Bpa-free random co-poly(hydroxycarbonate)

Abstract

The invention pertains to a process for preparing a random co- poly(hydroxycarbonate) comprising reacting a 6-membered di-cyclic carbonate with a polyol, or a monohydric alcohol, via a ring-opening polymerization (ROP) by catalytic control for carbonate unit formation, in the presence of a catalyst, through a ring- opening polymerization reaction. Also, the invention pertains to a random co- poly(hydroxycarbonate) being obtainable by said process

Description

[0001] BPA-FREE RANDOM CO-POL Y(HYDROXYCARBONATE)

[0002] Field of the Invention

[0003] The invention belongs to the technical field of polymer synthesis, in particular to the field of manufacture of BPA-free copolymers via ring-opening polymerization and the resulting co-polymers.

[0004] Background of the Invention

[0005] Polycarbonates have been used for a wide range of applications from automotive parts to electronic appliances, and are obtained from aromatic or aliphatic dioxy-compounds by means of a carbonate.

[0006] The main polycarbonate material is obtained from polymerization of 2,2-bis(4- hydroxyphenyl)propane (bisphenol A) with toxic phosgene or diphenylcarbonate, which is derived from reaction of phenol with phosgene, and the product requires high purity without the presence of chlorinated impurities. However, the main raw material, BPA shows estrogenic properties, and the release of BPA from polycarbonates has been studied on exposure and risk assessments in a large number of studies, because of the widespread use of polycarbonates in food and drink packaging, such as food cans, bottle caps, water supply pipes, and dental sealants and tooth coatings.

[0007] It is known that cyclic carbonates have attracted attention in recent years as potential monomers for the production of polyurethanes, polycarbonates and copolymers through phosgene- and isocyanate-free route [1],

[0008] Attempts have been made to develop routes to make BPA-free PC, and one way of getting around these toxic raw materials is to produce the polymers by ringopening polymerization (ROP) of cyclic carbonates [1,2,3].

[0009] Methods starting from five-membered alkylene carbonates as cyclic carbonates are one option. Five-membered alkylene carbonates have been considered to a less extent for commercial use owing to thermodynamic properties in the ROP, while sixmembered cyclic carbonates provide more opportunities to be used in the polymerization. The 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. The polymerization involves partial decarboxylation and the loss of CO2 such that the polymer produced contains both carbonate and ether linkages. Six-membered cyclic carbonates are thermodynamically more suitable precursors, however their production has not been straightforward, and the monomers are not commercially available. Thus, there is a need for the development of novel manufacturing methods for producing isocyanate-free and BPA-free polycarbonates.

[0010] Summary of the Invention

[0011] Accordingly, the present invention preferably seeks to mitigate, alleviate or eliminate one or more of the above-identified deficiencies in the art and disadvantages singly or in any combination and solves at least the above mentioned problems by providing a process for preparing a random co-poly(hydroxycarbonate) comprising reacting a 6-membered di-cyclic carbonate with a polyol, or a monohydric alcohol, via a ring-opening polymerization (ROP) by catalytic control for carbonate unit formation, in the presence of a catalyst, through a ring-opening polymerization reaction, by heating up a mixture of a 6-membered di-cyclic carbonate according to formula I, a polyol, or a monohydric alcohol, and a catalyst, to obtain a random co- poly(hydroxy carbonate) wherein; R is selected from the group consisting of oxygen (ether), C1-C20 dialkyl, C1-C20 alkylether, C1-C20 ketone, C1-C20 ester; Ri and R2, are independently of each other, 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 their derivatives.

[0012] Also provided is a process, wherein the 6-membered di-cyclic carbonate is a compound according to formula (II) wherein; R3 is selected from the group consisting of oxygen, C(O), OC(O), and C(O)O; R4 and R5, are independently of each other C1-C20 alkylene; Ri and R2, are independently of each other, selected from the group consisting ofH, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3-C20 alkylcarbonyl, C3-C20 carbonylalkyl, C4-C20 alkoxy carbonyl, C4-C20 alkoxy carbonyl oxy, C2-C20 carboxyl group or their derivatives.

[0013] Further is provided the process wherein the 6-membered di-cyclic carbonate is reacted with a polyol according to formula III, wherein; Re is selected from the group consisting of C1-C20 alkylene, such as C2 to C6 alkylene, C1-C20 hydroxyalkylene, C1-C20 dihydroxyalkylene, C5-C7 cycloalkylene, C1-C20 hydroxyalkylene, phenylene, Cl -CIO alkylene-phenylene-CO- C10 alkylene, Cl -CIO alkylene-C(O)-Cl-C10 alkylene, C1-C10C alkylene-C(O)O- Cl- C10C alkylene, or their derivatives; preferably Re being selected from the group consisting of C1-C20 alkylene, such as C2 to C6 alkylene, C1-C20 hydroxyalkylene, and C1-C20 dihydroxyalkylene; more preferably the polyol according to formula II being selected from the group consisting of 1,3 -propanediol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol; even more preferably the polyol according to formula II being selected from the group consisting of 1,3 -propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; or wherein the 6-membered di-cyclic carbonate is reacted with a monohydric Cl -CIO alcohol, such as a monohydric alcohol selected from the group consisting of methanol, ethanol, propanol, such as n-propanol, butanol, such as n-butanol, pentanol, such as n- pentanol, and hexanol, such as n-hexanol.

[0014] Also is provided the process wherein in formula I: R is oxygen; R4 and Rs is methylene; and Ri and R2, are independently of each other, selected from the group consisting of H, ethyl, or hydroxymethyl; preferably Ri and R2 both being ethyl.

[0015] Further is provided a random co-poly(hydroxycarbonate), said random co- poly(hydroxy carbonate) being obtainable by the process.

[0016] Further, for the random co-poly(hydroxy carbonate), an FT-IR spectra of the random co-poly(hydroxycarbonate) shows a hydroxyl peak at between 3000 to 3700 cm-1.

