EP3861050A1 - Procédé de préparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylène téréphtalate) - Google Patents
Procédé de préparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylène téréphtalate)Info
- Publication number
- EP3861050A1 EP3861050A1 EP19805361.3A EP19805361A EP3861050A1 EP 3861050 A1 EP3861050 A1 EP 3861050A1 EP 19805361 A EP19805361 A EP 19805361A EP 3861050 A1 EP3861050 A1 EP 3861050A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester
- nucleating agent
- dianhydrohexitol
- terephthalate
- poly
- 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.)
- Pending
Links
Classifications
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
Definitions
- PET Polyethylene terephthalate
- PET is a polyester comprising ethylene glycol and terephthalic acid units, used for example in the manufacture of containers, packaging, films or even fibers.
- polyesters do not exhibit a sufficient level of performance, in particular in terms of optical properties, impact resistance or thermal resistance.
- modified glycol PET PETg
- CHDM cyclohexanedimethanol
- modified PETs have also been developed by introducing 1,4, 3,6-dianhydrohexitol units into the polymer chain, in particular isosorbide. These are poly (ethylene-co-isosorbide terephthalate) or PEIT. These modified polyesters have higher glass transition temperatures than unmodified PETs or PETg comprising CHDM. In addition, 1,4: 3,6-dianhydrohexitols have the advantage that they can be obtained from renewable resources such as starch. These modified polyesters are especially useful for the manufacture of bottles, films, thick sheets, fibers or articles requiring high optical properties.
- polyesters based on isosorbide and incorporating CHDM units have emerged: (poly (isosorbide-co-cyclohexylene terephthalate) or PITg.
- PITg poly (isosorbide-co-cyclohexylene terephthalate)
- PITg poly (isosorbide-co-cyclohexylene terephthalate)
- Polyesters containing isosorbide, and in particular P ⁇ Tg are conventionally produced by the molten route.
- this synthesis technique makes it difficult to achieve the high molecular weights required for applications requiring high mechanical properties or high melt viscosities necessary for the transformation and shaping of these polymers.
- higher molecular weights can be obtained by carrying out a solid state post-condensation (PCS) of the polymer. It is the process conventionally used to obtain PET intended for the manufacture of fibers or bottles. PCS allows the chain reaction to continue, but on solid granules. To do this, the granules must first be crystallized in order to avoid the formation of aggregates at high temperature and in order to concentrate the chain ends in the amorphous domains.
- PCS solid state post-condensation
- the subject of the invention is therefore a process for the preparation of a polyester of poly (1, 4: 3,6-dianhydrohexitol-cocyclohexylene terephthalate) type, said process comprising: a) a step of synthesis of said polyester, by oligomerization then polycondensation ,; b) a step of recovering the polyester;
- the nucleating agent is added during step a) or during step c) when this is not optional.
- the crystallization time of poly (1,4: 3,6-dianhydrohexitol- cocyclohexylene terephthalate) is greatly reduced, compared to that of the same polyester synthesized in the absence of nucleating agent.
- the use of the nucleating agent prevents the formation of agglomerates during the post-condensation step by PCS.
- the mechanical, thermal and optical properties of the synthesized polyester are not affected by the use of this nucleating agent.
- the invention also relates to a composition
- a composition comprising a polyester of poly (1,4: 3,6-dianhydrohexitol-cocyclohexylene terephthalate) type and at least one nucleating agent.
- Another subject of the invention relates to a plastic article, finished or semi-finished, comprising the composition according to the invention.
- the subject of the invention is therefore a process for the preparation of a polyester of poly (1, 4: 3,6-dianhydrohexitol-cocyclohexylene terephthalate) type comprising: a) a step of synthesis of said polyester, by oligomerization then polycondensation,; b) a step of recovering the polyester;
- the reduced viscosity in solution [35 ° C; orthochlorophenol; 5 g of polyester / L] of said polyester is greater than 50 mL / g.
- polyesters comprising units 1, 4: 3,6-dianhydrohexitol with which, during shaping, the times of cycles during the injection of parts is reduced, and the mechanical and physical properties, such as the mechanical properties of the wires or the barrier properties of bottles, are improved.
- the synthesis of polyester is generally carried out using at least one 1,4: 3,6-dianhydrohexitol (A), at least one alicyclic diol (B) other than the 1,4: 3,6-dianhydrohexitols (A) and at least one terephthalic acid (C).
- the molar ratio ((A) + (B)) / (C) advantageously ranging from 1.05 to 1.5, said monomers being free of non-cyclic aliphatic diol or comprising, relative to all of the monomers introduced, an amount molar of non-cyclic aliphatic diol units of less than 5%.
- a non-cyclic aliphatic diol can be a linear or branched non-cyclic aliphatic diol. It can also be a saturated or unsaturated non-cyclic aliphatic diol.
- the saturated linear non-cyclic aliphatic diol can for example be 1, 3-propanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and / or 1,10-decanediol.
- a saturated branched non-cyclic aliphatic diol mention may be made of 2-methyl-1, 3-propanediol, 2,2,4-trimethyl-1, 3-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, propylene glycol and / or neopentylglycol.
