EP3230341A2 - Polycarbonates aliphatiques et procédés pour les produire à partir de carbonates cycliques - Google Patents

Polycarbonates aliphatiques et procédés pour les produire à partir de carbonates cycliques

Info

Publication number
EP3230341A2
EP3230341A2 EP15868537.0A EP15868537A EP3230341A2 EP 3230341 A2 EP3230341 A2 EP 3230341A2 EP 15868537 A EP15868537 A EP 15868537A EP 3230341 A2 EP3230341 A2 EP 3230341A2
Authority
EP
European Patent Office
Prior art keywords
cyclic carbonate
polycarbonate
carbonate
reaction
mercaptopropionate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15868537.0A
Other languages
German (de)
English (en)
Other versions
EP3230341A4 (fr
Inventor
Sang-Hyun Pyo
Rajni Hatti-Kaul
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP3230341A2 publication Critical patent/EP3230341A2/fr
Publication of EP3230341A4 publication Critical patent/EP3230341A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0216—Aliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0225—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/025—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates

Definitions

  • This invention relates to carbonate building blocks, chlorine- and bisphenol-free polycarbonates, their derivatives prepared from six-membered functional cyclic carbonates.
  • the invention further relates to production process of said building blocks and polymers, and use of those materials for different applications, e.g. plastics, resin, coatings, forms, biomedical, and biomaterial applications.
  • 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.
  • 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 [1].
  • BPA shows estrogenic properties
  • 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, as lacquers to coat metal products such as food cans, bottle caps, water supply pipes, and dental sealants and tooth coatings (reviewed in [2]).
  • Aliphatic polycarbonates have been less interesting compared to aromatic polycarbonates because of their poor thermal stability and easy hydrolysis. However, since the last decade, aliphatic polycarbonates have been attracting attention due to increasing awareness of risks of BPA exposure from aromatic polycarbonates, and also for their unique combination of biodegradability and biocompatibility for medical applications. Aliphatic polycarbonates can be prepared mainly by 3 reaction pathways [3]. Aliphatic carbonates were prepared by polymerization of CO 2 with an epoxide (propylene oxide and ethylene oxide) using highly efficient catalysts. These amorphous polymers are currently in the early stage of commercialization.
  • epoxide propylene oxide and ethylene oxide
  • the condensation polymerization of aliphatic diols with dimethyl carbonate produced high molecular weight aliphatic polycarbonates using a catalyst (NaH) by two stage reaction consisting of oligomerization and polymerization at over 180°C.
  • Aliphatic polycarbonates can also be obtained via ring opening polymerization (ROP) of their respective cyclic monomers using different kinds of initiators and catalysts according to cationic, anionic, coordination, and enzymatic mechanisms, or metallic compounds as catalysts, which allow full control over molecular parameters along with chain-end group fidelity (reviewed in [4]).
  • Cyclic carbonates used for preparation of aliphatic polycarbonates by ROP were reviewed, but were only mono-cyclic carbonates with limited functional groups [5].
  • Five-membered alkylene carbonates have been considered to a less extent for commercial use owing to thermodynamic properties in the ROP, while six-membered 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 CO 2 such that the polymer produced contains both carbonate and ether linkages. Therefore, six-membered cyclic carbonates are thermodynamically more suitable precursors, however their production has not been straightforward, and the monomers are not commercially available.
  • di-trimethylolpropane dicyclic carbonate has been prepared from di-trimethylolpropane with phosgene, chlorocarbonates, dialkylcarbonates and diarylcarbonates using strong base catalysts by a two-step process comprising polymerization and depolymerisation at 250°C under 0.01 mbar [7].
  • the essential point in polymerization step was that the reaction leads to a soluble product and not to an insoluble, strongly crosslinked polymer. Therefore this indicated that the process was to prepare the cyclic carbonate, and the intermediate was an oligomer or low molecular prepolymer rather than polycarbonate. Also no specification and properties of the polymer were provided.
  • Allylated trimethylolpropane cyclic carbonate, (meth)acrylated trimethylolpropane cyclic carbonate can be polymerized to polycarbonate through the cyclic carbonate, and then the resulting polycarbonates can be further polymerized with active groups of allyl and (meth)acryl groups by UV or thermal reaction in the presence of an initiator. Allyl group reacts with thiol group by the thiol-ene reaction mechanism by UV or thermal reaction.
  • Acrylate and methacrylate are common monomers in polymer plastics, forming the corresponding polymers because the ⁇ , ⁇ -unsaturated double bonds are very reactive. Resulting polymers can be used as plastic, sheet or resin for conventional purpose, and biomedical and biomaterial applications of polycarbonate and polycarbonate copolymers.
  • the resulting polymers can be novel materials having unique properties and structures, and the production process provides a mild environment-friendly process without using phosgene, other chlorinated materials, and bisphenol.
  • 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, since the main raw material, BPA shows estrogenic properties, thus 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, as lacquers to coat metal products such as food cans, bottle caps, water supply pipes, and dental sealants and tooth coatings.
  • the present invention provides a process for ROP of dicyclic carbonate, e.g. di-trimethylolpropane dicyclic carbonate (diTMP diCC) and di-trimethylolethane dicyclic carbonate (diTME diCC) to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • dicyclic carbonate e.g. di-trimethylolpropane dicyclic carbonate (diTMP diCC) and di-trimethylolethane dicyclic carbonate (diTME diCC)
