WO2018006146A1 - Method for obtaining hydroxylated oligomers of bisphenol a polycarbonate and use - Google Patents
Method for obtaining hydroxylated oligomers of bisphenol a polycarbonate and use Download PDFInfo
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- WO2018006146A1 WO2018006146A1 PCT/BR2017/000066 BR2017000066W WO2018006146A1 WO 2018006146 A1 WO2018006146 A1 WO 2018006146A1 BR 2017000066 W BR2017000066 W BR 2017000066W WO 2018006146 A1 WO2018006146 A1 WO 2018006146A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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- 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
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- 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
- C08G64/42—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- 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
- C08G64/04—Aromatic polycarbonates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to one. process of obtaining bisphenol A polycarbonate oligomers functionalized with terminal hydroxyls, said oligomer and its use.
- the present invention falls within the field of application of chemistry, more specifically in the area of polymers, in the production of polyols as reactive components. in. thermoplastic, thermoset and elastomer formulations.
- PC Bisphenol A
- PC polycarbonate
- Tg ⁇ 147 ° C glass transition temperature
- n ⁇ 1.58 high reign index
- Such attractive features give the PC the position of second most produced engineering thermoplastic in the world, having applications in various industrial sectors, such as aeronautics, automotive, construction, among others.
- the present invention relates to a process of obtaining terminally functioning PC oligomers with terminal hydroxyls and controlled molar mass by homogeneous PC soivolysis employing glycols in high boiling solvents and without the addition of catalysts.
- REGULATING THE POLYMERIZATION OF CYCLIC POLYCARTONATE WITH INITIATOR AND POLYHYDRIC PHENGl refers to a polymerization methodology for the production of 6,279 to 178,165 g / mol molar mass polycarbonates using cyclic carbonate and "polyhydric" phenols "as precursors. Additionally, in this document, phenols (compounds of high toxicity) are employed and the products obtained have high molar masses and dispersion (D M > 2.9).
- the present invention differs from this document mainly in that the methodology aims at the reduction of molar mass with simultaneous functionalization of PC, originally of high molar mass, with hydroxyls, resulting in low molar mass products with narrow dispersion (D M ⁇ 1.5).
- POLYCARBONATE WASTES WITM MICROWAVE IRRADIATION reports polycarbonate glycolysis in heterogeneous medium, aiming at the total recovery of bisphenol A from PC, while that the present invention relates to obtaining a terminal hydroxyl-functionalized oligameric polycarbonate was homogeneous so that it is reactive and can be employed in subsequent reactions.
- OLIGOMERS AND LOW MOLECULAR WETGHT POLYcARBGNATE FRACTIONS BY 13 C AND NMR SPECTROSCOPY is a study of possible polycarbonate end groups prepared by different routes using molar mass regulators or fractions of the same polycarbonate. However, it does not anticipate the knowledge of the production of hydroxyl functionalized PC oligomers. Additionally, said document mentions the use of phosgene in the toxic, unused process: in the present invention.
- the low molar mass enables the use of these oligomers in resin formulations for coatings (paints and varnishes), as well as other thermoplastic, thermoset and elastomer formulations.
- the present invention relates to a process of obtaining terminal hydroxyl-functional PC oligomers by homogeneously polycarbonate solvolysis using glycols at elevated temperatures and without the addition of catalysts.
- the PC oligomer obtained from this process has molar mass controlled by the process conditions and terminal hydroxyls, which enable subsequent reactions.
- the present invention generates bisphenol A as a by-product
- Figure 2 shows the FTIR spectrum for the product subjected to 2-fold purification by solubilization and precipitation.
- Figure 3 represents two 1 H spectra
- Figure 4. represents the behavior of the average numerical molar mass (M G ) as a function of synthesis time.
- the present invention relates to a process for obtaining hydroxylated PC oligomers, comprising the steps;
- Step 2 of such a process is optional according to the desired color of the final product, since without bubbling there is partial oxidation of the oligomers resulting in the product softening. Therefore, for applications where color is a critical point, inert gas bubbling is recommended.
- the process refers to the solvolysis of polycarbonate in homogeneous medium in which glycols are employed at elevated temperatures and no catalysts are added.