[0017] Further, an article comprising the random co-poly(hydroxycarbonate), wherein the article has been produced by blow moulding, injection moulding or sheet extrusion.

[0018] Also, a fdm, fibre or a pipe comprising a random co-poly(hydroxycarbonate). Further, the use of a random co-poly(hydroxy carbonate) for the production of a film, an article by blow moulding or injection moulding, a fibre or a pipe.

[0019] Brief Description of the Drawings

[0020] These and other aspects, features and advantages of which the invention is capable of will be apparent and elucidated from the following description of embodiments of the present invention, reference being made to the accompanying drawings, in which

[0021] Fig- 1 shows an example of a reaction overview of (A) a random polymerization process of the invention to produce BPA-free random co- poly(hydroxycarbonate) from dicyclic carbonates with polyol at a certain molar ratios. (B) shows a comparison example to produce polycarbonate from six-membered dicyclic carbonates without polyol;

[0022] Fig- 2 shows an example of a BPA-free random co-poly(hydroxy carbonate) according to one embodiment of the invention;

[0023] Fig- 3 shows an example of a random co-poly(hydroxycarbonate), prepared from Di-trimethylolpropane di-cyclic carbonate (DTMP-DC) and 1,4-butanediol (1,4- BDO), wherein x and y are random in the polymer chain (not sequentially repeating on the chain) according to one embodiment;

[0024] Fig. 4 shows a table summarizing examples and comparisons on the polymerization of Di-trimethylolpropane di-cyclic carbonate (DTMP-DC) with polyol at different ratios (%, mmol / mmol). Cat.: l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU);

[0025] Fig. 5 shows Shore D hardness of BPA-free polycarbonate (comparison 1), and BPA-free random co-poly (hydroxycarbonate)s (example 1-7);

[0026] Fig. 6 shows a FTIR spectra of (A) DTMP-DC, (B) Polycarbonate (comparison i);

[0027] Fig. shows an FTIR spectra of BPA-free random co-poly(hydroxy carbonate) (example 1);

[0028] Fig. 8 shows an FTIR spectra of BPA-free random co-poly(hydroxy carbonate) (example 2);

[0029] Fig. 9 shows an FTIR spectra of BPA-free random co-poly(hydroxy carbonate) (example 3),

[0030] Fig. 10 shows an FTIR spectra of BPA-free random co- poly(hydroxy carbonate) (example 4); Fig. 11 shows an FTIR spectra of BPA-free random co-poly(hydroxy carbonate) (example 5);

[0031] Fig. 12 shows an FTIR spectra of BPA-free random co- poly(hydroxycarbonate) (example 6);

[0032] Fig. 13 shows an FTIR spectra of BPA-free random co- poly(hydroxycarbonate) (example 7); and

[0033] Fig. 14 shows a picture of BPA-free random co-poly(hydroxycarbonate) from DTMP-DC and 1,4-butanediol at ratio of at ratio of 61% (mol / mol) (example 8).

[0034] Description of embodiments

[0035] The following description focuses on an embodiment of the present invention applicable to a method of manufacturing BPA-free co-poly(hydroxycarbonate)s via the ring-opening polymerization of di-cyclic carbonate with polyol at different ratios of di- cyclic carbonate and polyol under catalytic control for formation of different carbonate units (Fig. 1 A). Hydroxyl group can be formed from cyclic carbonate, or remained from polyol without participation in polymerization.

[0036] Attempts have been made to develop routes to make BPA-free PC, and one way of getting around these toxic raw materials is to produce the polymers by ringopening polymerization (ROP) of cyclic carbonates [1,2,3]. Five-membered alkylene carbonates have been considered to a less extent for commercial use owing to thermodynamic properties in the ROP. The 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 acetyl acetonates, and metal alkyls. The polymerization involves partial decarboxylation and the loss of CO2 such that the polymer produced contains both carbonate and ether linkages.

[0037] The reactivity of five- and six-membered cyclic carbonates substituted with allyl and homoallyl groups, 5-(2-propenyl)-l,3-dioxan-2-one and 4-(3-butenyl)-l,3- dioxolan-2-one with hexylamine and benzylamine was compared [4], The reaction rate of the six-membered cyclic carbonate at 30 - 70 °C was 29 to 62 times larger than those of the five-membered one. Thus, six-membered cyclic carbonates seem to provide more opportunities to be used in the polymerization. Although six-membered cyclic carbonates are thermodynamically more suitable precursors, their production has not been straightforward and the monomers are not readily commercially available. In the invention, it was found that di-cyclic carbonate can be used to manufacture BPA-free co-poly(hydroxycarbonate)s via the ring-opening polymerization with polyl at different ratio of di-cyclic carbonate and polyol under catalytic control (illustrated in Fig. 1 A). This is a mild environment-friendly process without using phosgene, other chlorinated materials, and bisphenol.

[0038] Cyclic carbonate can be ring-opened without polyol to polycarbonate in the presence of catalyst. Theoretically, the resulting polycarbonate do not contain hydroxyl group in the molecule, and may be long-chain polymer. Meanwhile, the polymerization of cyclic carbonate with polyol can produce random co-polycarbonate having hydroxyl group in the molecule. Therefore, in the invention, a ratio of polyl to di-cyclic carbonate is used to control the ratio of units in the co-poly(hydroxycarbonate)s.

[0039] It was found that the random co-polymers resulting from the reaction using both di-cyclic carbonate and polyol were novel materials having unique properties and structures, and that the ratio of polyol to di-cyclic carbonate in the production process can be used to control their properties.

[0040] The carbonate unites can be formed from ROP of cyclic carbonate with and without participation of polyol as random repeating unit of carbonate in the molecule. Hydroxyl group can be formed from cyclic carbonate, or remained from one of hydroxyl group in polyol without participation in polymerization.