  • the present invention provides a polycarbonate prepared from dicyclic carbonate, e.g. diTMP diCC and diTME diCC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • diTMP diCC and diTME diCC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention provides a process for ROP of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • ambient temperature room temperature, RT
  • temperature preferably 80 to 150°C.
  • the present invention provides a polycarbonate prepared from allylated cyclic carbonate, e.g. TMPME CC and TMEME CC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • a polycarbonate prepared from allylated cyclic carbonate, e.g. TMPME CC and TMEME CC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention provides a process for cross linking of polycarbonate prepared from allylated cyclic carbonate, e.g. TMPME CC and TMEME CC to cross linked polycarbonate through thermal reaction of polycarbonate with thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction with thiol compound in presence of initiator.
  • ambient temperature room temperature, RT
  • temperature ranging from ambient to 300°C, preferably 80 to 150°C or through UV reaction with thiol compound in presence of initiator.
  • the present invention provides cross linked polycarbonate prepared through polycarbonate prepared from allylated cyclic carbonate, e.g. TMPME CC and TMEME CC through thermal reaction of polycarbonate with thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction of polycarbonate with thiol compound in presence of initiator.
  • TMPME CC and TMEME CC through thermal reaction of polycarbonate with thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction of polycarbonate with thiol compound in presence of initiator.
  • the present invention provides a process for thermal reaction of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC with thiol compound to prepolymer in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • ambient temperature room temperature, RT
  • the present invention provides prepolymer prepared through thermal reaction of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC with thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or with thiol compound by UV reaction in presence of initiator.
  • allylated cyclic carbonate e.g. TMPME CC and TMEME CC
  • thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or with thiol compound by UV reaction in presence of initiator.
  • the present invention provides a process for direct (one-pot) preparation of cross linked polycarbonate from reaction of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC with thiol compound in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • allylated cyclic carbonate e.g. TMPME CC and TMEME CC with thiol compound
  • the present invention provides a process for ROP of (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention provides a polycarbonate prepared from (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • a polycarbonate prepared from (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention provides a process for cross linking of polycarbonate prepared from (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC to cross linked polycarbonate through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • ambient temperature room temperature, RT
  • the present invention provides cross linked polycarbonate prepared through polycarbonte prepared from (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • the present invention provides a process for ROP of mixture of (functional) cyclic carbonates to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention provides polycarbonates prepared from mixture of (functional) cyclic carbonates in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention provides a process for cross linking of polycarbonate prepared from mixture of (functional) cyclic carbonates to cross linked polycarbonate through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • ambient temperature room temperature, RT
  • temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • the present invention provides cross linked polycarbonate prepared through polycarbonte prepared from mixture of (functional) cyclic carbonates through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • novel materials of polycarbonates having unique properties and structures, and the production process thereof which provides a mild environment-friendly process without using phosgene, other chlorinated materials, and bisphenol.
  • Figure 1 shows general polymerization process from six-membered dicyclic carbonates.
  • Figure 2 shows FT-IR spectra of the reaction components and polycarbonate products formed during ROP of diTMP dicyclic carbonate (diTMPdiCC) at 110°C.
  • diTMPdiCC diTMP dicyclic carbonate
  • A diTMPdiCC
  • B product at 30 min of ROP
  • C product at 120 min in ROP.
  • Figure 3 shows general polymerization process from allylated cyclic carbonate.
  • FIG 4 shows FT-IR spectra of the reaction components and polycarbonate products formed during ROP of allylated trimethylolpropane cyclic carbonate (TMPME CC) prepared from trimethylolpropane allylether (TMPME), where (A) is TMPME, (B) is TMPME cyclic carbonate (TMPME CC), (C) is polycarbonate prepared from TMPME CC, (D) is pentaerythritol tetra(3-mercaptopropionate) (PETMP), and (E) is polymer from reaction of (C) with (D) by thermal polymerization.
  • TMPME allylated trimethylolpropane cyclic carbonate
  • TMPME CC trimethylolpropane allylether
  • Figure 5 shows general polymerization process from allylated cyclic carbonate via prepolymer.
  • FIG. 6 shows FT-IR spectra of the reaction components and polycarbonate products formed during ROP of allylated trimethylolpropane cyclic carbonate (TMPME CC) prepared from trimethylolpropane allylether (TMPME), where (A) is TMPME cyclic carbonate (CC), (B) is prepolymer prepared from reaction of TMPME CC and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) by thermal reaction, (C) is polycarbonate prepared from prepolymer (B) by ROP.
  • TMPME CC trimethylolpropane cyclic carbonate
  • PTMP pentaerythritol tetrakis(3-mercaptopropionate)
  • Figure 7 shows general direct polymerization process from allylated cyclic carbonate.
  • FIG 8 shows FT-IR spectra of the reaction components and polycarbonate products formed during ROP of allylated trimethylolpropane cyclic carbonate (TMPME CC), where (A) is TMPME cyclic carbonate (CC), (B) is polycarbonate prepared from TMP CC (A) with pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) by thermal reaction and ROP.
