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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
  • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
  • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
  • C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
  • C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
  • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
  • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
  • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
• • 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
  • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F14/18—Monomers containing fluorine
  • C08F14/22—Vinylidene fluoride

Definitions

• the present invention relates to biosourced vinylidene difluoride.
• the invention also relates to processes for the preparation of bio-based vinylidene difluoride from various renewable raw materials.
• the invention also relates to the homopolymers of vinylidene difluoride obtained by polymerization of said monomer, as well as the copolymers obtained by copolymerization of said monomer with one or more compatible co-monomers.
• the invention finally relates to the use of said homopolymers or copolymers in all applications where the appearance of these polymers is essential and / or their properties depend on their degree of purity; these are applications in the automotive industry, filtration of fluids, especially water, offshore, medical, transport of drinking water, the semiconductor market, cables, batteries Li-ion, photovoltaics, sporting goods and sports textiles. Preferred applications are chemical engineering and electronics, including consumer electronics.
• Vinylidene difluoride (1,1-difluoroethylene or VDF) is a colorless, odorless and non-toxic gas.
• This fluorinated olefin has the advantage of not containing a chlorine or bromine atom, therefore its toxicity is lower compared to chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene (BrTFE).
• CTFE chlorotrifluoroethylene
• BrTFE bromotrifluoroethylene
• it does not have the explosive nature of tetrafluoroethylene (TFE) and it is much less expensive than TFE, hexafluoropropene (HFP), CTFE or BrTFE.
• VDF is well known for its use as a monomer in the manufacture of polyvinylidene fluoride (PVDF) and as a co-monomer in the manufacture of various types of fluoropolymers.
• VDF is obtained by steam cracking or catalytic cracking of petroleum fractions. It is synthesized industrially by pyrolytic dehydrochlorination of l-chloro-l, l-difluoroethane according to the reaction: 800 ° C
• H3C-CCIF2 ® H 2 C CF 2 + HC1
• the precursor l-chloro-l, l-difluoroethane can be prepared in four ways:
• H 2 C CCl 2 + 2 HF ® H 3 C-CClF 2 + HCl
• 1,1,2 trichlorethylene leads by hydrofluorination to 1,2-dichloro-1,1-difluoroethane, which itself can give difluoroethylene by hydrogenolysis.
• VDF synthesis processes are mainly of fossil or petroleum origin. These production processes thus contribute to the increase in the greenhouse effect and are considered as pollutants for the environment.
• the world's reserves of raw materials of fossil origin oil and natural gas
• fluoropolymers made from conventional VDF have undesirable properties; in particular, they may contain impurities which increase the yellowing index (YI) which is particularly feared for applications such as chemical engineering or even consumer electronic devices, where the aesthetics and respect for the constant of the staining is required.
• YI yellowing index
• the invention relates firstly to bio-based vinylidene difluoride.
• the renewable carbon content of the biobased VDF is at least 1 atomic%, as determined by the 14 C content according to standard NF EN 16640 of April 15, 2017. This corresponds to an isotopic ratio of 14 C / 12 C in the VDF molecule of at least 1.2x10 14 .
• the content of renewable carbon in the biobased VDF is greater than 5%, preferably greater than 10%, preferably greater than 25%, preferably greater than or equal to 33%, preferably greater than 50% , preferably greater than or equal to 66%, preferably greater than 75%, preferably greater than 90%, preferably greater than 95%, preferably greater than 98%, preferably greater than 99%, advantageously equal to 100% .
• the subject of the invention is also a process for preparing the compound according to the invention, comprising the step of supplying biobased ethylene having a renewable carbon content of at least 1%, and the transformation by synthesis into several stages into bio-based vinylidene difluoride.
• the first synthesis step is the manufacture of vinyl chloride from this bio-based ethylene. Several synthetic routes are then possible.
• the biobased vinyl chloride is transformed into biobased VDF via the following synthesis intermediates: l, l, 2-trichloroethane, l, l, l-trichloroethane and l-chloro-l, l-difluoroethane.