[0041] Mono-cyclic carbonate with polyol may be limited on the physical properties since degree of polymerization may be not high by termination with formation of hydroxyl group. Meanwhile, di-cyclic carbonate with polyol can form networked co- poly(hydroxy carbonate) having hydroxyl group. The degree of hydroxyl group can be depended on the ratio of polyol to cyclic carbonate. Therefore the ratio of polyol can control the ratio of carbonate unites and degree of hydroxyl group, thus the physical properties of the resulting random co-poly(hydroxycarbonate)s can be controlled. The resulting co-poly(hydroxycarbonate)s can be relatively hydrophilic due to the hydroxyl group, depending the degree of hydroxyl group.

[0042] As a the random co-poly(hydroxycarbonate) may comprise a free hydroxyl group, a FT-IR spectra of the random co-poly(hydroxycarbonate) may show a hydroxyl peak at between 3000 to 3700 cm'1.

[0043] A mono-alcohol can be used instead of a polyol. Using of a mono-alcohol blocks polymerization over the diol, and results in a polymer as can be seen in Figure X and Example 7. Alcohols may be Monohydric alcohols, straight-chained or branched- chain, unsaturated aliphatic alcohols or aromatic alcohols. Examples of alcohols are 1- butanol or benzyl alcohol.

[0044] In order to achieve the above objective, there is according to an aspect provided a process for preparing a random co-poly (hydroxy carbonate). The process comprises polymerisation of a 6-membered di-cyclic carbonate with a polyol, or a monohydric alcohol, via a ring-opening polymerization by catalytic control for carbonate unit formation, in the presence of a catalyst. The process may be a multistage process. The process may comprise the steps of: providing a 6-membered di-cyclic carbonate, adding a polyol and a catalyst, and heating the resulting mixture to obtain the random co-poly(hydroxycarbonate) through a polymerization reaction.

[0045] More specifically, the process comprises heating up a mixture of a 6-membered di-cyclic carbonate according to formula I, a polyol, or a monohydric alcohol, and a catalyst, to obtain a random co-poly (hydroxycaronate):

[0046] Here, R is selected from the group consisting of oxygen (ether), C1-C20 dialkyl, C1-C20 alkylether, C1-C20 ketone, C1-C20 ester; Ri and R2, are independently of each other, 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 their derivatives.

[0047] The 6-membered di-cyclic carbonate may also be a compound according to formula (II)

[0048] Here, R3 is selected from the group consisting of a direct bond, oxygen, C(O), OC(O), and C(O)O; R4 and R5, are independently of each other C1-C20 alkylene; Ri and R2, are independently of each other, 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 alkoxy carbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group or their derivatives.

[0049] Further, the 6-membered di-cyclic carbonate may be reacted with a polyol according to formula III,

[0050] Here, Re is selected from the group consisting of C1-C20 alkylene, such as C2 to C6 alkylene, C1-C20 hydroxyalkylene, C1-C20 dihydroxyalkylene, C5-C7 cycloalkylene, C1-C20 hydroxyalkylene, phenylene, Cl -CIO alkylene-phenylene-CO- C10 alkylene, Cl -CIO alkylene-C(O)-Cl-C10 alkylene, C1-C10C alkylene-C(O)O-Cl- C10C alkylene, or their derivatives; preferably Re being selected from the group consisting of C1-C20 alkylene, such as C2 to C6 alkylene, C1-C20 hydroxyalkylene, and C1-C20 dihydroxyalkylene. More preferably the polyol according to formula II being selected from the group consisting of 1,3 -propanediol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol. Even more preferably the polyol according to formula II being selected from the group consisting of 1,3 -propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Or, the 6-membered di-cyclic carbonate is reacted with a monohydric C1-C10 alcohol, such as a monohydric alcohol selected from the group consisting of methanol, ethanol, propanol, such as n-propanol, butanol, such as n-butanol, pentanol, such as n-pentanol, and hexanol, such as n-hexanol.

[0051] Also, in formula I: R may be oxygen; R4 and Rs may be methylene; and Ri and R2, may, independently of each other, be selected from the group consisting of H, ethyl, or hydroxymethyl; preferably Ri and R2 both being ethyl.

[0052] In the process, the six-membered di-cyclic carbonate may be ditrimethylolpropane di-cyclic carbonate (DTMP-DC), pentaerythritol dicarbonate (PE- DC) or combinations thereof. DTMO and PE are both well-known commercial products making the invention readily available for use. Preferably the 6-membered di-cyclic carbonate is di-trimethylolpropane di-cyclic carbonate (DTMP-DC).

[0053] In the process, a mixture of more than one type of 6-membered di-cyclic carbonate may be used. The alcohol may be a linear or cyclic alcohol, such as mono-alcohol of alkyl and aryl compounds; and the polyol is a linear or cyclic polyol, such as di-, tri-, polyalcohol of alkyl and aryl compounds.

[0054] Examples of such polyols are 1,4-butanediol, 1,3 -propanediol, 1,5 -pentanediol, 1,6-hexanediol, 1,6-hexanediol, Pripol® (Croda), trimethylolpropane, glycerol, dihydroxybenzen, 2-benzyl-l,3-propanediol, ethylenglycol, 2,2,4,4-tetramethyl 1,3- cyclobutanediol, and 1,4-cyclohexanedimethanol.

[0055] The Pripol® (Croda) may be the Pripol 2033 by CRODA, having the formula

[0056] A mono-alcohol may be used instead of a polyol, such as 1 -butanol or benzyl alcohol.

[0057] In the process, a mixture of more than one type of polyol, or a monohydric alcohol, may be used.

[0058] The reaction may also comprise the addition of a modifying agent.

