0080] The duration of the melting step can be from 0 to 60 minutes, depending on the amount of the material, but preferably 1 to 30 minutes, such as 5 minutes. In Examples 1 - 8, the melting step is 5 minutes.

[0081] One advantage of melting the six-membered bicyclic carbonate is that the six-membered bicyclic carbonate, which is usually in solid form, will have a higher mixing efficiency with polyamines and catalysts (which are usually in liquid form) when melted. This is especially beneficial when the reaction occurs in a solution-free environment. Conducting the reaction in a solution-free environment makes it a mild and environmentally friendly method.

[0082] Therefore, the method can be solvent-free.

[0083] The reaction and application can be carried out in solution form, and any organic solvent can be used, although this is not necessary for the reaction. However, preferred solvents are alcohols (such as methanol, ethanol, and propanol), (cyclic) ethers (such as diethyl ether and THF), ketones (such as acetone, ethyl methyl ketone), toluene, acetonitrile, haloalkanes (dichloromethane and chloroform), dimethylformamide, and pyridine, or mixtures thereof, or mixtures containing the above solvents. Using a solvent may be beneficial for homogenization, polymerization, and application.

[0084] The catalyst is a heterogeneous catalyst or a homogeneous catalyst.

[0085] The catalyst can be an inorganic catalyst, an organometallic catalyst, or an organic catalyst.

[0086] The inorganic catalyst and the organometallic catalyst can be selected from a variety of well-known systems, the well-known systems being based on metal centers such as sodium, potassium, zinc, magnesium, calcium, tin, titanium, cesium, or rare earth metals and bearing suitable ancillary ligands

[0087] Metal-based catalysts have high catalytic efficiency but can cause metal contamination in the product, which may affect the application of the polymer in the biomedical field. Therefore, it may be advantageous to use an organic catalyst.

[0088] Organic catalysts can be used to initiate the ROP of bicyclic carbonates, which include commercially available amines (such as 4-N,N-dimethylaminopyridine), guanidines (such as 1,5,7-triazabicyclo-[4.4.0]dec-5-ene), phosphazenes (such as 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine), amidines (such as 1,8-diazabicycloundec-7-ene), tertiary amines (such as dimethylethanolamine), N-heterocyclic carbenes, and bifunctional thiourea-tertiary amine catalysts.

[0089] In Examples 1-8, the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). In one embodiment, the organic catalyst is an amidine catalyst. In another embodiment, the organic catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0090] The weight ratio of the catalyst to the bicyclic carbonate used is not limited. Preferably, the weight ratio of the catalyst to the bicyclic carbonate used is from 0.000001:1 to 1:1, such as 0.000001:1 or 0.00001:1, such as from 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 when the amount of the initiator is too small, the polymerization reaction will crosslink to form a gel in a short time; while when the amount of the inhibitor is too large, the crosslinking will be uneven.

[0091] Therefore, in a preferred embodiment, the weight ratio of the catalyst to the bicyclic carbonate used is 0.001 to 10 wt%, such as 0.01 to 1 wt%.

[0092] The organic catalyst can be used in the presence of an alcohol. Alcohols, such as benzyl alcohol, 1,3-propanediol, glycerol, and 1-propanol, can be used together with the catalyst as co-initiators, chain transfer agents, and modifiers. These reagents can play a role in controlling the properties and properly mixing the monomers during the process. The weight ratio of the alcohol to the bicyclic carbonate used is not limited, but a ratio of 0.01 to 100 wt% is preferably used, such as 0.01, 0.1, 1, 10, and 100 wt%, or even more preferably a ratio of 0.1 to 30 wt%.

[0093] The method may further include adding a modifying reagent (modifier).

[0094] The modifier can play a role in controlling the properties and properly mixing the monomers during the process, and thus it has been found that the material properties of the copolymer (such as Shore D hardness) can be further modified by the modifier.

[0095] The modifying reagent can be an alcohol, such as benzyl alcohol, 1,3-propanediol, glycerol, and / or 1-propanol. The modifying reagent can also be 1,4-butanediol.