  • TMPME CC allylated trimethylolpropane cyclic carbonate
  • PETMP pentaerythritol tetrakis(3-mercaptopropionate
  • Figure 9 shows general polymerization process from (meth)acrylated cyclic carbonate.
  • Figure 10 shows FTIR spectra where (A) is TMPmMA, (B) is TMPmMA cyclic carbonate (CC), (C) is polycarbonate prepared from TMPmMA CC.
  • Figure 11 shows FTIR spectra where (A) is mixture of TMPmMA and TMPCC, (B) is polycarbonate prepared from TMPmMACC and TMPCC, (C) is crosslinked polycarbonate in methacrylate group from (C).
  • the present invention relates to a process for ROP of dicyclic carbonate, e.g. diTMP diCC and diTME diCC to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • ambient temperature room temperature, RT
  • temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention relates to a polycarbonate prepared from dicyclic carbonate, e.g. diTMP diCC and diTME diCC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • diTMP diCC and diTME diCC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention relates to a process for ROP of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • ambient temperature room temperature, RT
  • temperature preferably 80 to 150°C.
  • the present invention relates to a polycarbonate prepared from allylated cyclic carbonate, e.g. TMPME CC and TMEME CC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • ambient temperature room temperature, RT
  • temperature preferably 80 to 150°C.
  • the present invention relates to a process for cross linking of polycarbonate prepared from allylated cyclic carbonate, e.g. TMPME CC and TMEME CC to cross linked polycarbonate through thermal reaction of polycarbonate with thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction with thiol compound in presence of initiator.
  • ambient temperature room temperature, RT
  • the present invention relates to cross linked polycarbonate prepared through polycarbonate prepared from allylated cyclic carbonate, e.g. TMPME CC and TMEME CC through thermal reaction of polycarbonate with thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction of polycarbonate with thiol compound in presence of initiator.
  • the present invention relates to a process for thermal reaction of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC with thiol compound to prepolymer in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • ambient temperature room temperature, RT
  • temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention relates to prepolymer prepared through thermal reaction of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC with thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or with thiol compound by UV reaction in presence of initiator.
  • allylated cyclic carbonate e.g. TMPME CC and TMEME CC
  • thiol compound in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or with thiol compound by UV reaction in presence of initiator.
  • the present invention relates to a process for direct (one-pot) preparation of cross linked polycarbonate from reaction of allylated cyclic carbonate, e.g. TMPME CC and TMEME CC with thiol compound in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • allylated cyclic carbonate e.g. TMPME CC and TMEME CC with thiol compound
  • the present invention relates to a process for ROP of (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention relates to a polycarbonate prepared from (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • a polycarbonate prepared from (meth)acrylated cyclic carbonate e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC by ROP in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention relates to a process for cross linking of polycarbonate prepared from (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC to cross linked polycarbonate through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • ambient temperature room temperature, RT
  • the present invention relates to cross linked polycarbonate prepared through polycarbonte prepared from (meth)acrylated cyclic carbonate, e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA CC through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • the present invention relates to a process for ROP of mixture of (functional) cyclic carbonates to polycarbonate in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention relates to polycarbonates prepared from mixture of (functional) cyclic carbonates in presence of catalyst at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • the present invention relates to a process for cross linking of polycarbonate prepared from mixture of (functional) cyclic carbonates to cross linked polycarbonate through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • ambient temperature room temperature, RT
  • temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • the present invention relates to cross linked polycarbonate prepared through polycarbonte prepared from mixture of (functional) cyclic carbonates through thermal reaction of polycarbonate in presence of initiator at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C, or through UV reaction in presence of initiator.
  • This invention is directed to aliphatic polycarbonates to be used as plastics and resins, and a method of manufacturing polycarbonates without using phosgene and bisphenol ( Figure 1, 3 and 5).
  • Cyclic carbonate can be selected from general formula in Figure 1, 3 and 5.
  • DiTMP-diCC and di-trimethylolethane dicyclic carbonate (DiTME-diCC), TMPME CC, trimethylolethane allylether cyclic carbonate (TMEME CC), TMPmMA CC, trimethylolethane methacrylate cyclic carbonate (TMEmMA CC), trimethylolethane acrylate cyclic carbonate TMPmA CC, and trimethylolethane acrylate cyclic carbonate (TMEmA CC) are preferable examples.
  • Cyclic carbonate can be polymerized by ROP using catalysts and initiators at increased temperature. Polycarbonates were formed by the reaction.
  • the process can be carried out in mould to provide the corresponding plastic shapes, and by extruders.
  • Typical organic solvents can be used, but are not necessary for the reaction.
  • the ROP may be performed in solution and any organic solvent selected from the group consisting of C1-C10 alcohols (e.g. methanol and ethanol), C1-C10 hydrocarbone (e.g. n-hexane), ether (e.g. diethylether), acetonitrile, chlorohydrocarbones (dichloromethane, chloroform), dimethylsulfoxide, and a mixture thereof may be used.