[0059] The modifying agent can play roles to control property and to properly mix monomers in the process. One such example is that organocatalysts can be used in the presence of an alcohol. The alcohol acts as a co-initiator, a chain-transfer and a modifier agent, and can be used with catalysts. These agents can play roles to control property and to properly mix monomers in the process.

[0060] The weight ratio of modifying agent to di-cyclic carbonate is not limited, but the ratio can preferably be used at a ratio of 0.0001 : 1 to 1 : 1, such as from 0.0001, or 0.001, or 0.01, or 0.1 to 1:1, preferably 0.001: 1 to 0.3:1 (wt:wt).

[0061] The weight ratio of modifying agent to di-cyclic carbonate may also be expressed as a percentage of from such as 0.01 to 100 wt% such as 0.01, 0.1, 1, 10 and 100 wt%, or even more preferred 0.1 to 30 wt%.

[0062] The modifying agent may be a monohydric alkohol, such as benzyl alcohol.

[0063] For the reaction to result in a random co-polymer, the weight ratio of polyol to di-cyclic carbonate is not limited, 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 0.11 :1, or 0.21 : 1 to 1:0.25 (wt:wt), such as from 0.21:1, or 0.25:1 to 1 :2, or even more preferably from 0.25:1 to 1 : 1 or 0.3:1 to 0.9:1 (wt:wt).

[0064] The weight ratio of polyol to di-cyclic carbonate may also be expressed as a percentage of from 1 wt%, or 11 wt%, or 21 wt% to 200 wt% such as 21, 30, 50, 100 and 200 wt%, or even more preferred 21 to 100 wt%, or even more preferred 30 to 90 wt%.

[0065] The polyol to di-cyclic carbonate may be at a non-equivalent molar ratio. This to promote formation of a random copolymer.

[0066] The ratio of polyol to di-cyclic carbonate may thus be expressed as a molar ratio, such as a range from 0.01-0.99:1 to 1:0.99-0.01, such as from 0.1-0.9: 1 to 1:0.1- 0.9, such as from 0.2-0 8:1 to 1:0.8-0.2, or from 0.3-0.8:1 to 1 :0.8-0.3 (mobmol).

[0067] A mixture of di-cyclic carbonates, mixture of di-cyclic carbonate with mono- cyclic carbonate, and mixture of polyols can be used for the polymerization, respectively. In one example of the invention, di-cyclic carbonates are used in the method of the invention. In one further example, a mixture of di-cyclic carbonate with mono-cyclic carbonate is used.

[0068] The polymerization temperature is selected according to different monomers and initiators and required requirements. The polymerization temperature may be at least 0°C, such as at least 30°C, such as at least 60°C, such as at least 100°C, at least 140°C, or at least 180°C.

[0069] By having a polymerization temperature of at least 80 °C, such as 80 to 180 °C, the resulting material will be strong and elastic, as shown by the compound properties of the co-polymers of examples 1 to 8, where the polymerization temperature was 95 degrees. In one example, the polymerization temperature of at least 80 °C, such as 80 to 180 °C, is used.

[0070] The polymerization reaction time for the ring-opening polymerization reaction may be from 1 minute to 24 hours, such as from 20 minutes to 3 hours, such as from 30 minutes to 2 hours, for example 1 hour. In Examples 1-8, the duration of the polymerization reaction was 1 hour.

[0071] The process may include a melting step, wherein the 6-membered di-cyclic carbonate is melted before the addition of polyol and a catalyst.

[0072] Alternatively, the melting step takes place after the addition of the polyol and / or catalyst.

[0073] The temperature in the melting step may be at least 0°C, such as at least 30 °C, such as at least 60°C, such as at least 100°C, at least 140°C, or at least 180°C.

[0074] Preferably, the temperature in the melting step at least corresponds to the melting point of the 6-membered di-cyclic carbonate. In examples 1 to 8, the melting temperature was 105 °C for the co-carbonate DTMP-DC. The melting temperature may also be slightly higher than the melting point of the 6-membered di-cyclic carbonate, such as 5, 10, 15, 20 or 50 degrees higher than the melting point of the 6-membered di- cyclic carbonate.

[0075] The duration of the melting step may be from 30 seconds to 60 minutes, depending on the amount of material, but is preferably 1 to 30 minutes, such as 2 to 15 minutes, for example 5 minutes. In Examples 1-8, the melting step was 5 minutes.

[0076] One advantage of melting the 6-membered di-cyclic carbonate is that the often solid form 6-membered di-cyclic carbonate will mix much more efficient with the polyamine and a catalyst (which are often in liquid form) if melted. This is especially beneficial when the reaction takes place in a solution-free environment. Having the reaction take place in a solution-free environment makes it a mild environment-friendly process.

[0077] The method may thus be solvent-free (wherein the reaction is performed without addition of any solvent).

[0078] The reaction and application may however also be performed in solution form and any organic solvent may be used, although this is not necessary for the reaction.

[0079] According to an alternative embodiment, a solvent is used. Preferred solvents are organic solvent being selected from alcohols (e.g. methanol, ethanol and propanol), cyclic ethers (e.g. diethyl ether and THF), ketones (e.g. acetone, ethylmethylketone), toluene, acetonitrile, halogenated alkane (di chloromethane and chloroform), dimethylformamide, and pyridine or mixtures thereof. Use of solvents may provide benefits for homogenization, polymerization and application.

[0080] The catalyst in the process may be a heterogeneous or homogeneous catalyst. The catalyst in the process may be an inorganic catalyst, an organometallic catalyst or an organocatalyst.

[0081] An inorganic and organometallic catalyst can be selected from various proficient systems based on metal centers, such as sodium, potassium, zinc, magnesium, calcium, tin, titanium, caesium or rare-earth metals, bearing suitable ancillary ligands.

[0082] Metal-based catalysts have high catalytic efficiency but can lead to metal pollution in the product, which may impact on the application of the polymer in the field of biomedicine. Therefore, it may be beneficial to use organic catalysts.