• the biobased vinyl chloride is transformed into biobased VDF via the following synthesis intermediates: l, l, 2-trichloroethane, l, l-dichloroethene, and l-chloro-l, l-difluoroethane.
• the biobased vinyl chloride is transformed into biobased VDF via the following synthesis intermediates: l, l-dichlorethane, l, l, l-trichloroethane and 1 -chloro-1, 1 -difluoroethane.
• Another subject of the invention is a bio-based vinylidene difluoride (PVDF) homopolymer prepared by polymerization of said bio-based monomer.
• PVDF bio-based vinylidene difluoride
• the invention also relates to biobased fluorinated copolymers obtained by copolymerization of said biobased monomer with one or more compatible co-monomers.
• the present invention also relates to the use of biobased PVDF and biobased fluorinated copolymers conforming to those defined above in various applications, such as chemical engineering or electronics, in particular consumer electronic devices: audio and video equipment for use. domestic and commercial, electronic games and entertainment equipment, bowling and billiard equipment, cable and satellite communication equipment, electronic components used in audio and video equipment, CCTV equipment and musical instruments.
• the biobased fluoropolymers according to the invention are used in all applications where the appearance of these polymers is essential and / or their properties depend on their degree of purity; these are applications in the automotive industry, filtration of fluids, especially water, offshore, medical, transport of drinking water, the semiconductor market, cables, batteries Li-ion, photovoltaics, sporting goods and sports textiles.
• biobased PVDF and / or the biobased fluorinated copolymers of the invention are used alone or as a mixture with other polymers, said biobased fluoropolymers representing by mass from 5 to 100%, preferably from 5 to 70%, of preferably 5 to 30%.
• the present invention overcomes the drawbacks of the state of the art. More particularly, it supplies biosourced vinylidene difluoride made from biosourced raw materials, thus meeting the requirements of sustainable development. It is particularly suitable for the manufacture of fluoropolymers for applications requiring constant properties and high purity. Thus, the purpose of biobased fluoropolymers is not limited to simply replacing fluoropolymers of fossil origin, but to provide high performance biobased products.
• the invention relates to the vinylidene difluoride compound characterized in that it has a renewable carbon content of at least 1 atomic%.
• the carbon of a biomaterial comes from the photosynthesis of plants and therefore from atmospheric C0 2 .
• Degradation by degradation, we also mean combustion / incineration at end of life
• C0 2 The C0 2 balance of biomaterials is therefore much better and contributes to reducing the carbon footprint of the products obtained (only the energy for manufacturing is to be taken into account).
• a material of fossil origin also degrading into C0 2 will contribute to the increase in the rate of C0 2 and therefore to global warming.
• the compounds according to the invention will therefore have a carbon footprint which will be better than that of compounds obtained from a fossil source.
• the invention therefore also improves the ecological balance during the manufacture of vinylidene difluoride monomers and fluoropolymers prepared from these monomers.
• renewable carbon indicates that the carbon is of natural origin and comes from a biomaterial (or biomass), as shown below.
• biomass means "from biomass”.
• a material of renewable origin also called biomaterial, is an organic material in which the carbon comes from CO 2 recently fixed (on a human scale) by photosynthesis from the atmosphere. On land, this C0 2 is captured or fixed by plants. At sea, C0 2 is captured or fixed by bacteria or plankton carrying out photosynthesis.
• a biomaterial (100% natural carbon) has an isotopic ratio 14 C / 12 C greater than 10 12 , typically of the order of 1.2 x 10 12 , while a fossil material has a zero ratio.
• the 14 C isotope forms in the atmosphere and is then integrated by photosynthesis, on a time scale of a few tens of years at most. The half-life of 14 C is 5730 years. Therefore the materials resulting from photosynthesis, namely plants in general, necessarily have a minimum content of 14 C isotope.