- Oligomers obtained by said process are hydroxyl PC oligomers.
- Terminals: here called PC (OH :) a with controlled molar mass under process conditions (glycol / PC ratio, time, temperature and concentration of reaction medium), as exemplified in Table 1, allowing modulation of product properties according to the purpose of the application.
- Table 1 presents various reaction conditions with respect to temperature (T), concentration (C) and ethylene glycol / polycarbonatQ (EG / PC) molar ratio, and their effects on products and by-products.
- FC (OH) 2 with desired molar mass of 3,000 g / mol from 1.0 g PC ⁇ 02: 6]
- PC ethylene glycol
- DMAc N-dimethyl acetamide solvent
- the PC / DMAc mixture in the 40/100 mass ratio, was stirred and heated to 150 ° C for PC dissolution. After 1 hour, argon was bubbled for up to 10 minutes at a flow rate of up to 3 L min- 1 and 20.8 ⁇ EG of EG was added. Then, the reaction solution was stirred for up to: 48 h at 150 ° C and under argon flow. At the end of this period, the reaction was stopped by sudden cooling in running water at 22 ° C. Recovery / purification of hydroxylated PC oligomers was by ethanol precipitation. The volumetric, non-solvent / reaction solution ratio was 10/1. The precipitate was recovered by vacuum filtration and dried. Drying was accelerated in a vacuum oven for up to.
- Figure 1 shows the profile of the DSC curves for the 1st and 2nd heating for oligomers produced from 100g and!, Okg of PC. Note that the profiles of the two pilot batches (“P1") and "P2" respectively) are similar in both 1st and 2nd heating.
- FIG. 3 shows two 1 H NMR spectra: one of the product as synthesized (black) and the other after reaction with trifluoracetyl anhydride (red), which is a specific reagent for hydroxy.
- red trifluoracetyl anhydride
- the signal suppression ⁇ 4.7 ppm relative to the hydrogens of the PC (OH) 2-chain chain hydroxy has been suppressed.
- M n was performed and the value of 1,800 g / mol -1 was estimated. Hydrogen assignments were also performed based on the literature and are shown in Figure 3.
- Figure 4 shows the behavior of the average numerical molar mass (M n ) as a function of reaction time.
- An exponential and asymptotic reduction of M n is noted with increasing glycolysis time, characteristic of a depolymerization mechanism. by random splitting of chains. After the first hour of reaction, a 30% reduction in molar mass is observed and after 1.5 h this reduction in molar mass reaches 85%, showing that this is a rapid process. From two hours of synthesis the molar mass does not change significantly.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
"PROCESSO DE OBTENÇÃO DE OLIGÔMEROS HIDROXILADOS DE "PROCESS FOR OBTAINING HYDROXYLED OLIGOMERS OF
POLICÃRBONATO DE BISFENOL A E USO" BISPHENOL A POLYCORBONATE AND USE "
CAMPO DA INVENÇÃO FIELD OF INVENTION
[001] A presente invenção refere-se a um. processo de obtenção de olígômeros de policarbonato de bisfenol A funcionalizados com hidroxilas terminais , o dito oligômero e seu uso. The present invention relates to one. process of obtaining bisphenol A polycarbonate oligomers functionalized with terminal hydroxyls, said oligomer and its use.
[002] A presente- invenção se insere no campo de aplicação da química, mais especificamente, na área de polímeros, na produção de políóis como componentes reativos. em. formulações de termoplásticos, termofixos e elastômeros. [002] The present invention falls within the field of application of chemistry, more specifically in the area of polymers, in the production of polyols as reactive components. in. thermoplastic, thermoset and elastomer formulations.