[0083] Organocatalysts can be used to lead ROP of dicyclic carbonates, and include commercially available amine (such as 4-N,N-dimethylaminopyridine), guanidines (such as l,5,7-triazabicyclo-[4.4.0]dec-5-ene), phosphazene (such as 2-tert-butylimino- 2-diethylamino-l,3-dimethylperhydro-l,3,2-diazaphosphorine), amidine (such as 1,8- Diazabicycloundec-7-ene), tertiary amines (such as dimethylethanolamine), N- heterocyclic carbenes, and bifunctional thiourea-tertiary amine catalysts.

[0084] In one example, the catalyst is the organocatalyst 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU). This is for instance the case in Examples 1-8.

[0085] The weight ratio of catalyst to used di-cyclic carbonate is not limited. Preferably, the weight ratio of catalyst to used di-cyclic carbonate is from 0.000001:1 to 1:1, such as from 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 from 0.0001 to 1 :1 (wt:wt).

[0086] The weight ratio of catalyst to used di-cyclic carbonate may also be expressed as a percentage of from such as 0.0001, 0.001, 0.01, 0.1, 1, 10 and 100 wt%, or even more preferred 0.01 to 1 wt%.

[0087] It was found that when the amount of catalyst is too small, the polymerization reaction would cross-link to form a gel in a short time, while a too large amount of inhibitor the crosslinking will be inhomogeneous.

[0088] Thus, in one preferred example, the weight ratio of catalyst to used di-cyclic carbonate is from 0.0001 : 1 to 1:1 (wt:wt), 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 (wt:wt).

[0089] The reaction was performed under normal pressure (1 atm), however, it may also be performed under higher or lower pressure, for instance a higher pressure may be used to allow for higher temperatures in the presence of solvents.

[0090] The polymerization can be performed by means of molding, casting, coating, brown film or extrusion.

[0091] Thus, in the invention, a random co-poly(hydroxy carbonate) may be obtained using the process of the invention as described above.

[0092] The structure of the random co-poly(hydroxy-carbonate)s in the Examples were confirmed by FT-IR spectras, as can be seen in figures 6 to 13, showing inter alia the presence of a free hydroxyl group.

[0093] As seen, an FT-IR spectra of the random co-poly (hydroxy carbonate) shows a hydroxyl peak at between 3000 to 3700 cm'1.

[0094] Also, an illustration of the formula for a random co-poly(hdroxycarbonate) prepared from Di-trimethylolpropane di-cyclic carbonate (DTMP-DC) and 1,4- butanediol (1,4-BDO), wherein x and y are random in the polymer chain, is shown in figure 4. The resulting BPA-free co-poly(hydroxy carbonate) material can be seen in figure 14, which depicts the co-poly(hydroxy carbonate) prepared from DTMP-DC and

[0095] 1,4-butanediol at ratio of 33 / 61 in molder (according to example 8).

[0096] As can be seen in figure 5, the co-polymer of the invention obtain different properties from polycarbonate produced using ROP of DTMP-DC without polyol (Comparison 1).

[0097] The Shore D hardness of the polycarbonate (Comparison 1) was 90. For the Examples supplied of the random co-polymers of the invention, the shore D hardness is in the range of 1 to 85. In examples 1 to 8, the shore hardness is between 3 to 78, and excluding Example 3, in the range from 62 to 78. It follows that by increasing the amount of polyol used, the Shore D hardness may de decreased.

[0098] In example 3, it was found that a DTMP-DC to 1,4-butanediol ratio of 91% (mol / mol) resulted in a shore D hardness of as low as 2.8. However, a DTMP-DC to

[0099] 1.4-butanediol ratio of 61% (mol / mol) in Example 2 resulted in a shore D hardness of 69.6 and a DTMP-DC to 1,4-butanediol ratio of 31% (mol / mol) in Example 1 a Shore D hardness of 77.8.

[0100] Thus, the material properties such as shore D hardness can be adjusted by changing the ratio of polyol to di-cyclic carbonate, to optimize the material properties for the intended use or application (as can be seen in figure 4, and Examples 1 to 3).

[0101] In one aspect of the invention, the shore D hardness is from is in the range of 1 to 85, or less than 80, such as in the range from 3 to 78, such as in the range of 62 to 78.

[0102] The material properties can also be adjusted through the selection of alcohol or polyol. In Examples one to 8, 1,4-butanediol (1,4-BDO), 1,3 -propanediol (1,3-PDO),

[0103] 1.5 -pentanediol (1,5-PtDO), 1,6-hexanediol (1,6-HDO), 1-Butanol are used, and the change in properties with relation to shore D hardness is shown in figure 4.

[0104] Thus, the method of the invention will lead to a strong and resilient random copolymer. The co-polymer being random, it is also easy to obtain a broad range of melting point and seal initiation temperature (SIT), and the random co-polymers will also achieve good radiation resistance.

[0105] Thus, the random co-poly(hydroxycarbonate) is suitable for many applications, such as articles produced by blow moulding, injection moulding or sheet extrusion. Such articles may be a film, fibre or a pipe.

[0106] The invention thus also pertains to the use of a random co- poly(hydroxycarbonate) according for the production of a film, of an article by blow moulding or injection moulding, of a fibre or of a pipe. According to a specific but non-limiting embodiment of the invention, a resulting BPA-free random co-poly(hydroxycarbonate) was found to have the having the formula IV:

[0107] [Formula IV] wherein

[0108] R is selected from the group consisting of oxygen (ether), C1-C20 alkyl, C3- C20 ketone, C3-C20 ester;

[0109] Ri, 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 their derivatives;

[0110] The integer “n” is at least 1, and for each n, the integer “x” is from 1 to 100000 and the integer “y” is from 1 to 100000, such as from 1 to 1000 and y is from 1 to 1000, such as from 1 to 10 and y is from 1 to 100000.