  • C1-C10 alcohols e.g. methanol and ethanol
  • C1-C10 hydrocarbone e.g. n-hexane
  • ether e.g. diethylether
  • acetonitrile chlorohydrocarbones (dichloromethane, chloroform), dimethylsulfoxide, and a mixture thereof
  • Heterogeneous and homogeneous catalysts are used according to the invention.
  • An inorganic and organometallic catalysis can be selected from various proficient systems based on metal centers, such as sodium, potassium, zinc, magnesium, calcium, or rare-earth metals, bearing suitable ancillary ligands.
  • organocatalysts can be used to lead ROP of dicyclic carbonates, and include commercially available 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-1,3,2-diazaphosphorine), amidine (1,8-Diazabicycloundec-7-ene), tertiary amines (dimethylethanolamine), N-heterocyclic carbenes, and bifunctional thiourea-tertiary amine catalysts.
  • amine 4-N,N-dimethylaminopyridine
  • guanidines (1,5,7-triazabicyclo-[4.4.0]dec-5-ene
  • phosphazene [2-tert-butylimino-2-diethylamino-1,3-d
  • organocatalysts are used in the presence of an alcohol.
  • An alcohol such as benzyl alcohol, 1,3-propanediol, glycerol that acts both as a co-initiator and a chain-transfer agent, can be used with catalysts.
  • Polycarbonates were formed by the reaction.
  • Catalyst can preferably be used at a ratio of 0.001 to 100 wt% of cyclic carbonate.
  • the weight ratio of used catalyst to cyclic carbonate is not limited. But the ratio can preferably be used at a ratio of 0.001 to 100 wt% such as 0.001, 0.01, 0.1, 1, 10 and 100 wt%, or even more preferred 0.01 to 1 wt%.
  • the weight ratio of used alcohols to cyclic carbonate is not limited. But the ratio can preferably be used at a ratio of 0.01 to 100 wt% such as 0.01, 0.1, 1, 10 and 100 wt%, or even more preferred 0.1 to 1 wt%.
  • ROP could be carried out at ambient temperature (room temperature, RT), or at temperature ranging from ambient to 300°C, preferably 80 to 150°C.
  • reaction time could be 1 minute or longer, or 1 hour or longer, or 1 day or longer, 10 days or longer.
  • General additives such as hardener, softener, catalyst, pigment and binder can be used in the plastics, sheets, chips and resins formation.
  • the obtained ring opened polycarbonate of e.g. TMPME CC and TMEME CC may be further polymerized via an ene functional group in allyl group (General scheme in Figure 3).
  • the ring opened polycarbonate of e.g. TMPME and TMEME may be reacted with thiol compounds using UV or thermal energy.
  • the thiol compounds may be chosen from dithiols, such as 1,2-ethylenedithiol; or trithiols, such as trimethylolpropane tris(3-mercaptopropionate); tetrathiols, such as pentaerythritol tetrakis (3-mercaptopropionate); and polythiols.
  • the UV or thermal reaction may be initiated by an initiator.
  • the obtained ring opened polycarbonate of e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA may be polymerized via an (meth)acrylate functional group (General scheme in Figure 5).
  • the ring opened polycarbonate of e.g. TMPmMA CC, TMEmMA CC, TMPmA CC and TMEmA may be polymerized by UV or thermal reaction. Any typical polymerization method may be used in the polymerization of methacrylate group by UV and/or thermal reaction in the absence or presence of an initiator and/or catalyst. The UV or thermal reaction may be initiated by an initiator.
  • An initiator may be used in the reaction and polymerization process in above cross linking polymerizations in allyl and (meth)acryl group, and may be selected from the group azo compounds of azobisisobutyronitrile (AIBN) and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure®), and organic peroxides of di-ter-butyl peroxide and benzoyl peroxide.
  • AIBN azobisisobutyronitrile
  • ABCN 1,1'-azobis(cyclohexanecarbonitrile)
  • Darocure® 2-hydroxy-2-methyl-1-phenyl-propan-1-one
  • organic peroxides of di-ter-butyl peroxide and benzoyl peroxide organic peroxides of di-ter-butyl peroxide and benzoyl peroxide.
  • the reaction and application may be performed in solution form and any organic solvent may be used.
  • preferred solvents are alcohols (e.g. methanol, ethanol and propanol), (cyclic) ethers (e.g. diethyl ether and THF), ketones (e.g. acetone, ethylmethylketone), toluene, acetonitrile, halogenated alkane (dichloromethane and chloroform), dimethylformamide, and pyridine or mixtures of the same or mixtures containing said solvents.
  • Use of solvent provides the homogenization, polymerization and coating application.
  • the temperature may be at least 20°C, such as at least 90°C, at least 100°C, at least 120°C, at least 140°C, or at least 160°C.
  • the thermal property (glass transition temperature, Tg) was measured by differential scanning calorimeter (DSC). The apparent transparency of the material was determined, and the results were indicated with leads ranging in transparency from 1 (low) to 5 (high transparency, colorless).
  • the formation of linear carbonate group from cyclic carbonate was determined from samples collected from polymerized material by FT-IR analysis.
  • the present invention relates to a process for preparing polycarbonate comprising polymerizing dicyclic carbonate, allylated cyclic carbonate, (meth)acrylated cyclic carbonate, or a mixture thereof as shown below to polycarbonate as shown below through Ring Open Polymerization (ROP) in presence of catalyst at temperature ranging from ambient temperature (room temperature, RT) to 300°C. according to the schemes (I) - (III) given below:
  • R oxygen (ether), C1-10 alkyl, C3-10 ketone, C3-10 ester.
  • R and R 1 H, C1-10 alkyl, hydroxyl, C1-10 hydroxyalkyl, C3-10
  • the above process for preparing polycarbonate can comprises thermally reacting polycarbonate prepared from allylated cyclic carbonate, (meth)acrylated cyclic carbonate, or a mixture thereof with thiol compound in presence of initiator at temperature ranging from ambient temperature (room temperature, RT) to 300°C, or UV reacting polycarbonate with thiol compound in presence of initiator, thus obtaining cross linked polycarbonate or highly cross linked polycarbonate.
  • the dicyclic carbonate is di-trimethylolpropane dicyclic carbonate (diTMP diCC), di-trimethylolethane dicyclic carbonate (diTME diCC) or a mixture thereof