FUNDAMENTOS DA INVENÇÃO BACKGROUND OF THE INVENTION
[003] O policarbonato de Bisfenol A (PC) ê um polímero predominantemente amorfo, que apresenta elevada temperatura de transição vítrea (Tg ≈ 147°C) , elevada resistência mecânica e combina transparência com ura alto índice de reinação (n ≈ 1,58), além de ser pr.ocessável por diversos métodos. Tais características atraentes ao mercado, conferem ao PC a posição de segundo termoplástico de engenharia mais produzido no mundo, tendo aplicações em diversos setores industriais, como aeronáutico, automotivo, de construção civil, entre outros. Bisphenol A (PC) polycarbonate is a predominantly amorphous polymer which has a high glass transition temperature (Tg ≈ 147 ° C), high mechanical strength and combines transparency with a high reign index (n ≈ 1.58). ), besides being accessible by various methods. Such attractive features give the PC the position of second most produced engineering thermoplastic in the world, having applications in various industrial sectors, such as aeronautics, automotive, construction, among others.
[004] A presente invenção se refere a um processo de obtenção de olígômeros de PC funciona 1 i zadoS: com hidroxilas terminais e massa molar controlada por meio da soivolise do PC em meio homogéneo, empregando --se glicóís em solventes de elevado ponto de ebulição e sem a adição cie catalisadores . [004] The present invention relates to a process of obtaining terminally functioning PC oligomers with terminal hydroxyls and controlled molar mass by homogeneous PC soivolysis employing glycols in high boiling solvents and without the addition of catalysts.
[005] Alguns documentos do estado da técnica descrevem processos e tecnologias envolvendo a produção de PC e, outros, a sua despalimerização, porém nenhum, destes documentos apresenta os diferenciais técnicos da presente invenção . Some prior art documents describe processes and technologies involving the production of PC and others their depalimerization, but none of these documents present the technical differentials of the present invention.
[006] O documento de patente US4849502, METHOD GF US4849502, METHOD GF
REGULATING THE POLYMERIZATION OF CYCLIC POLYCARTONATE WITH INITiATOR AND POLYHYDRIC PHENGl, se refere a uma metodologia de polimerização, visando à produção de policarbonatos de massa molar compreendida entre 6.279 e 178.165 g/mol e hidroxí-funcionalizados, empregando-se carbonato cíclicos e fenóis "polihídricos" como precursores. Adicionalmente, no referido documento, empregam-se fenòis (compostos de alta toxicidade) e os produtos obtidos apresentam elevadas massas molares e dispersidade (DM > 2,9) . Já a presente invenção se difere deste documento principalmente pelo fato de que a metodologia visa a redução da massa molar com simultânea funcionalizaçáo do PC, originalmente de elevada massa molar, com hidroxilas, resultando em produtos de baixa massa molar e com estreita dispersidade(DM < 1,5). REGULATING THE POLYMERIZATION OF CYCLIC POLYCARTONATE WITH INITIATOR AND POLYHYDRIC PHENGl refers to a polymerization methodology for the production of 6,279 to 178,165 g / mol molar mass polycarbonates using cyclic carbonate and "polyhydric" phenols "as precursors. Additionally, in this document, phenols (compounds of high toxicity) are employed and the products obtained have high molar masses and dispersion (D M > 2.9). The present invention differs from this document mainly in that the methodology aims at the reduction of molar mass with simultaneous functionalization of PC, originally of high molar mass, with hydroxyls, resulting in low molar mass products with narrow dispersion (D M <1.5).
[007] O artigo de NIKJE, MIR M. A., GLYCOLYSIS GF [007] The article by NIKJE, MIR M. A., GLYCOLYSIS GF
POLYCARBONATE WASTES WITM MICROWAVE IRRADIATION, relata a glicólise de policarbonatos em meio heterogéneo, visando à recuperação total do bisfenol A partindo-se do PC, enquanto que a presente invenção se refere à obtenção de um policarbonato oligamérico e funcionalizado com hidroxilas terminais era meio homogéneo, para que este seja reativo e possa ser empregado em reações subsequentes. POLYCARBONATE WASTES WITM MICROWAVE IRRADIATION, reports polycarbonate glycolysis in heterogeneous medium, aiming at the total recovery of bisphenol A from PC, while that the present invention relates to obtaining a terminal hydroxyl-functionalized oligameric polycarbonate was homogeneous so that it is reactive and can be employed in subsequent reactions.