- an unsaturated aliphatic diol mention may be made, for example, of cis-2-butene-1,4-diol.
- a stage of deoxygenation of the monomers is preferably carried out prior to the first stage of oligomerization. It can be done for example by carrying out, after having introduced the monomers into the reactor, a vacuum and then by introducing an inert gas such as nitrogen into the reactor.
- This vacuum-introduction cycle of inert gas can be repeated several times, for example from 3 to 5 times.
- this vacuum-nitrogen cycle is carried out at a temperature between 60 and 80 ° C. so that certain reagents, and in particular the diols, are completely melted.
- This deoxygenation step has the advantage of improving the coloring properties of the polyester obtained at the end of the process.
- the first stage of the polymerization stage preferably has a duration ranging from 20 minutes to 5 hours.
- the second stage has a duration ranging from 30 minutes to 6 hours, the beginning of this stage consisting in the moment when the reactor is placed under vacuum, that is to say at a pressure of less than 1 bar.
- the method according to this embodiment comprises a step of introducing a catalytic system into the reactor. This step can take place before or during the polymerization step described above.
- the catalyst is used in suitable amounts to obtain a high viscosity polymer in accordance with the invention.
- esterification catalyst is advantageously used during the oligomerization stage.
- This esterification catalyst can be chosen from tin, titanium, zirconium, hafnium, zinc, manganese, calcium, strontium derivatives, organic catalysts such as para-toluene sulfonic acid (APTS ), methane sulfonic acid (AMS) or a mixture of these catalysts.
- APTS para-toluene sulfonic acid
- AMS methane sulfonic acid
- the catalyst of the first stage can be optionally blocked by the addition of phosphorous acid or phosphoric acid, or else as in the case of tin (IV) reduced by phosphites such as phosphite of triphenyl or the phosphites of the tris (nonylephenyl) or those mentioned in paragraph [0034] of the application US201 1282020A1.
- the second stage of condensation of the oligomers can optionally be carried out with the addition of a catalyst.
- This catalyst is advantageously chosen from tin derivatives, preferably tin, titanium, zirconium, germanium, antimony, bismuth, hafnium, magnesium, cerium, zinc, cobalt, iron, manganese, calcium, strontium, sodium, potassium, aluminum, lithium or a mixture of these catalysts. Examples of such compounds can be, for example, those given in patent EP 1 882 712 B1 in paragraphs [0090] to [0094]
- the catalyst is a derivative of tin, titanium, germanium, aluminum or antimony.
- polymerization additive into the reactor at least one compound capable of limiting parasitic etherification reactions, such as sodium acetate, tetramethylammonium hydroxide, or tetraethylammonium hydroxide.
- the polyester thus recovered has a reduced viscosity in solution greater than 40 ml / g and generally less than 70 ml / g.
- the method can include an optional step c) of extruding the polyester obtained after step b) of recovery.
- the extrusion can be carried out in an extruder of any type, in particular a single-screw extruder, a co-rotating twin-screw extruder or a counter-rotating twin-screw extruder. However, it is preferred to carry out this extrusion step using a co-rotating extruder.
- the temperature inside the extruder is adjusted to be above the melting temperature.
- the temperature inside the extruder can range from 150 ° C to 320 ° C, preferably between 190 and 290 ⁇ .
- the process for preparing the polyester according to the invention comprises a step d) of post-condensation in solid phase (PCS).
- This is a step of increasing molar mass by post-polymerization of a polymer of reduced viscosity in a lower solution, which comprises at least one 1,4: 3,6-dianhydrohexitol unit (A), at least one alicyclic diol unit (B) other than the units 1, 4: 3,6-dianhydrohexitol (A) and at least one terephthalic acid unit (C), said polymer of reduced viscosity in lower solution being free of non-cyclic aliphatic diol units or comprising a molar amount of aliphatic diol units non-cyclic, with respect to all of the monomeric units of the polymer, less than 5%.
- PCS solid phase
- the method of the invention further comprises at least one step of introducing at least one nucleating agent.
- the introduction of at least one nucleating agent is carried out during the synthesis a) of the polyester, in particular during step a1) described previously
- the nucleating agent is chosen from talc, sodium benzoate, calcium carbonate, sodium stearate, ADK STAB® Na-05, Bruggolen® P282 and sodium montanate. More preferably, the nucleating agent is chosen from talc, sodium benzoate and ADK STAB® Na-05.
- the additive which is useful for the composition according to the invention can also comprise opacifying agents, dyes and pigments. They can be chosen from cobalt acetate and the following compounds: HS-325 Sandoplast® RED BB (which is a compound carrying an azo function also known under the name Solvent Red 195), HS-510 Sandoplast® Blue 2B which is an anthraquinone, Polysynthren® Blue R, and Clariant® RSB Violet.
- composition according to the invention can also comprise other additives such as stabilizers, for example light stabilizers, UV stabilizers and thermal stabilizers, fluidizers, flame retardants and antistatic agents.
- stabilizers for example light stabilizers, UV stabilizers and thermal stabilizers, fluidizers, flame retardants and antistatic agents.