  • the allylated cyclic carbonate is trimethylolpropane allylether cyclic carbonate (TMPME CC), trimethylolethane allylether cyclic carbonate (TMEME CC) or a mixture thereof
  • the (meth)acrylated cyclic carbonate is (meth)acrylated trimethylolpropane cyclic carbonate (TMPmMA CC), trimethylolethane methacrylate cyclic carbonate (TMEmMA CC), trimethylolethane acrylate cyclic carbonate (TMPmA CC), trimethylolethane acrylate cyclic carbonate (TMEmA CC) or a mixture thereof.
  • the present invention relates to a polycarbonate prepared by the process for preparing polycarbonate according to the present invention.
  • the present invention relates to a process for preparing prepolymer comprising reacting allylated cyclic carbonate as shown below with thiol compound through thermal reaction in presence of catalyst at temperature ranging from ambient temperature (room temperature, RT) to 300°C, or through UV reaction in presence of initiator according to the scheme given below:
  • R H, C1-10 alkyl, hydroxyl, C1-10 hydroxyalkyl, C3-10 alkylcarbonyl, C3-10 carbonylalkyl, C4-10 alkoxycarbonyl, C4-10 alkoxycarbonyloxy and C2-10 carboxyl group, respectively;
  • the present invention relates to a prepolymer prepared by the a process for preparing prepolymer according to the present invention.
  • the present invention relates to a process for directly (one-pot) preparing cross linked polycarbonate comprising reacting allylated cyclic carbonate as shown below with thiol compound through thermal reaction in presence of catalyst at temperature ranging from ambient temperature (room temperature, RT) to 300°C or through UV reaction in presence of initiator according to the scheme given below:
  • R H, C1-10 alkyl, hydroxyl, C1-10 hydroxyalkyl, C3-10 alkylcarbonyl, C3-10 carbonylalkyl, C4-10 alkoxycarbonyl, C4-10 alkoxycarbonyloxy and C2-10 carboxyl group, respectively;
  • the present invention relates to a cross linked polycarbonate prepared by the process for preparing cross linked polycarbonate according to the present invention.
  • the thiol compound used in the precess for preparing cross linked polycarbonate is chosen from dithiols, trithiols, tetrathiols, and polythiols.
  • the above thiol compound is chosen from 1,2-ethylenedithiol, trimethylolpropane tris(3-mercaptopropionate), and pentaerythritol tetrakis(3-mercaptopropionate).
  • cyclic carbonates are dicyclic carbonates having six-membered rings from polyols such as di-trimethylolpropane (diTMP), di-trimethylolethane (diTME) and derivatives thereof.
  • Polycarbonates according to the present invention can be prepared by polymering dicyclic carbonates as shown in the scheme below (see also Figure 1):
  • R oxygen (ether), C1-10 alkyl, C3-10 ketone, C3-10 ester.
  • figure 2 shows FT-IR spectra of the reaction components and polycarbonate products formed during ROP of diTMP dicyclic carbonate (diTMPdiCC) at 110°C.
  • P2 indicates linear C-O-C asymmetric stretching band peak at 1290-1180 cm -1 .
  • FT-IR analyses were performed using Nicolet-iS5 (Thermo Scientific, USA).
  • the ROP of diTMP diCC was performed with 0.1% (w/w) 4-(dimethylamino)pyridine (DMAP) as a catalyst and 1% (w/w) 1,3-propanediol as an initiator/chain transfer agent at 110°C in a thermoshaker.
  • DMAP dimethylaminopyridine
  • FT-IR spectra show the peak shifts of functional groups in the reaction at 110°C.
  • P1 indicates peak shift of 9 cm -1 from cyclic carbonyl group of diTMP diCC at 1731 cm -1 to linear carbonyl group of polycarbonate at 1740 cm -1 .
  • C-O-C asymmetric stretching band peak is typically appeared at 1290-1180cm -1 .
  • the functionality change (P2) of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1229 cm -1 with decreasing intensity in range of 1100-1200 cm -1 .
  • the hydroxyl group at 3400 cm -1 did not appear and indicated that the polymerization and crosslinking was quickly achieved after opening of the cyclic carbonate ring.
  • cyclic carbonates are functionalized cyclic carbonates having an allyl group in polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • TMP trimethylolpropane
  • TME trimethylolethane
  • Polycarbonates according to the present invention can be prepared by polymering functionalized cyclic carbonates having an allyl group as shown in the scheme below (see also Figure 3):
  • R H, C1-10 alkyl, hydroxyl, C1-10 hydroxyalkyl, C3-10 alkylcarbonyl, C3-10 carbonylalkyl, C4-10 alkoxycarbonyl, C4-10 alkoxycarbonyloxy or C2-10 carboxyl group, respectively;
  • Example shows highly cross linked polycarbonate prepared from reaction of allylated polycarbonate and pentaerythri
  • figure 4 shows FT-IR spectra of the reaction components and polycarbonate products formed during ROP of allylated trimethylolpropane cyclic carbonate (TMPME CC) prepared from trimethylolpropane allylether (TMPME), where (A) is TMPME, (B) is TMPME cyclic carbonate (TMPME CC), (C) is polycarbonate prepared from TMPME CC, (D) is pentaerythritol tetra(3-mercaptopropionate) (PETMP), and (E) is polymer from reaction of (C) with (D) by thermal polymerization.
  • FT-IR spectra show the peak shifts of functional groups in each reaction step.
  • TMPME the strong broad peak in 3364 cm -1 indicates -OH group.
  • B TMPME CC: a new peak at 1747 cm -1 indicates carbonyl group of cyclic carbonate, and the strong broad peak of -OH group in 3364 cm -1 disappeared with formation of cyclic carbonate.
  • C Polycarbonate from TMPME CC: a peak at 1237 cm -1 is strongly increased, which is C-O-C asymetric stretching.
  • PTMP Pentaerythritol tetrakis(3-mercaptopropionate)
  • the ROP of TMPME CC (200mg) was performed with 4-(dimethylamino)pyridine (DMAP, 1mg) as a catalyst and 1,3-propanediol (0.01mL) as an initiator/chain transfer agent at 90°C in a thermoshaker.
  • DMAP 4-(dimethylamino)pyridine
  • 1,3-propanediol (0.01mL) as an initiator/chain transfer agent at 90°C in a thermoshaker.
  • FT-IR spectra show the peak shifts of functional groups in the reaction at 110°C.
  • C-O-C asymmetric stretching band peak is typically appeared at 1290-1180 cm -1 (P3).
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1237 cm -1 with decreasing intensity in range of 1100-1200 cm -1 .
  • cyclic carbonates are functionalized cyclic carbonates having an allyl group in polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • TMP trimethylolpropane
  • TME trimethylolethane