[008] O artigo de SJrman, Ya . G . et al , STUDY OF [008] The article by SJrman, Ya. G et al, STUDY OF
OLIGOMERS AND LOW MOLECULAR WETGHT POLYcARBGNATE FRACTIONS BY 13C AND NMR SPECTROSCOPY, tratá-se de um estudo de possíveis grupos terminais de policarbonatos preparados por diferentes rotas e empregando-se agentes reguladores de massa molar ou de frações de um mesmo policarbonato. Contudo não antecipa o conhecimento da produção de oiigômeros de PC funcionalizados com hidroxilas. Adicionalmente, o referido documento menciona o uso de fosgênio no processo, produto tóxico, não utilizado: na presente invenção. OLIGOMERS AND LOW MOLECULAR WETGHT POLYcARBGNATE FRACTIONS BY 13 C AND NMR SPECTROSCOPY is a study of possible polycarbonate end groups prepared by different routes using molar mass regulators or fractions of the same polycarbonate. However, it does not anticipate the knowledge of the production of hydroxyl functionalized PC oligomers. Additionally, said document mentions the use of phosgene in the toxic, unused process: in the present invention.
[009] Diante do exposto, nenhum dos documentos do estada da técnica descreve um processo de obtenção de oiigômeros de PC hidroxilados, de massa molar controlada por meio de solvólise em meio homogéneo empregándo-se glicóis esolventes de elevado ponto de ebulição. In the light of the foregoing, none of the prior art documents describe a process for obtaining hydroxylated molar mass PC oligomers controlled by homogeneous solvolysis using high boiling solvents glycols.
[010] A baixa massa molar viabiliza o emprego destes oligômeros era formulações de resinas para o ramo de revestimentos (tintas e vernizes), bem come demais formulações de termoplásticos, termofixos e elastômeros. [010] The low molar mass enables the use of these oligomers in resin formulations for coatings (paints and varnishes), as well as other thermoplastic, thermoset and elastomer formulations.
[011] A incorporação destes oiigômeros em formulações visa à -modulação, de propriedades físico- químicas, ópticas e mecânicas do produto final. [012] Adicionalmente, o processo proposto nesta invenção é uma alternativa para reciclagem química dos rejeitos de PC, gerando produtos com valor agregado (oligômeros funcionalizados e de baixa díspersidade de massa molar): além da possibilidade de se recuperar o monome.ro (bisfenoi A) . [011] The incorporation of these oligomers into formulations aims at modulating physicochemical, optical and mechanical properties of the final product. Additionally, the process proposed in this invention is an alternative for chemical recycling of PC tailings, generating value-added products (functionalized oligomers and low molar mass dispersion): in addition to the possibility of recovering monomer (bisphenyl). THE) .
BREVE DESCRIÇÃO DÃ INVENÇÃO BRIEF DESCRIPTION GIVES INVENTION
[013] A presente invenção refere-se a um processo de obtenção de oligômeros de PC funcionâlizados com hidroxilas terminais, por meio da solvôlise do policarbonato, por via homogénea e empregando-se glícois a elevadas temperaturas e sem a adição de catalisadores. [013] The present invention relates to a process of obtaining terminal hydroxyl-functional PC oligomers by homogeneously polycarbonate solvolysis using glycols at elevated temperatures and without the addition of catalysts.
[014] O oligômero de PC obtido deste processo apresenta massa molar controlada pelas condições de processo e hidroxilas terminais,: que viabilizam reaçóes subsequentes. The PC oligomer obtained from this process has molar mass controlled by the process conditions and terminal hydroxyls, which enable subsequent reactions.
[015] Adicionalmente, a presente invenção gera bisfenol A como produto secundário, Additionally, the present invention generates bisphenol A as a by-product,
BREVE DESCRIÇÃO DAS FIGURAS BRIEF DESCRIPTION OF THE FIGURES
[016] A Figura 1 apresenta as curvas de DSC para o [016] Figure 1 shows the DSC curves for the
1° e 2° aquecimento dos produtos dos processos de obtenção do PC (08) 2 realizados em laboratório (lOOg) e em escala piloto (PI e P2) após purificação. Ss setas no gráfico referente ao 20 aquecimento indicara a transição vítrea. 1st and 2nd heating of the products obtained from the PC (08) 2 processes obtained in the laboratory (100g) and pilot scale (PI and P2) after purification. The arrows on the warming graph will indicate the glass transition.