[0096] The weight ratio of the modifier to the bicyclic carbonate used is not limited, but a ratio of from 0.0001:1 to 1:1 (weight:weight) is preferably used, such as from 0.0001:1, or 0.001:1, or 0.01:1, or 0.1:1 to 1:1, or preferably a ratio of 0.001:1 to 0.3:1 (weight:weight).

[0097] 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 a modifier. The Shore D hardness results showed that as the amount of the modifier was increased, the hardness decreased successively to 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 ).

[0098] In one embodiment of the present invention, the molar ratio of the polyamine to the bicyclic carbonate used is 30 to 91 wt%, the 6-membered bicyclic carbonate is ditrimethylolpropane bicyclic carbonate (DTMP-DC), the polyamine is a block copolymer having a polyether framework composed of polyethylene glycol and polypropylene glycol and having a terminal amino functional group, and the catalyst can be the organic catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and the method further includes adding the modifying reagent 1,4-butanediol.

[0099] The reaction is carried out at atmospheric pressure (1 atm), however, it can also be carried out at higher or lower pressures. For example, higher pressures can be used to achieve higher temperatures in the presence of a solvent.

[0100] The polymerization can be carried out by means of molding, casting, coating, brown film, and extrusion.

[0101] Therefore, in the present invention, the random copolymerization (urethane-carbonate) can be obtained using the method of the present invention as described above.

[0102] The structure of the random copolymerization (urethane-carbonate) in the examples was confirmed by FT-IR spectroscopy, as Figures 5 to 7 can be seen, which particularly shows the presence of free hydroxyl groups.

[0103] As can be seen from the figure, the FT-IR spectrum of the random copolymerization (urethane-carbonate) of the present invention shows a hydroxyl peak at about 3200 cm -1 .

[0104] As a random copolymer, the monomer residues are randomly located in the polymer molecule (rather than in a block linear arrangement like a block copolymer).

[0105] The resulting isocyanate-free and BPA-free copolymerization (urethane-carbonate) can be seen in Figure 8 which depicts the copolymerization (urethane-carbonate) prepared in a mold from DTMP-DC and diamine (Jeffamine® ED-600) at a ratio of 30 / 5 (according to Example 6).

[0106] As can be seen in Figure 4 the copolymers of the present invention exhibit different properties compared to polycarbonates produced by ROP using DTMP-DC without using polyamines (Comparative Example 2), or polyurethanes produced by ring-opening polymerization using equimolar ratios of DTMP-DC and diamine (Jeffamine® ED-600).

[0107] The Shore D hardness of the copolycarbonate (Comparative Example 2) produced by ROP using DTMP-DC without using polyamines is close to 90 (88.4), while the polyurethane produced by ring-opening polymerization using equimolar ratios of DTMP-DC and diamine (Jeffamine® ED-600) is <1.

[0108] For the copolymers of the present invention, the Shore D hardness is in the range of >1 to 85, for example, in the range of 1 to 80 or 5 to 75. Thus, it can be seen that as the ratio of polyamine is decreased, the Shore D hardness increases from <1 (Example 1) to 15.2 (Example 2), to 28.6 (Example 3), to 70.8 (Example 4), and to 88.4 (Comparative Example 2, no polyamine used).

[0109] For the examples using modifiers, the Shore D hardness can be decreased by increasing the amount of the modifier. The Shore D hardness results show that as the amount of the modifier is increased, the hardness decreases in sequence: 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 ).

[0110] In one aspect of the present invention, the Shore D hardness is in the range of 1 to 85, for example, in the range of 1 to 80.

[0111] Thus, the method of the present invention will result in a tough and resilient random copolymer. Since the copolymer is random, it is easy to obtain a wide range of melting points and sealing initiation temperatures (SIT), and the random copolymer will also exhibit good radiation resistance.

[0112] Furthermore, the glass transition temperature (Tg) will be >50 °C.

[0113] Therefore, the random co-poly(urethane-carbonate) is suitable for a variety of applications, such as articles produced by blow molding, injection molding, or sheet extrusion. Such articles can be films, fibers, or tubes.

[0114] Accordingly, the present invention also relates to the use of the random co-poly(urethane-carbonate) for producing films, articles produced by blow molding or injection molding, fibers, or tubes.