  • Polycarbonates according to the present invention can be prepared by polymering functionalized cyclic carbonates having an allyl group via prepolymer as shown in the scheme below (see also Figure 5):
  • R H, C1-10 alkyl, hydroxyl, C1-10 hydroxyalkyl, C3-10 alkylcarbonyl, C3-10 carbonylalkyl, C4-10 alkoxycarbonyl, C4-10 alkoxycarbonyloxy and C2-10 carboxyl group, respectively;
  • Example shows highly cross linked polycarbonate prepared from reaction of allylated polycarbonate and pentaerythr
  • firgue 6 show FT-IR spectra of the reaction components and polycarbonate products formed during ROP of allylated trimethylolpropane cyclic carbonate (TMPME CC) prepared from trimethylolpropane allylether (TMPME), where (A) is TMPME cyclic carbonate (CC), (B) is prepolymer prepared from reaction of TMPME CC and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) by thermal reaction, (C) is polycarbonate prepared from prepolymer (B) by ROP.
  • TMPME CC trimethylolpropane cyclic carbonate
  • PETMP pentaerythritol tetrakis(3-mercaptopropionate)
  • FT-IR spectra show the peak shifts of functional groups in each reaction step.
  • A TMPME CC: A peak at 1737 cm -1 indicates carbonyl group of cyclic carbonate, and a peak at 927 cm -1 indicates C-H of mono-substituted alkene.
  • B Prepolymer (TMPMECC-PETMP): The alkene peak at 927 cm -1 disappeared by reaction of alkene with thiol group of PETMP.
  • C Polycarbonate from prepolymer (B): A peak at 1240 cm -1 is strongly increased, which is C-O-C asymetric stretching by ROP of cyclic carbonate. FT-IR analyses were performed using Nicolet-iS5 (Thermo Scientific, USA).
  • the ROP of prepolymer (B) was performed with 4-(dimethylamino)pyridine (DMAP, 3mg) as a catalyst and 1,3-propanediol (0.03mL) as an initiator/chain transfer agent to polycarbonate (C) at 110°C in a thermoshaker.
  • DMAP 4-(dimethylamino)pyridine
  • 1,3-propanediol (0.03mL)
  • C-O-C asymmetric stretching band peak is typically appeared at 1290-1180cm -1 (P3).
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1240 cm -1 with decreasing intensity in range of 1100-1200 cm -1 .
  • cyclic carbonates are functionalized cyclic carbonates having an allyl group in polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • TMP trimethylolpropane
  • TME trimethylolethane
  • Polycarbonates according to the present invention can be prepared by polymering functionalized cyclic carbonates having an allyl group as shown in the scheme below (see also Figure 7):
  • R H, C1-10 alkyl, hydroxyl, C1-10 hydroxyalkyl, C3-10 alkylcarbonyl, C3-10 carbonylalkyl, C4-10 alkoxycarbonyl, C4-10 alkoxycarbonyloxy and C2-10 carboxyl group, respectively;
  • Example shows highly cross linked polycarbonate prepared from reaction of allylated polycarbonate and pentaerythr
  • FIG 8 it shows FT-IR spectra of the reaction components and polycarbonate products formed during ROP of allylated trimethylolpropane cyclic carbonate (TMPME CC), where (A) is TMPME cyclic carbonate (CC), (B) is polycarbonate prepared from TMP CC (A) with pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) by thermal reaction and ROP.
  • TMPME CC allylated trimethylolpropane cyclic carbonate
  • PETMP pentaerythritol tetrakis(3-mercaptopropionate
  • FT-IR spectra show the peak shifts of functional groups in each reaction step.
  • A TMPME CC: A peak at 1737 cm -1 indicates carbonyl group of cyclic carbonate, and a peak at 927 cm -1 indicates C-H of mono-substituted alkene.
  • B Polycarbonate: The alkene peak at 927 cm -1 disappeared by reaction of alkene with thiol group of PETMP. A peak at 1240 cm -1 is strongly increased, which is C-O-C asymetric stretching by ROP of cyclic carbonate.
  • FT-IR analyses were performed using Nicolet-iS5 (Thermo Scientific, USA).
  • TMPME CC 200mg
  • PETMP 122mg, equivalent to TMPMECC
  • azobisisobutyronitrile AIBN, 3mg in 0.03mL acetonitrile
  • DMAP 4-(dimethylamino)pyridine
  • FT-IR spectra show the peak shifts of functional groups in the reaction at 110°C.
  • P4 (B) a peak at 927 cm -1 in (A), which is C-H of mono-substituted alkene, disappeared by reaction of alkene with thiol group of PETMP.
  • C-O-C asymmetric stretching band peak is typically appeared at 1290-1180cm -1 (P3).
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1240 cm -1 with decreasing intensity in range of 1100-1200 cm -1 .
  • cyclic carbonates are functionalized cyclic carbonates having an (meth)acrylic group in polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • polyols such as trimethylolpropane (TMP), trimethylolethane (TME) and derivatives thereof.
  • Polycarbonates according to the present invention can be prepared by polymering functionalized cyclic carbonates having an (meth)acrylic group as shown in the scheme below (see also Figure 9):
  • R and R 1 H, C1-10 alkyl, hydroxyl, C1-10 hydroxyalkyl, C3-10 alkylcarbonyl, C3-10 carbonylalkyl, C4-10 alkoxycarbonyl, C4-10 alkoxycarbonyloxy and C2-10 carboxyl group, respectively.
  • FIG 10 shows FTIR spectra where (A) is TMPmMA, (B) is TMPmMA cyclic carbonate (CC), (C) is polycarbonate prepared from TMPmMA CC.
  • FT-IR spectra show the peak shifts of functional groups in each reaction step.
  • TMPmMA CC trimethylolpropane cyclic carbonate
  • TMPmMA CC trimethylolpropane methacrylate
  • A is TMPmMA
  • B is TMPmMA cyclic carbonate
  • C is polycarbonate prepared from TMPmMA CC by thermal polymerization.
  • FT-IR spectra show the peak shifts of functional groups in each reaction step.
  • TMPmMA the strong broad peak at 3364 cm -1 indicates -OH group, and doublet peak in 1699 cm -1 indicates carbonyl group of carbonate and methacrylate.
  • TMPmMA CC a new peak at 1747 cm -1 indicates carbonyl group of cyclic carbonate, and the strong broad peak of -OH group at 3364 cm -1 disappeared with formation of cyclic carbonate.
  • C Polycarbonate from TMPmMA CC: a peak at 1239 cm -1 is strongly increased, which is C-O-C asymetric stretching, and a peak of carbonyl group of cyclic carbonate at 1747 cm -1 is shifted to linear carbonyl group at 1723 cm -1 .
  • FT-IR analyses were performed using Nicolet-iS5 (Thermo Scientific, USA).
  • the ROP of TMPmMA CC (200mg) was performed with 4-(dimethylamino)pyridine (DMAP, 1mg) as a catalyst and 1,3-propanediol (0.01mL) as an initiator/chain transfer agent at 90°C in a thermoshaker.
  • DMAP 4-(dimethylamino)pyridine
  • 1,3-propanediol (0.01mL) as an initiator/chain transfer agent at 90°C in a thermoshaker.