[017] A Figura 2 apresenta o espectro de FTIR para o produto submetido à purificação por 2 vezes através de soiubilização e precipitação. [018] A Figura 3 representa dois espectros de 1 H[017] Figure 2 shows the FTIR spectrum for the product subjected to 2-fold purification by solubilization and precipitation. [018] Figure 3 represents two 1 H spectra
NMR, sendo um referente ao produto originalmente sintetizado e outro após reação com anidrido trifluoracético . NMR, one referring to the originally synthesized product and another after reaction with trifluoroacetic anhydride.
[018] A Figura 4. representa o comportamento da massa molar numérica média (MG) em função do tempo de síntese. [018] Figure 4. represents the behavior of the average numerical molar mass (M G ) as a function of synthesis time.
DESCRIÇÃO DETALHADA DA INVENÇÃO DETAILED DESCRIPTION OF THE INVENTION
[020] A presente invenção refere-se a um processo de obtenção de oligômeros de PC hidroxilados, que compreende as etapas; [020] The present invention relates to a process for obtaining hydroxylated PC oligomers, comprising the steps;
1) Dissolução do policarbonato a temperaturas variáveis entre 1G:0 e 250 °C, a concentrações entre 1% e 50% em solvente, sendo este solvente de elevado ponto de ebulição, preferencialmente Ν,Ν-dimetiIacetamida (DMAc) , N , N- dimetilformamida (DMF) e l-metii-2-pirrolidona (NMP) ; 1) Dissolving the polycarbonate at varying temperatures between 1G : 0 and 250 ° C, at concentrations between 1% and 50% in solvent, this solvent having a high boiling point, preferably Ν, Ν-dimethylacetamide (DMAc), N, N dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (NMP);
2 ) Borbulhamento com gás inerte ; 2) Inert gas bubbling;
3) Adição de um glicol na razão molar glicol/policarbonato variável entre 0,1 e 50, a temperaturas variáveis entre 20 e 250 °C; sendo utilizados glicóis variados, preferencialmente etileno glicol, propileno glicol e dietileno glicol; 4) Interrupção da reação por resfriamento súbito; 3) Addition of a glycol in the glycol / polycarbonate molar ratio varying from 0.1 to 50, at varying temperatures between 20 and 250 ° C; various glycols being used, preferably ethylene glycol, propylene glycol and diethylene glycol; 4) Interruption of reaction by sudden cooling;
5) Precipitação por adição de não-solvente , como o etanol e outros solventes mi seiveis com o solvente do meio reacional e imiscíveis com os oligômeros; 6) Filtração; 5) Precipitation by addition of non-solvent such as ethanol and other solvents miscible with the reaction medium solvent and immiscible with the oligomers; 6) Filtration;
7 ) Secagem . 7) Drying.
[021] A Λ etapa 2 de tal processo é opcional, de acordo com a cor desejada do produto finai, posto: que, sem o borbulhamento ocorre a oxidação parcial dos oligomeros resultando no amareiecimento do produto. Desta maneira, para aplicações nas quais a cor é um ponto critico, recomenda-se o borbulhamento com gás inerte. [021] Step 2 of such a process is optional according to the desired color of the final product, since without bubbling there is partial oxidation of the oligomers resulting in the product softening. Therefore, for applications where color is a critical point, inert gas bubbling is recommended.
[022] O processo se refere à solvolise do policarbonato em meio homogéneo, no qual se empregam glieóis a elevadas temperaturas e não se adiciona catalisadores. [022] The process refers to the solvolysis of polycarbonate in homogeneous medium in which glycols are employed at elevated temperatures and no catalysts are added.