[0115] According to specific but non-limiting embodiments, it has been found that the resulting isocyanate-free and BPA-free random copolymer (urethane-carbonate) has the formula III:

[0116]

[0117] [Formula III]

[0118] Wherein:

[0119] R is selected from the group consisting of oxygen (ether), C1-C20 alkyl ethers, C1-C20 alkyls, C3-C20 ketones, C3-C20 esters, C1 to C20 carbonates;

[0120] R1, R2, and R3 are each independently selected from the group consisting of none, H, C1-C20 alkyls, hydroxyl, C1-C20 hydroxyalkyls, C6-C20 phenyls, C6-C20 phenylalkyls, C3-C20 alkyl carbonyls, C3-C20 carbonyl alkyls, C4-C20 alkoxy carbonyls, C4-C20 alkoxy carbonyl oxys, C2-C20 carboxyls or their derivatives;

[0121] n is at least 1, and for each n, x ranges from 1 to 100,000 and y ranges from 1 to 100,000.

[0122] In this copolymer, the ratio of x to y in the random copolymer (urethane-carbonate) is from 1:99 to 99:1, or from 1:66 to 66:1, or from 30:40 to 30:5 (mole / mole).

[0123] Comparative Examples and Examples

[0124] The present invention will be explained in more detail with reference to the following examples. However, these examples should not be construed as limiting the scope of the present invention.

[0125] The reaction and production were monitored by FT-IR analysis using a Nicolet-iS5 (Thermo Scientific, USA). The Shore D hardness of the resulting material was measured at room temperature using a digital hardness tester (BGD 935 / D, Biuged Laboratory Instruments). The results were taken as the average of five tests performed on multiple areas of the sample.

[0126] In the following examples, the number-average molecular weight of the polymer was determined by gel permeation chromatography (GPC), where tetrahydrofuran was used as the solvent and polystyrene with a known average molecular weight was used as the standard sample. GPC is a size exclusion chromatography (SEC) that typically separates analytes based on size in an organic solvent. This technique is commonly used for the analysis of polymers.

[0127] Comparative Example 1 - Production of isocyanate-free PU from DTMP-DC and diamine (Jeffamine® ED-600)

[0128] Ring-opening polymerization of DTMP-DC with an equimolar amount of polyamine produces PU. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, and then 18 g (equimolar, 30 mmol) of preheated Jeffamin ED-600, which was premixed with 0.25 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C, was added. After 5 minutes, the polymerization was continued at 95 °C for 1 hour and the polymerization was completed. The structure was confirmed by FT-IR ( Figure 5 C), and the Shore D hardness was measured to be <1 ( Figure 4 ).

[0129] Comparative Example 2 - Production of BPA-free PC from DTMP-DC

[0130] Ring-opening polymerization of DTMP-DC produces PC without the need for polyamine. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, and then 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) was added at 110 °C. After 5 minutes, the polymerization was continued at 95 °C for 1 hour and the polymerization was completed. The structure was confirmed by FT-IR ( Figure 5 D), and the Shore D hardness was measured to be 88.4 ( Figure 4 ).

[0131] Figure 5 . FTIR spectra of (A) DTMP-DC, (B) polyamine (Jeffamine® ED-600), (C) polyurethane (Comparative Example 1), and (D) polycarbonate (Comparative Example 2).

[0132] Example 1 - Production of isocyanate-free and BPA-free co-poly(urethane-carbonate) from DTMP-DC and diamine (Jeffamine® ED-600) at a ratio of 30 / 40 (Table 1).

[0133] Since the carbonate group is not sufficient to react with the amine end group, using an excess molar ratio of polyamine to DTMP-DC can catalytically produce shorter isocyanate-free and BPA-free copoly(urethane-carbonate) chains. However, at the same time, some of the carbonate units can be generated by the catalyst. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, and then 24 g (40 mmol) of preheated Jeffamin ED-600 was added, which was mixed with 0.3 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued at 95 °C for 1 hour and the polymerization was completed. The structure was confirmed by FT-IR( Figure 6 A), and the Shore D hardness was measured to be <1( Figure 4 ).

[0134] Example 2 - Production of isocyanate-free and BPA-free copoly(urethane-carbonate) with a random distribution of urethane units / carbonate units in a ratio of 30 / 20 from DTMP-DC and diamine (Jeffamine® ED-600) (Table 1 and Figure 9 ).