- the composition may also comprise an additional polymer, different from the polyester according to the invention.
- the article can also be transformed by extrusion of profiles which can find their application in the fields of building and construction.
- the resin thus obtained has a viscosity in solution of 50.8 ml / g.
- the 1 H NMR analysis of the polyester shows that it contains 12.4 mol% of isosorbide relative to all of the monomeric units.
- the kinetics of crystallization were then measured by DSC. First the samples are quickly melted at 280 ° C for 2 minutes. Then the temperature is rapidly reduced to 190 ⁇ for the time necessary for the maximum crystallization of the sample. The time necessary to obtain 50% of the maximum crystallization of the sample is noted t 1/2
- the temperatures and enthalpies of hot crystallization obtained from the melt by non-isothermal crystallization at 10 ° / min are given in Table 2.
- the rate of crystallization of polymers synthesized with each of the nucleating agents is measured and compared with the speed of crystallization of a polymer synthesized without nucleating agent. The results are presented in Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1859090A FR3086663B1 (fr) | 2018-10-02 | 2018-10-02 | Procede de preparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylene terephtalate) |
PCT/FR2019/052331 WO2020070445A1 (fr) | 2018-10-02 | 2019-10-02 | Procédé de préparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylène téréphtalate) |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3861050A1 true EP3861050A1 (fr) | 2021-08-11 |
Family
ID=65244058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19805361.3A Pending EP3861050A1 (fr) | 2018-10-02 | 2019-10-02 | Procédé de préparation d'un polyester de type poly(1,4:3,6-dianhydrohexitol-cocyclohexylène téréphtalate) |
Country Status (6)
Country | Link |
---|---|
US (1) | US20220002476A1 (fr) |
EP (1) | EP3861050A1 (fr) |
KR (1) | KR20210070313A (fr) |
CN (1) | CN112955491A (fr) |
FR (1) | FR3086663B1 (fr) |
WO (1) | WO2020070445A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111320748A (zh) * | 2020-04-15 | 2020-06-23 | 河南功能高分子膜材料创新中心有限公司 | 一种耐高温聚酯的制备方法及耐高温聚酯 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5959066A (en) * | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyesters including isosorbide as a comonomer and methods for making same |
WO2006115226A1 (fr) | 2005-04-22 | 2006-11-02 | Mitsubishi Chemical Corporation | Polyester derive de la biomasse et son procede de fabrication |
FR2934272B1 (fr) | 2008-07-24 | 2013-08-16 | Roquette Freres | Procede de preparation de compositions a base de matiere amylacee et de polymere synthetique. |
NL2002382C2 (en) | 2008-12-30 | 2010-07-01 | Furanix Technologies Bv | A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers. |
KR20110028696A (ko) | 2009-09-14 | 2011-03-22 | 에스케이케미칼주식회사 | 아이소소바이드와 1,4-사이클로헥산디메탄올이 공중합된 폴리에스테르 수지 및 그 제조방법 |
US8796356B2 (en) * | 2009-09-23 | 2014-08-05 | Sabic Innovative Plastics Ip B.V. | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
KR20120121477A (ko) * | 2011-04-27 | 2012-11-06 | 에스케이케미칼주식회사 | 단단한 폴리(1,4:3,6-디안히드로헥시톨 에스테르) 제조방법 |
MX351452B (es) | 2011-10-24 | 2017-10-16 | Furanix Technologies Bv | Proceso para preparar un producto polimerico que tiene una porcion 2,5-furandicarboxilato dentro de la estructura polimerica que se va a usar en aplicaciones de botellas, peliculas o fibras. |
US20170335054A1 (en) | 2014-11-21 | 2017-11-23 | Ester Industries Limited | Heat resistant polyethylene terephthalate and process of manufacturing thereof |
FR3036400B1 (fr) | 2015-05-22 | 2019-04-26 | Roquette Freres | Polyester de haute viscosite aux proprietes choc ameliorees |
FR3054804B1 (fr) * | 2016-08-05 | 2019-07-12 | Roquette Freres | Utilisation d'un polyester thermoplastique pour la fabrication de pieces injectees |
-
2018
- 2018-10-02 FR FR1859090A patent/FR3086663B1/fr active Active
-
2019
- 2019-10-02 CN CN201980069970.8A patent/CN112955491A/zh active Pending
- 2019-10-02 WO PCT/FR2019/052331 patent/WO2020070445A1/fr unknown
- 2019-10-02 US US17/281,664 patent/US20220002476A1/en active Pending
- 2019-10-02 KR KR1020217012022A patent/KR20210070313A/ko not_active Application Discontinuation
- 2019-10-02 EP EP19805361.3A patent/EP3861050A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
CN112955491A (zh) | 2021-06-11 |
FR3086663B1 (fr) | 2020-11-13 |
KR20210070313A (ko) | 2021-06-14 |
WO2020070445A1 (fr) | 2020-04-09 |
US20220002476A1 (en) | 2022-01-06 |
FR3086663A1 (fr) | 2020-04-03 |
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