[023] Os oligomeros obtidos por meio do referido processo se tratam de oligõmeros de PC com hidroxilas. terminais:, chamados aqui de PC (OH:) a, com massa molar controlada peias condições do processo (razão glicol/PC, tempo, temperatura e concentração do meio reacional ) , conforme exemplificado na Tabela 1, permitindo a modulação de propriedades do produto final de acordo com a finalidade da aplicação. Oligomers obtained by said process are hydroxyl PC oligomers. Terminals: here called PC (OH :) a, with controlled molar mass under process conditions (glycol / PC ratio, time, temperature and concentration of reaction medium), as exemplified in Table 1, allowing modulation of product properties according to the purpose of the application.
Tabela 1. A. Tabela 1 apresenta diversas condiçoes de reação com respeito a temperatura (T) , à concentração ( C ) e à razão molar etileno glicol/policarbonatQ (EG/PC), e os resp.eetivps efeitos sobre os produtos e subprodutos Table 1. A. Table 1 presents various reaction conditions with respect to temperature (T), concentration (C) and ethylene glycol / polycarbonatQ (EG / PC) molar ratio, and their effects on products and by-products.
[024] 0 referido processo de solvóli se : do policarbonato também resulta em bis feno1 A oomo produto secundário e seu rendimento pode ser controlado pelas condições de processo (razão glicol /PC, tempof temperatura e concentração do meio reacional). [024] 0 solvóli said process is: Polycarbonate also results in oomo bis feno1 The secondary product and its performance can be controlled by process conditions (ratio glycol / PC, time and temperature f concentration of the reaction medium).
Exemplos de concretização Embodiment Examples
[025] Para exemplificar a obtenção do PC(OH) 2 e caracteriza-lo, os seguintes testes foram realizados. Obtenção do FC (OH) 2 com massa molar desejada de 3.000 g/mol, a partir de 1,0 g de PC {02:6] Os seguintes materiais foram utilizados: PC na concentração de. 40%, etileno glicol (EG) , solvente N, N- dimetil-acetamida (DMAc) e o não-soivente etanol comercial . [025] To exemplify the obtaining of PC (OH) 2 and characterize it, the following tests were performed. Obtaining FC (OH) 2 with desired molar mass of 3,000 g / mol from 1.0 g PC {02: 6] The following materials were used: PC at the concentration of. 40%, ethylene glycol (EG), N, N-dimethyl acetamide solvent (DMAc) and the non-soluble commercial ethanol.
[027] A mistura PC/DMAc, na proporção mássica 40/100, foi agitada e aquecida a 150 °C para dissolução do PC. Após 1 hora, borbulhou-se argônio por até 10 minutos à vazão de até 3 L min-1 e adieionou-se 20,8 μΐ, de EG. Então, a solução reacional foi submetida à agitação por até: 48 h a 150 °C e sob fluxo de argônio. Ao término deste período, a reação foi interrompida por resfriamento súbito em água corrente a 22 °C. A recuperação/purificação dos oligômeros de PC hidroxilados ocorreu por precipitação em etanol. A razão volumétrica, não-solvente/solução reacional foi de 10/1. 0 precipitado foi recuperado por filtração a vácuo e seco. A secagem foi acelerada em estufa a vácuo por até. 24 h a 70 *C. Apôs este procedimento, o sólido foi lavado: por mais 2 vezes com etanol comerciai a fim de se retirar o bisfenol A residual, produto secundário deste processo. Obtençâo do PC (OH) 2 com massa molar desejada de 3.000 g/mol , a partir de 1,0 Kg de PC The PC / DMAc mixture, in the 40/100 mass ratio, was stirred and heated to 150 ° C for PC dissolution. After 1 hour, argon was bubbled for up to 10 minutes at a flow rate of up to 3 L min- 1 and 20.8 μ EG of EG was added. Then, the reaction solution was stirred for up to: 48 h at 150 ° C and under argon flow. At the end of this period, the reaction was stopped by sudden cooling in running water at 22 ° C. Recovery / purification of hydroxylated PC oligomers was by ethanol precipitation. The volumetric, non-solvent / reaction solution ratio was 10/1. The precipitate was recovered by vacuum filtration and dried. Drying was accelerated in a vacuum oven for up to. 24 h at 70 ° C. After this procedure, the solid was washed 2 more times with commercial ethanol to remove residual bisphenol A, a by-product of this process. Obtaining PC (OH) 2 with desired molar mass of 3,000 g / mol from 1.0 kg of PC
[028] Utilizando-se os seguintes materiais: PC na concentração de 4QS, etileno glicol (E.G1 , solvente DMAc e o não-soivente etanol comercial . Using the following materials: PC at 4QS concentration, ethylene glycol (E.G1, DMAc solvent and commercial non-soluble ethanol.