  • FT-IR spectra show the peak shifts of functional groups in the reaction at 90°C.
  • C-O-C asymmetric stretching band peak typically appeared at 1290-1180cm -1 (P3).
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1239 cm -1 with decreasing intensity in range of 1100-1200 cm -1 .
  • the hydroxyl group at 3364 cm -1 did not appear and indicated that the polymer
  • Functional cyclic carbonates can be mixed at different ratio and polymerized with other functional cyclic carbonates or cyclic carbonates to obtain different physical properties in ring-opening polymerization.
  • (Functional) cyclic carbonate can be selected from diTMPdiCC , TMPmMACC, TMPMECC, trimethylolpropane cyclic carbonate (TMPCC), trimethylene carbonate, 1-methyl-trimethylene carbonate, 2-methyl-trimethylene carbonate, 2-(methoxycarbonyl)-2-methyl-trimethylene carbonate, 1,1-dimethyl-trimethylene carbonate, but not limited.
  • diTMPdiCC and TMPmMACC diTMPdiCC and 1-methyl-trimethylene carbonate
  • TMPMECC 1,1-dimethyl-trimethylene carbonate
  • TMPMA CC and TMPCC are examples of TMPCC.
  • FIG 11 shows FTIR spectra where (A) is mixture of TMPmMA and TMPCC, (B) is polycarbonate prepared from TMPmMACC and TMPCC, (C) is crosslinked polycarbonate in methacrylate group from (C).
  • FT-IR spectra show the peak shifts of functional groups in each reaction step.
  • the ROP of mixture of TMPmMA CC (91mg) and trimethylolpropane cyclic carbonate (65mg) was performed with triethylamine (3mg) as a catalyst and 1,3-propanediol (0.003mL) as an initiator/chain transfer agent at 90°C in a thermoshaker.
  • Resulting polycarbonate was further polymerized and solidified using UV initiator by UV for 1 min.
  • FT-IR spectra show the peak shifts of functional groups in the reaction at 90°C.
  • C-O-C asymmetric stretching band peak typically appeared at 1290-1180cm -1 .
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1239 cm -1 with decreasing intensity in range of 1100-1200 cm -1 .
  • the hydroxyl group at 3364 cm -1 did not appear and indicated that the polymerization was quickly achieved after opening of the cyclic carbonate ring. Peaks of carbonyl group are shifted after polymerization.
  • Example 1 Polycarbonate synthesis from diTMPdiCC with FT-IR monitoring
  • Example 4 Polycarbonate from TMPME CC with FT-IR monitoring
  • TMPME CC 200mg TMPME CC was placed in 4mL glass vial and heated at 90°C using thermomixer. 10 mg 1,3-propanediol and 1 mg DMAP were added at 90°C. After 30 minutes, the ROP was monitored using FT-IR.
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1237 cm -1 for C-O-C asymmetric stretching band peak with decreasing intensity in range of 1100-1200 cm -1 .
  • the resulting polycarbonate was liquid phase (amorphous) at room temperature.
  • Liquid phase of sample resulting from Example 4 was reacted with a cross linker, PETMP (122mg, equivalent to TMPMECC) using azobisisobutyronitrile (AIBN, 3mg in 0.03mL acetonitrile) at 90°C. After 10 minutes, cross linked polycarbonate (solid phase) was obtained, and the reaction was monitored using FT-IR. By the functionality change, a peak at 900 cm -1 , which is C-H of mono-substituted alkene, disappeared by reaction of alkene with thiol group of PETMP.
  • PETMP 122mg, equivalent to TMPMECC
  • AIBN azobisisobutyronitrile
  • PETMP 200mg TMPME CC with a cross linker
  • PETMP 122mg, equivalent to TMPMECC
  • AIBN azobisisobutyronitrile
  • a peak at 927 cm -1 which is C-H of mono-substituted alkene, disappeared by reaction of alkene with thiol group of PETMP.
  • the resulting prepolymer was liquid phase (amorphous) at room temperature.
  • Example 7 ROP of prepolymer prepared from reaction of TMPME CC with PETMP with FT-IR monitoring
  • Liquid phase of sample resulting from Example 6 was polymerized using 30 mg 1,3-propanediol and 3 mg DMAP at 110°C by ROP. After 60 minutes, cross linked polycarbonate (solid phase) was obtained, and the reaction was monitored using FT-IR.
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1240 cm -1 for C-O-C asymmetric stretching band peak with decreasing intensity in range of 1100-1200 cm -1 .
  • Example 8 Direct polymerization of TMPME CC with PETMP with FT-IR monitoring
  • PETMP 200mg TMPME CC with a cross linker
  • PETMP 122mg, equivalent to TMPMECC
  • AIBN azobisisobutyronitrile
  • 3mg in 0.03mL acetonitrile 30 mg 1,3-propanediol
  • 3 mg DMAP 3 mg DMAP at 110°C.
  • cross linked polycarbonate solid phase
  • a peak at 927 cm -1 which is C-H of mono-substituted alkene, disappeared by reaction of alkene with thiol group of PETMP.
  • the functionality change of C-O-C group from cyclic carbonate to linear polycarbonate provided a strong new peak at 1240 cm -1 for C-O-C asymmetric stretching band peak with decreasing intensity in range of 1100-1200 cm -1 .
  • Example 9 Polycarbonate from TMPmMA CC with FT-IR monitoring
  • Example 10 Polycarbonate from mixture of (functional) cyclic carbonates with FT-IR monitoring
  • Example 9 Resulting polycarbonate from Example 9 was further polymerized and solidified on the surface of glass using UV initiator, 1mg 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure®) by UV lamp (365nm).
  • UV initiator 1mg 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure®) by UV lamp (365nm).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne des polycarbonates aliphatiques préparés par polymérisation par ouverture de cycle de carbonates cycliques à six chaînons ou de mélanges en divers rapports de carbonates cycliques à six chaînons en employant des catalyseurs. Les matériaux obtenus sont ensuite polymérisés en utilisant le groupe fonctionnel supplémentaire, comme un 2nd carbonate cyclique, (méth)acrylate et allylate supplémentaire. Ce procédé et le ou les matériaux obtenus permettent d'obtenir des polycarbonates sans chlore (par exemple phosgène et chloroformiate) et sans bisphénol, et leurs dérivés pour des applications respectueuses de l'environnement.
EP15868537.0A 2014-12-08 2015-12-07 Polycarbonates aliphatiques et procédés pour les produire à partir de carbonates cycliques Withdrawn EP3230341A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201462088751P 2014-12-08 2014-12-08
US201562199983P 2015-08-01 2015-08-01
PCT/KR2015/013331 WO2016093581A2 (fr) 2014-12-08 2015-12-07 Polycarbonates aliphatiques et procédés pour les produire à partir de carbonates cycliques