[0135] Using a lower molar ratio of polyamine to DTMP-DC can catalytically produce isocyanate-free and BPA-free copoly(urethane-carbonate). The amine group reacts with the cyclic carbonate group, and the latter polymerizes under the action of the catalyst to form a carbonate. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, and then 12 g (20 mmol) of preheated Jeffamin ED-600 was added, which was mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued at 95 °C for 1 hour and the polymerization was completed. The structure was confirmed by FT-IR( Figure 6 B), and the Shore D hardness was measured to be 15.2( Figure 4 ).

[0136] Example 3 - Production of isocyanate-free and BPA-free copoly(urethane-carbonate) from DTMP-DC and diamine (Jeffamine® ED-600) in a ratio of 30 / 10 (Table 1).

[0137] Using a lower molar ratio of polyamine to DTMP-DC can catalytically produce an isocyanate-free and BPA-free co-poly(urethane-carbonate). The amine groups react with the cyclic carbonate groups, which polymerize to form carbonates under the action of a catalyst. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, and then 6 g (10 mmol) of preheated Jeffamin ED-600 was added, which was mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued at 95 °C for 1 hour and the polymerization was completed. The structure was confirmed by FT-IR ( Figure 6 C), and the Shore D hardness was measured to be 28.6( Figure 4 ).

[0138] Example 4 - Production of an isocyanate-free and BPA-free co-poly(urethane-carbonate) (Table 1) from DTMP-DC and diamine (Jeffamine® ED-600) at a ratio of 30 / 5.

[0139] Using a lower molar ratio of polyamine to DTMP-DC can catalytically produce an isocyanate-free and BPA-free co-poly(urethane-carbonate). The amine groups react with the cyclic carbonate groups, which polymerize to form carbonates under the action of a catalyst. As the ratio of the polyamine used is decreased, the carbonate units in the polymer chain can increase. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, and then 3 g (5 mmol) of preheated Jeffamin ED-600 was added, which was mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued at 95 °C for 1 hour and the polymerization was completed. The structure was confirmed by FT-IR ( Figure 6 D), and the Shore D hardness was measured to be 70.8( Figure 4 ). By decreasing the ratio of the polyamine used, the Shore D hardness increased from <1 (Example 1) to 15.2 (Example 2), to 28.6 (Example 3), to 70.8 (Example 4), and to 88.4 (Comparative Example 2, no polyamine used).

[0140] Figure 6. FTIR spectra of (A) isocyanate-free and BPA-free co-poly(urethane-carbonate) (Example 1), (B) isocyanate-free and BPA-free co-poly(urethane-carbonate) (Example 2), (C) isocyanate-free and BPA-free co-poly(urethane-carbonate) (Example 3), and (D) isocyanate-free and BPA-free co-poly(urethane-carbonate) (Example 4).

[0141] Examples 5 - 7 - Isocyanate-free and BPA-free co-poly(urethane-carbonate) was produced from DTMP-DC and diamine (Jeffamine® Ed-600) at a ratio of 30 / 5 under the action of modifiers (1,4-butanediol at 1 g, 2 g, and 3 g respectively) (Table 1).

[0142] In addition, the polymer can be further modified by modifiers. Modifiers can play a role in controlling properties and properly mixing monomers in the process. For example, the use of 1,4-butanediol can form ester units in the polymer chain or at the end groups. According to Example 4 above, 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, then 1 g of 1,4-butanediol and 3 g (5 mmol) of preheated Jeffamin ED-600 were added, and it was mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued at 95 °C for 1 hour and the polymerization was completed. 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 ). In addition, the Shore D hardness results show that with the increase in the amount of modifier, the hardness decreases in turn: 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 ).

[0143] Figure 7 . FTIR spectra of (A) isocyanate-free and BPA-free co-poly(urethane-carbonate) with 1 g modifier (Example 5), (B) isocyanate-free and BPA-free co-poly(urethane-carbonate) with 2 g modifier (Example 6), and (C) isocyanate-free and BPA-free co-poly(urethane-carbonate) with 3 g modifier (Example 7).