[029] A mistura PC/DMAc, na proporção mássica [029] The PC / DMAc mixture in mass ratio
40/100, foi agitada e aquecida a 150 °C para dissolução do PC. Após 1 hora, borbulhou-se. o nitrogénio por até 30 minutos à vazão de 3 L min-1 e adicionou- se 20,8 ml, de EG. Então, a solução reacional foi submetida à agitação e a aquecimento por até 48 h a 150 °C. Ao término deste período, a reação foi interrompida por resfriamento súbito pela adição do meio reacional ao etanol comercial a temperaturas em torno de 20 °C. Esta etapa também resultou na purificação dos oligômeros. A razão volumétrica etanol /solução reacional foi de 10/1. O precipitado foi recuperado por filtração (a vácuo) e seco em estufa a vácuo por até 36h a 10 °C. Após este. procedimento, o sólido foi lavado por 2 vezes com etanol comercial . 40/100, was stirred and heated to 150 ° C for PC dissolution. After 1 hour, it bubbled. nitrogen for up to 30 minutes at 3 L min -1 flow rate and 20.8 ml of EG was added. Then, the reaction solution was stirred and heated for up to 48 h at 150 ° C. At the end of this period, the reaction was stopped by sudden cooling by the addition of the reaction medium to commercial ethanol at temperatures around 20 ° C. This step also resulted in purification of the oligomers. The ethanol / reaction solution volume ratio was 10/1. The precipitate was recovered by filtration (vacuum) and dried in a vacuum oven for up to 36h at 10 ° C. After this one. procedure, the solid was washed 2 times with commercial ethanol.
Aplicação de técnica DSC (DIFFERENTIAL SCANNING CALORIMETRY) para as amostras obtidas a partir de 100 g e 1,0 Kg de PC (P1 e P2 ) Application of DSC (DIFFERENTIAL SCANNING CALORIMETRY) technique to samples obtained from 100 g and 1.0 Kg PC (P1 and P2)
[030] A Figura 1 mostra o perfil das curvas de DSC referentes ao 1° e ao 2° aquecimento para os oligômeros produzidos a partir de lOOg e de !, Okg de PC. Nota-se oue os perfis das duas bateladas piloto ("P1")e "P2" respectivamente) são similares tanto no 1° quanto no 2° aquecimento . Figure 1 shows the profile of the DSC curves for the 1st and 2nd heating for oligomers produced from 100g and!, Okg of PC. Note that the profiles of the two pilot batches ("P1") and "P2" respectively) are similar in both 1st and 2nd heating.
Aplicação de técnica FTIR (Fourier Transform Infrared Spectroscopy) mostrando á funcionalização do PC a BC (OH) 2. Application of Fourier Transform Infrared Spectroscopy (FTIR) technique showing PC functionalization to BC (OH) 2.