[0111] The integers “x” and “y” are random in the polymer chain (not sequantial repeating on the chain). Being a random copolymer, the monomer residues are located randomly in the polymer molecule (instead of in linear arrangement of blocks, such in block co-polymers).

[0112] In the co-polymer, the ratio of “x” to “y” in the random co-poly(hydroxy- carbonate), is from 1 :99 to 99:1, or 1 :66 to 66:1, 1:33 to 33: 1 or 4:1 to 1 : 1 (mol / mol).

[0113] Comparisons and Examples The present invention is further explained in more detail with reference to the following examples. These examples, however, should not be interpreted as limiting the scope of the present invention.

[0114] The reaction and production were monitored by FT-IR analyses using Nicolet- iS5 (Thermo Scientific, USA). The Shore D hardness of the resulting materials was measured at room temperature by using a digital hardness durometer (BGD 935 / D, Biuged Laboratory Instruments). The results were averaged from five tests conducted in several zones of the samples. The test may follow the standard ASTM D2240.

[0115] The number average molecular weight of the polymer in the following examples is determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and polystyrene of a known average molecular weight as a standard sample. GPC is a type of size-exclusion chromatography (SEC), that separates analytes on the basis of size, typically in organic solvents. The technique is often used for the analysis of polymers.

[0116] Comparison 1. - Production of BPA-free polycarbonate from DTMP-DC

[0117] The ring opening polymerization of DTMP-DC produces PU. 10g (33mmol) DTMP-DC was melted at 110 °C in 50 mL reaction vessel, followed by addition of catalyst, 0.20mL l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR (Figure 6B; showing an FTIR spectra of (A) DTMP- DC, (B) Polycarbonate), which showed no hydroxyl peak in 3500 cm-1, and Shore D hardness was measured as 90 (Figure 5).

[0118] Example 1. Production of BPA-free random co-poly(hydroxycarbonate) from DTMP-DC and 1,4-butanediol at ratio of 30% (mol / mol)

[0119] Use of polyol at a certain ratio to DTMP-DC can produce shorter chain and less networked BPA-free co-poly(hydroxycarbonate)s by catalysis since the polymerization may be terminated with lake of carbonate group to hydroxyl group. Thus hydroxyl group can be located in the inside carbonate unit formed from ROP of di-cyclic carbonate, or in terminal unit of carbonate unit as an end group.

[0120] In Example 1, 10g (33mmol) DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 1g 1,4-butanediol and 0.02 mL 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR, which showed broad hydroxyl peak in around 3500 cm-1 (Figure 7), and Shore D hardness was measured as 77.8 (Figure 5).

[0121] Example 2. Production of BPA-free random co-poly(hydroxy carbonate) from DTMP-DC and 1,4-butanediol at ratio of at ratio of 61% (mol / mol)

[0122] In Example 2, 10g DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 2g 1,4-butanediol and 0.02 mL 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR, which showed broad hydroxyl peak in around 3500 cm-1 (Figure 8), and Shore D hardness was measured as 69.6 (Figure 5).

[0123] Example 3. Production of BPA-free random co-poly(hydroxy carbonate) from DTMP-DC and 1,4-butanediol at ratio of at ratio of 91% (mol / mol)

[0124] 10g DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 3g 1,4-butanediol and 0.02 mL l,8-Diazabicyclo[5.4.0]undec-7- ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR, which showed broad hydroxyl peak in around 3500 cm-1 (Figure 9), and Shore D hardness was measured as 2.8 (Figure 5).

[0125] Example 4. Production of BPA-free random co-poly(hydroxy carbonate) from DTMP-DC and 1,3-propanediol at ratio of at ratio of 61% (mol / mol)

[0126] 10g DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 2g 1,3-propanediol and 0.02 mL l,8-Diazabicyclo[5.4.0]undec-7- ene (DBU, catalyst) at 110 oC. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR, which showed broad hydroxyl peak in around 3500 cm-1 (Figure 10), and Shore D hardness was measured as 72.4 (Figure 5).

[0127] Example 5. Production of BPA-free random co-poly(hydroxy carbonate) from DTMP-DC and 1,5-pentanediol at ratio of at ratio of 61% (mol / mol)

[0128] In Example 5, 10g DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 2g 1,5-pentanediol and 0.02 mL 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR, which showed broad hydroxyl peak in around 3500 cm-1 (Figure 11), and Shore D hardness was measured as 75.4 (Figure 5).

[0129] Example 6. Production of BPA-free random co-poly(hydroxy carbonate) from DTMP-DC and 1,6-hexanediol at ratio of at ratio of 61% (mol / mol)

[0130] In Example 6, 10g DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 2g 1,6-hexanediol and 0.02 mL 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR, which showed broad hydroxyl peak in around 3500 cm-1 (Figure 12), and Shore D hardness was measured as 62 4 (Figure 5).

[0131] Example 7. Production of BPA-free random co-poly(hydroxy carbonate) from DTMP-DC and 1-butanol at ratio of at ratio of 61% (mol / mol)

[0132] Use of mono-alcohol at a certain ratio to DTMP-DC can produce even shorter chain and less networked BPA-free co-poly(hydroxycarbonate)s by catalysis since the polymerization may be terminated with lake of carbonate group to hydroxyl group. Thus hydroxyl group can be located in the inside carbonate unit formed from ROP of di-cyclic carbonate, but not in terminal unit of carbonate unit as an end group.

[0133] 10g DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 2g 1-butanol and 0.02 mL l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed at 95 °C for Ihour. The structure was confirmed by FT-IR, which showed broad hydroxyl peak in around 3500 cm-1 (Figure 13), and Shore D hardness was measured as 70.2 (Figure 5).