[0144] Example 8 - In-situ forming and producing isocyanate-free and BPA-free co-poly(urethane-carbonate) from DTMP-DC and diamine (Jeffamine® ED-600) at a ratio of 30 / 5 (Table 1).

[0145] For Example 4, the polymerization can be carried out in a mold. 9.1 g (30 mmol) of DTMP-DC was melted in a 50 mL reaction vessel at 110 °C, and then 3 g (5 mmol) of preheated Jeffamin ED-600 was added, which was mixed with 0.2 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued in the mold at 95 °C for 1 hour and the polymerization was completed ( Figure 8 ).

[0146] Figure 8 . Picture of the isocyanate-free and BPA-free copolymer (urethane-carbonate) prepared from DTMP-DC and diamine (Jeffamine® ED-600) in a 30 / 5 ratio in a mold (Example 6).

[0147] Although the present invention has been described above in connection with one or more specific embodiments, it is not intended to be limited to the specific forms described herein. On the contrary, the present invention is only limited by the appended claims, and other embodiments, such as those different from the above-described embodiments, may also fall within the scope of the appended claims.

[0148] In the claims, the term "comprising" does not exclude the presence of other elements or steps. Further, although listed separately, multiple devices, elements or method steps may be implemented. In addition, although individual features may be included in different claims, these features may be advantageously combined, and inclusion in different claims does not mean that the combination of features is not feasible and / or not advantageous. In addition, a single reference does not exclude a plurality. The terms "a", "an", "first", "second", etc. do not exclude a plurality. The reference signs in the claims are provided only as illustrative examples and should not be construed as limiting the scope of the claims in any way.

[0149] References

[0150] [1] Pyo, S.H., Persson, P., Mollaahmad, M.A., Sörensen, K., Lundmark,S., and Hatti-Kaul, R., 2011. Cyclic carbonates as monomers for phosgene-and isocyanate-free polyurethanes and polycarbonates (Cyclic carbonates as monomers for phosgene-and isocyanate-free polyurethanes and polycarbonates). Pure and Applied Chemistry (Pure and Applied Chemistry), 84(3), pp.637-661.

[0151] [2] Wang, P., Park, J.H., Sayed, M., Chang, T.S., Moran, A., Chen, S., and Pyo, S.H., 2018. Sustainable synthesis and characterization of a bisphenol A-free polycarbonate from a six-membered dicyclic carbonate (Sustainable synthesis and characterization of a bisphenol A-free polycarbonate from a six-membered dicyclic carbonate). Polymer chemistry (Polymer chemistry), 9(27), pp.3798-3807.

[0152] [3] Carré, C., Ecochard, Y., Caillol, S., and Avérous, L., 2019. From the synthesis of biobased cyclic carbonate to polyhydroxyurethanes: A promising route towards renewable NonIsocyanate Polyurethanes (From the synthesis of biobased cyclic carbonate to polyhydroxyurethanes: A promising route towards renewable NonIsocyanate Polyurethanes). ChemSusChem, 12(15), pp.3410-3430.

[0153] [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. A method for preparing a random copolymer (urethane - carbonate), the method comprising: In the presence of a catalyst, by heating a mixture of a 6-membered bicyclic carbonate according to formula I, a polyamine, and a catalyst, via catalytically controlled ring-opening polymerization (ROP) for carbonate unit formation, the 6-membered bicyclic carbonate reacts with the polyamine through a ring-opening polymerization reaction to obtain a random copolymer (urethane-carbonate). (I) Wherein: 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; R1 and R2 are each independently selected from the group consisting of: H, C1-C20 alkyl, hydroxy, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl or derivatives thereof.

2. The method according to claim 1, wherein the 6-membered bicyclic carbonate is a bicyclic carbonate according to formula II: (II) 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 C1-C20 alkylene; R1 and R2 are each independently selected from the group consisting of: H, C1-C20 alkyl, hydroxy, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxycarbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl or derivatives thereof.

3. The method according to any one of claims 1 to 2, wherein the molar ratio of the polyamine to the 6-membered bicyclic 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 0.1:1, or 0.2:1 to 1:2, or from 1:0.01, or 1:0.1, or 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 0.3:1 to 0.9:

1.

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

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

6. The method according to any one of claims 1 to 5, wherein a mixture of more than one type of 6-membered bicyclic carbonate is used.