[031] 0 espectro de FTIR (FigUía 2) para o produto purificado por duas vezes ísolubilizado em clorofórmio -e- precipitado em etanol) apresenta as mesmas bandas de absorção observadas para o PC puro, além da banda na região de 3.500 cm1 atribuída á inserção de hidroxilas terminais às cadeias dos oligômeros, indicando a funcionalizaçâo destes a PC (OH) 2 · Aplicação de técnica 1H NMR (groton Nuclear Magnetic Resonance Spectroscopy) evidenciando a funcionalizaçao do PC a PC (OH) 2 -The FTIR spectrum (Fig. 2) for the chloroform-soluble twice-ethanol-precipitated twice-purified product shows the same absorption bands as for pure PC, in addition to the 3,500 band. cm 1 attributed to the insertion of terminal hydroxyls into the oligomer chains, indicating their functionalization to PC (OH) 2 · Application of 1 H NMR technique (groton Nuclear Magnetic Resonance Spectroscopy) showing the functionalization of PC to PC (OH) 2 -
[032] A. Figura 3 apresenta dois espectros de 1H NMR: um do produto tal qual sintetizado (preto) e outro após reação com anidrído trifluoracétieo (vermelho) , que é um reagente especifico para hidroxiias. Mo espectro do oligômero acetilado (vermelho) ocorreu a supressão do sinal δ = 4,7 ppm relativo aos hidrogêníos das hidroxiias de ponta de cadeia dos oligômeros PC (OH) 2- Uma vez identificados os hidroçênios, o cálculo de massa molar numérica média (Mn) foi realizado sendo estimado o valor de 1.800 g/mol-1. As atribuições dos hidrogêníos foram realizadas, também, com base na literatura e estão indicados na Figura 3. A. Figure 3 shows two 1 H NMR spectra: one of the product as synthesized (black) and the other after reaction with trifluoracetyl anhydride (red), which is a specific reagent for hydroxy. In the acetylated oligomer spectrum (red), the signal suppression δ = 4.7 ppm relative to the hydrogens of the PC (OH) 2-chain chain hydroxy has been suppressed. M n ) was performed and the value of 1,800 g / mol -1 was estimated. Hydrogen assignments were also performed based on the literature and are shown in Figure 3.
Aplicação de técnica 62?C (Gel Fermeation Chromatography) para demonstrar o controle de massa molar com o "tempo, Application of 62? C (Gel Fermeation Chromatography) technique to demonstrate the control of molar mass with "time,
[033] A Figura 4 mostra o comportamento da massa molar numérica média (Mn) em função do tempo de reação. Nota- se uma redução exponencial e assimptótica de Mn com o aumento do tempo de glicólise, característica de um mecanismo de despolimerização. por cisão aleatória de cadeias. Após a primeira hora de reação nota-se á redução de 30% da massa molar e, após 1,5 h esta redução de massa molar atinge 85%, mostrando que se trata de um processo rápido. A partir de duas horas de síntese a massa molar não se altera significativamente. [033] Figure 4 shows the behavior of the average numerical molar mass (M n ) as a function of reaction time. An exponential and asymptotic reduction of M n is noted with increasing glycolysis time, characteristic of a depolymerization mechanism. by random splitting of chains. After the first hour of reaction, a 30% reduction in molar mass is observed and after 1.5 h this reduction in molar mass reaches 85%, showing that this is a rapid process. From two hours of synthesis the molar mass does not change significantly.
Claims
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| US5652275A (en) * | 1994-06-21 | 1997-07-29 | Bayer Aktiengesellschaft | Process for the chemical recycling of polycarbonates |
| US6034142A (en) * | 1997-12-12 | 2000-03-07 | General Electric Company | Method for recycling aromatic polycarbonates |
| US7105632B2 (en) * | 2002-12-11 | 2006-09-12 | General Electric Company | Recycle method for polycarbonate resin waste |
| WO2015063642A1 (en) * | 2013-10-28 | 2015-05-07 | Sabic Global Technologies B.V. | Melt polymerization polycarbonate quenching with inert gas saturation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5652275A (en) * | 1994-06-21 | 1997-07-29 | Bayer Aktiengesellschaft | Process for the chemical recycling of polycarbonates |
| US6034142A (en) * | 1997-12-12 | 2000-03-07 | General Electric Company | Method for recycling aromatic polycarbonates |
| US7105632B2 (en) * | 2002-12-11 | 2006-09-12 | General Electric Company | Recycle method for polycarbonate resin waste |
| WO2015063642A1 (en) * | 2013-10-28 | 2015-05-07 | Sabic Global Technologies B.V. | Melt polymerization polycarbonate quenching with inert gas saturation |
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| NIKJE , MIR M. A. ET AL.: "Glycolysis of polycarbonate wastes with microwave irradiation", POLIMERY, vol. 56, no. 5, 2011, pages 381 - 384, XP055450271 * |
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| WO2022159040A1 (en) * | 2021-01-25 | 2022-07-28 | Nanyang Technological University | Method of upcycling condensation polymers in plastic waste via co-catalytic partial depolymerization |
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