[0134] Example 8. In situ molding and production of BPA-free random co- poly(hydroxy carbonate) from DTMP-DC and 1,4-butanediol at ratio of at ratio of 61% (mol / mol)

[0135] For example 3, 10g (33mmol) DTMP-DC was melt at 110 °C in 50 mL reaction vessel, followed by addition of mixture of 2g pre-heated 1,4-butanediol and 0.02 mL l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU, catalyst) at 110 °C. After 5 minutes, the polymerization was continued and completed in a molder at 95 °C for Ihour. The resulting random co-poly (hydroxy carbonate) is shown in Figure 14. Although the present invention has been described above with reference to (a) specific embodiment s), it is not intended to be limited to the specific form set forth herein. Rather, the invention is limited only by the accompanying claims and, other embodiments than the specific above are equally possible within the scope of these appended claims, e.g. different than those described above.

[0136] In the claims, the term "comprises / comprising" does not exclude the presence of other elements or steps. Furthermore, although individually listed, a plurality of means, elements or method steps may be implemented by e.g. a single unit or processor. Additionally, although individual features may be included in different claims, these may possibly advantageously be combined, and the 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 a plurality. The terms "a", "an", “first”, “second” etc do not preclude a plurality. 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.

[0137] References

[0138] [1] Pyo, S.H., Persson, P., Mollaahmad, M.A., Sorensen, K., Lundmark, S. and Hatti-Kaul, R., 2011. Cyclic carbonates as monomers for phosgene-and isocyanate-free polyurethanes and polycarbonates. Pure and Applied Chemistry, 84(3), pp.637-661.

[0139] [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. Polymer chemistry, 9(27), pp.3798-3807.

[0140] [3] Carre, C., Ecochard, Y., Caillol, S. and Averous, L., 2019. From the synthesis of biobased cyclic carbonate to polyhydroxyurethanes: A promising route towards renewable Nonisocyanate Polyurethanes. ChemSusChem, 12(15), pp.3410- 3430.

[0141] [4] Tomita H , Sanda F , Endo T., Reactivity comparison of five- and sixmembered cyclic carbonates with amines: Basic evaluation for synthesis of poly(hydroxyurethane), J. Polym. Sci. Part A: Polym. Chem. 2001:39:162-168.

Claims

CLAIMS1. A process for preparing a random co-poly(hydroxy carbonate) comprising reacting a 6-membered di-cyclic carbonate with a polyol, or a monohydric alcohol, via a ring-opening polymerization (ROP) by catalytic control for carbonate unit formation, in the presence of a catalyst, through a ring-opening polymerization reaction, by heating up a mixture of a 6-membered di-cyclic carbonate according to formula I, a polyol, or a monohydric alcohol, and a catalyst, to obtain a random co- poly(hydroxy carbonate)wherein;R is selected from the group consisting of oxygen (ether), C1-C20 di-alkyl, Cl- C20 alkylether, C1-C20 ketone, C1-C20 ester;Ri and R2, are independently of each other, selected from the group consisting of H, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3- C20 alkylcarbonyl, C3-C20 carbonyl alkyl, C4-C20 alkoxy carbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group or their derivatives;2. The process according to claim 1, wherein the 6-membered di-cyclic carbonate is a compound according to formula (II)wherein;R3 is selected from the group consisting of oxygen, C(0), 0C(0), and C(0)0;R4 and Rs, are independently of each other C1-C20 alkylene;Ri and R2, are independently of each other, selected from the group consisting of H, C1-C20 alkyl, hydroxyl, C1-C20 hydroxyalkyl, phenyl, C6-C20 phenylalkyl, C3- C20 alkylcarbonyl, C3-C20 carbonyl alkyl, C4-C20 alkoxy carbonyl, C4-C20 alkoxycarbonyloxy, C2-C20 carboxyl group or their derivatives.

3. The process according to claim 1 or 2, wherein the 6-membered di-cyclic carbonate is reacted with a polyol according to formula III,wherein;Re is selected from the group consisting of C1-C20 alkylene, such as C2 to C6 alkylene, C1-C20 hydroxyalkylene, C1-C20 dihydroxyalkylene, C5-C7 cycloalkylene, C1-C20 hydroxyalkylene, phenylene, Cl -CIO alkylene-phenylene-CO-ClO alkylene, Cl -CIO alkylene-C(O)-Cl-C10 alkylene, C1-C10C alkylene-C(O)O- C1-C10C alkylene, or their derivatives; preferably Re being selected from the group consisting of C1-C20 alkylene, such as C2 to C6 alkylene, C1-C20 hydroxyalkylene, and C1-C20 dihydroxyalkylene; more preferably the polyol according to formula II being selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,5 -pentanediol, 1,6- hexanediol, trimethylolpropane, pentaerythritol; even more preferably the polyol according to formula II being selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; or wherein the 6-membered di-cyclic carbonate is reacted with a monohydric Cl- C10 alcohol, such as a monohydric alcohol selected from the group consisting of methanol, ethanol, propanol, such as n-propanol, butanol, such as n-butanol, pentanol, such as n-pentanol, and hexanol, such as n-hexanol.

4. The process according to any one of claims 1 to 3, wherein in formula I:R is oxygen;R4 and R5 is methylene; andRi and R2, are independently of each other, selected from the group consisting of H, ethyl, or hydroxymethyl; preferably Ri and R2 both being ethyl.

5. The process according to any one of claims 1 to 4, wherein the 6-membered di-cyclic carbonate is selected from the group consisting of di-trimethylolpropane di- cyclic carbonate (DTMP-DC) and pentaerythritol dicarbonate (PE-DC); preferably the 6-membered di-cyclic carbonate being di-trimethylolpropane di-cyclic carbonate (DTMP-DC).

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

7. The process according to any one of claims 1 to 6, wherein the weight ratio of polyol, or monohydric alcohol, to 6-membered di-cyclic 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 0.11 :1, or 0.21 : 1 to 1:0.25 (wt:wt), such as from 0.21:1, or 0.25:1 to 1 :2, or even more preferably from 0.25:1 to 1:1 or 0.3:1 to 0.9: 1 (wt:wt).