Publications (2)

Publication Number Publication Date
EP3230341A2 true EP3230341A2 (fr) 2017-10-18
EP3230341A4 EP3230341A4 (fr) 2018-11-14

Family

ID=56108327

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15868537.0A Withdrawn EP3230341A4 (fr) 2014-12-08 2015-12-07 Polycarbonates aliphatiques et procédés pour les produire à partir de carbonates cycliques

Country Status (3)

Country Link
EP (1) EP3230341A4 (fr)
KR (1) KR20170121156A (fr)
WO (1) WO2016093581A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745495A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 一种耐拉伸聚碳酸酯的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112980175A (zh) * 2021-02-07 2021-06-18 陕西科技大学 一种聚氨酯/木质素复合材料的制备方法
WO2024064363A2 (fr) * 2022-09-22 2024-03-28 The Florida State University Research Foundation, Inc. Polymères biodégradables à base de lignine et leurs procédés de fabrication

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057360B1 (fr) * 1981-01-30 1984-09-26 Bayer Ag Dérivés d'acide carbonique cycliques, procédé pour leur préparation et leur utilisation comme constituants de copolymérisation pour la préparation de polycarbonates
DE10138216A1 (de) * 2001-08-03 2003-02-20 Bayer Ag Aliphatische Polycarbonathomo- und -copolymere durch DMC-Katalyse
US8415448B2 (en) * 2008-07-31 2013-04-09 Total Petrochemicals Research Feluy Catalytic process for polymerising cyclic carbonates issued from renewable resources
FR2943679B1 (fr) * 2009-03-31 2016-10-21 Arkema France Systeme organique pour la polymerisation par ouverture de cycle de carbonates cycliques pour l'obtention de (bio)- polycarbonates.
EP2709995B1 (fr) * 2011-05-14 2018-06-13 Sang-Hyun Pyo Procédé pour produire des carbonates cycliques
US8912303B1 (en) * 2011-11-03 2014-12-16 U.S. Department Of Energy Poly(hydroxyl urethane) compositions and methods of making and using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745495A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 一种耐拉伸聚碳酸酯的制备方法
CN112745495B (zh) * 2019-10-30 2022-12-27 中国石油化工股份有限公司 一种耐拉伸聚碳酸酯的制备方法

Also Published As

Publication number Publication date
WO2016093581A2 (fr) 2016-06-16
KR20170121156A (ko) 2017-11-01
WO2016093581A3 (fr) 2016-08-04
EP3230341A4 (fr) 2018-11-14

Similar Documents

Publication Publication Date Title
WO2016117872A1 (fr) Nouveau procédé de préparation d'un ester de polycarbonate très transparent et très résistant à la chaleur
WO2019147051A1 (fr) Ester de polycarbonate d'origine biologique et son procédé de préparation
WO2016093581A2 (fr) Polycarbonates aliphatiques et procédés pour les produire à partir de carbonates cycliques
WO2020055178A1 (fr) Composé diol, polycarbonate et son procédé de production
WO2011030991A1 (fr) Composé durcissable à base de furane dérivé de la biomasse, composition durcissable sans solvant, et leur procédé de préparation
WO2015023027A1 (fr) Macro-polyol composé de polycarbonate aliphatique et copolymère de polyester aromatique associé
WO2015041441A1 (fr) Résine de copolycarbonate et produit comportant celle-ci
WO2021133048A1 (fr) Copolymère de polycarbonate comprenant des unités dérivées d'alcool d'anhydrosucre et d'alcool d'anhydrosucre-alkylène glycol, son procédé de production, et article moulé le comprenant
KR101548044B1 (ko) 신규 산 이무수물, 이의 제조방법 및 이로부터 제조된 폴리이미드
JP5792070B2 (ja) オキセタン環含有（メタ）アクリル酸エステル化合物
JPH0762065A (ja) 新規ポリカーボネート樹脂の製法および新規ポリカーボネート樹脂
CN113667110B (zh) 一种光学聚碳酸酯树脂及其制备方法
WO2013100288A1 (fr) Copolymère polycarbonate-polysiloxane ramifié et son procédé de préparation
WO2023200247A1 (fr) Composition de monomères pour la synthèse de plastique recyclé, procédé de fabrication, plastique recyclé et produit moulé l'utilisant
WO2023200244A1 (fr) Composition de monomères pour la synthèse de matières plastiques recyclées, procédé pour leur fabrication, et matières plastiques recyclées et articles moulés les utilisant
JPH0774202B2 (ja) 置換された不飽和スルホニルオキシ基含有ビシクロイミド及びその製法
CN115087648B (zh) 化合物、热塑性树脂、光学构件、光学透镜
JPH02214721A (ja) 新規なポリカーボネート樹脂およびその製造法
JP2005272735A (ja) ポリカーボネート重合体、該重合体の製造方法及び該重合体よりなる光学成形品
Yamaye et al. Chemical recycling of polyesters. One-pot–two-step conversion of poly (ethylene 2, 6-naphthalenedicarboxylate) and poly (tetramethylene terephthalate), producing the corresponding hydroxamic acids and hydrazides
WO2020032721A1 (fr) Polycarbonate et son procédé de production
JP5366740B2 (ja) 含エーテル環状構造含有ポリマー、光学材料用樹脂組成物、並びにその成形体、光学部品及びレンズ
WO2021045527A1 (fr) Composé diol, polycarbonate et procédé de production correspondant
JP7168200B2 (ja) 官能基化シクロオレフィンポリマー
SE2251532A1 (en) Isocyanate-free and bpa-free co-poly(urethane-carbonate)

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170706

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: C08G 64/02 20060101ALI20180704BHEP

Ipc: C08G 64/30 20060101AFI20180704BHEP

A4 Supplementary search report drawn up and despatched

Effective date: 20181011

RIC1 Information provided on ipc code assigned before grant

Ipc: C08G 64/30 20060101AFI20181005BHEP

Ipc: C08G 64/02 20060101ALI20181005BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190510