7. The method according to 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; biobased diamines such as amine derivatives of dimer fatty acids; and polymeric diamines, triamines, and polyamines such as block copolymers having a polyether framework composed of polyethylene glycol and polypropylene glycol and having terminal amino functional groups.

8. The method according to claim 7, wherein the polyamine is a block copolymer having a polyether framework composed of polyethylene glycol and polypropylene glycol and having terminal amino functional groups.

9. The method according to any one of claims 1 to 8, wherein a mixture of more than one type of polyamine is used.

10. The method according to any one of claims 1 to 9, wherein the catalyst is an inorganic catalyst, an organometallic catalyst, or an organic catalyst.

11. The method according to any one of claims 1 to 10, wherein: the inorganic catalyst and the organometallic catalyst are selected from the group comprising skilled systems based on metal centers such as sodium, potassium, zinc, magnesium, calcium, tin, titanium, cesium, or rare earth metals and carrying suitable auxiliary 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-diazaphospholane], amidines (1,8-diazabicycloundec-7-ene), tertiary amines (dimethyl ethanolamine), N-heterocyclic carbenes, and bifunctional thiourea-tertiary amine catalysts.

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

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

14. The method according to 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, such as from 30 minutes to 2 hours.

15. The method according to any one of claims 1 to 14, wherein the method further comprises adding a modifying reagent.

16. The method according to claim 15, wherein the weight ratio of the modifying reagent to the bicyclic carbonate is the following ratio: from 0.0001:1 to 1:1 (weight:weight), such as from 0.0001:1, or 0.001:1, or 0.01:1, or 0.1:1 to 1:1, or preferably from 0.001:1 to 0.3:1 (weight:weight).

17. The method according to any one of claims 15 to 16, wherein the modifying reagent is an alcohol such as benzyl alcohol, 1,3-propanediol, glycerol, and / or 1-propanol.

18. The method according to any one of claims 15 to 16, wherein the modifying reagent is 1,4-butanediol.

19. The method according to any one of claims 1 to 18, wherein: the molar ratio of the polyamine to the bicyclic carbonate used is 0.3:1 to 0.9:1, the 6-membered bicyclic carbonate is ditrimethylolpropane bicyclic carbonate (DTMP-DC), the polyamine is a block copolymer having a polyether framework composed of polyethylene glycol and polypropylene glycol and having a terminal amino functional group, and the catalyst is an organic catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and wherein the method further comprises adding a modifying reagent, and wherein the modifying reagent is 1,4-butanediol.

20. The method according to any one of claims 1 to 19, the method further comprising a melting step, wherein the 6-membered bicyclic carbonate is melted, preferably before adding the polyamine and the catalyst.

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

22. The method according to any one of claims 20 to 21, wherein the melting temperature of the melting step is at least as high as the melting point of the 6-membered bicyclic carbonate.

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

24. The method according to any one of claims 1 to 23, wherein the reaction is carried out in a solution, wherein the solution contains an organic solvent selected from alcohols, cyclic ethers, ketones, toluene, acetonitrile, haloalkanes, dimethylformamide and pyridine, or a mixture thereof.

25. The method according to claim 24, wherein: 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 haloalkane is selected from dichloromethane and chloroform.

26. The method according to any one of claims 1 to 25, wherein the polymerization is carried out by molding, casting, coating, calendaring or extrusion.

27. An atactic copolymer (urethane-carbonate), the atactic copolymer (urethane-carbonate) obtainable by the method according to any one of claims 1 to 26.

28. The atactic copolymer (urethane-carbonate) according to claim 27, wherein the Shore D hardness is less than 85, for example in the range of 1 to 80.

29. The random copolymer (urethane - carbonate) according to any one of claims 27 to 28, wherein the FT - IR spectrum of the random copolymer (urethane - carbonate) shows a hydroxyl peak at about 3200 cm -1 -1.

30. The atactic copolymer (urethane-carbonate) according to any one of claims 27 to 29, wherein the atactic copolymer (urethane-carbonate) is free of isocyanate and BPA.

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

32. Use of the atactic copolymer (urethane-carbonate) according to any one of claims 27 to 31 for the production of films, articles made by blow molding or injection molding, fibers or tubes.

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