8. The process according to any one of claims 1 to 7, wherein the weight ratio of catalyst to 6-membered di-cyclic carbonate is in a from 0.000001 : 1 to 1 : 1, such as from 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 from 0.0001 to 1:1 (wt:wt).

9. The process according to any one of claims 1 to 8, wherein the alcohol is a linear or cyclic alcohol, such as mono-alcohol of alkyl and aryl compounds; and the polyol is a linear or cyclic polyol, such as di-, tri-, poly-alcohol of alkyl and aryl compounds.

10. A process according to any one of claims 1 to 9, wherein a mixture of more than one type of polyol, or a monohydric alcohol, is used.

11. The process according to any one of claims 1 to 10, wherein the catalyst is an inorganic, organometallic catalyst or organocatalyst.

12. The process according to any one of claims 1 to 11, wherein the catalyst is an inorganic, organometallic catalyst, the inorganic or organometallic catalyst being selected the group containing proficient systems based onmetal centers, such as sodium, potassium, zinc, magnesium, calcium, tin, titanium, caesium or rare-earth metals, bearing suitable ancillary ligands, and / or the catalyst is an organocatalyst, the organocatalysts being selected from the group consisting of amine (4-N,N-dimethylaminopyridine), guanidines (1,5,7- triazabicyclo-[4.4.0]dec-5-ene, phosphazene [2-tert-butylimino-2-diethylamino- 1,3- dimethylperhydro-l,3,2-diazaphosphorine), amidine (l,8-Diazabicycloundec-7-ene), tertiary amines (dimethylethanolamine), N-heterocyclic carbenes, and bifunctional thiourea-tertiary amine catalysts.

13. The process according to according to claim 12, wherein the catalyst is l,8-Diazabicyclo[5.4.0]undec-7-ene (DBU).

14. The process according to claim 1 to 11, wherein the alcohol or polyol is selected from 1,4-butanediol, 1,3 -propanediol, 1,5- pentanediol, 1,6-hexanediol, 1-butanol, 1,6-hexanediol, Pripol® (Croda), trimethylolpropane, pentaerythritol, glycerol, dihydroxybenzen, 2 -benzyl- 1,3- propanediol, ethylenglycol, 2,2,4,4-tetramethyl 1,3 -cyclobutanediol, and 1,4- cyclohexanedimethanol.

15. The process according to any one of claims 1 to 14, wherein the polymerization temperature is 30°C or higher, 60 or higher 100°C or higher, or 140°C or higher, or 180°C or higher.

16. The process according to any one of claims 1 to 15, wherein the polymerization reaction time of is from 1 minute to 24 hours, such as from 20 minutes to 3 hours, such as from 30 minutes to 2 hours.

17. The process according to any one of claims 1 to 16, wherein the process also comprises addition of a modifying agent, such as at benzyl alcohol.

18. The process according to claim 17, wherein the weight ratio of modifying agent to di-cyclic carbonate is in a ratio of 0.0001 : 1 to 1 : 1 (wt:wt), 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 (wt:wt).

19. The process according to any one of claims 1 to 18, further comprising a melting step wherein the 6-membered di-cyclic carbonate is melted, preferably the melting step is performed before the addition of polyamine and / or catalyst.

20. The process according to claim 19, wherein the melting temperature of the melting step is at least 30°C, at least 60, such as at least 100°C, at least 140°C, or at least 180°C.

21. The process according to any one of claims 19 to 20, wherein the melting temperature of the melting step least corresponds to the melting point of the 6- membered di-cyclic carbonate.

22. The process according to any one of claims 19 to 21, wherein the duration of the melting step is 1 from 30 seconds to 60 minutes, preferably 1 minute to 30 minutes, such as 2 minutes to 15 minutes.

23. The process according to any one of claims 1 to 22, wherein the reaction is performed without addition of any solvent.

24. The process according to any one of claims 1 to 22, wherein the reaction takes place in solution, wherein the solution comprises an organic solvent selected from alcohols, cyclic ethers, ketones, toluene, acetonitrile, halogenated alkanes, dimethylformamide, and pyridine or mixtures thereof.

25. The process according to claim 24, wherein: the solvent is an alcohol selected from the group consisting of methanol, ethanol and propanol; the solvent is a cyclic ether selected from the group consisting of diethyl ether and THF ; the solvent is a ketone selected from the group consisting of acetone and ethylmethylketone; and / or the solvent is a halogenated alkane selected from the group consisting of dichloromethane and chloroform.

26. The process according to any one of claims 1 to 25, wherein the polymerization is performed by means of molding, casting, coating, blown film, or extrusion.

27. A random co-poly(hydroxycarbonate), said random co- poly(hydroxy carbonate) being obtainable by the process according to any one of claims 1 to 24.

28. The random co-poly(hydroxycarbonate) according to claim 27, wherein its shore D hardness is in the range of 1 to 85; preferably the shore D hardness is less than 80, such as in the range from 3 to 78, such as in the range of 62 to 78.

29. The random co-poly(hydroxycarbonate) according to any one of claims 27 or 28, wherein an FT-IR spectra of the random co-poly(hydroxy carbonate) shows a hydroxyl peak at between 3000 to 3700 cm-1.

30. The random co-poly(hydroxycarbonate) according to any one of claims 27 to 29, wherein the random co-poly(hydroxycarbonate) is BPA-free.

31. An article comprising a random co-poly(hydroxycarbonate) according to any one of claims 27 to 30, wherein the article has been produced by blow moulding, injection moulding, or sheet extrusion.

32. Use of a random co-poly(hydroxycarbonate) according to any one of claims 27 to 31, for the production of a film, an article by blow moulding or injection moulding, a fibre, or a pipe.

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