• Biomass is therefore any material of biological origin and this term excludes materials buried in geological and / or fossilized formations. Examples of biomass are plants, trees, algae, marine organisms, microorganisms, animals, etc. (all or part of these organisms). Renewable materials are composed of biomass and can be replenished continuously.
• the content of biomaterial or renewable carbon content is determined in application of standard NE EN 16640 which has as its object "Biosourced products— Biosourced carbon content - Determination of the biosourced carbon content by the radiocarbon method".
• This European Standard describes a method for determining the content of biobased carbon in products from the measurement of the 14 C content. It also specifies two test methods to be used to determine the 14 C content, from which the bio-based carbon content is calculated:
• a third method, Method C: beta ionization (IB) can also be used to determine the 14 C content.
• the content of biobased carbon is expressed as a fraction of sample mass or a fraction of the total carbon content.
• test and analysis methods specified in European Standard EN 16640: 2017 are compatible with the methods described in ASTM D 6866-12.
• the isotopic ratio of 14 C / 12 C is at least 1.2x10 14 .
• the invention relates, according to a second aspect, to a process for preparing the compound according to the invention, using products of natural origin as starting materials for the manufacture of vinylidene difluoride.
• the starting product is ethylene obtained from ethanol produced directly from biomass.
• a carbohydrate biomass such as cereals, beets
• yeast for example Saccharomyces Cerevisiae
• bacterium for example Zymomonas or Clostridium
• Another way is to produce ethanol from a lignocellulosic biomass (wood, sugar cane, straw).
• Such methods include for example the fermentation of plant materials in the presence of one or more yeasts, followed by a distillation allowing the ethanol to be recovered in the form of a more concentrated aqueous solution which is then treated with a view to further increasing its molar concentration in ethanol.
• the ethanol obtained by fermentation is then dehydrated in a first reactor in a mixture of ethylene and water. It is preferred that the alcohol be injected at the top of the first reactor.
• This dehydration step is generally carried out in the presence of a catalyst, which can in particular be based on g-alumina. By way of example, it has been shown that a ratio of the volume flow rate of liquid ethanol to the volume of catalyst of 1 h 1 and an average temperature of the catalytic bed of 400 ° C. led to an almost total conversion of the ethanol with an ethylene selectivity of the order of 98% mol.
• Dehydration can also be carried out in the presence of water vapor, which then also serves as a fluid coolant compensating for the heat consumption of the dehydration reaction which is endothermic.
• the method according to the invention comprises a step of supplying biobased ethylene having a renewable carbon content of at least 1 atomic% and the transformation by synthesis in several stages into biobased vinylidene difluoride.
• the first synthesis step is the manufacture of vinyl chloride monomer (CVM) from this bio-based ethylene.
• CVM synthesis is carried out by oxychlorination of ethylene in the presence of oxygen and hydrochloric acid, or by direct chlorination of ethylene in the presence of dichlor (Cl 2 ) followed by distillation and cracking at 500 ° C and then a further distillation in order to separate the dichloroethane from the vinyl chloride.
• CVM can also be produced by hydrochlorination of acetylene, as shown below.
• the biobased vinyl chloride is transformed into biobased VDF via the following synthesis intermediates: l, l, 2-trichloroethane, l, l, l-trichloroethane and l-chloro-l, l-difluoroethane.
• the biobased vinyl chloride is transformed into biobased VDF via the following synthesis intermediates: l, l, 2-trichloroethane, l, l-dichloroethene, and l-chloro-l, l-difluoroethane.
• the biobased vinyl chloride is transformed into biobased VDF via the following synthesis intermediates: l, l-dichlorethane, l, l, l-trichloroethane and 1 -chloro-1, 1 -difluoroethane.
• the reaction steps are indicated below:
• Biosourced acetylene is made from biogas containing methane and / or from calcium carbide which has itself been prepared from a renewable carbon source (charcoal, lignin or others). Such a process starting from acetylene is described in the Engineering Techniques, reference J 6250 and also in document FR 2939132.
• VDF biosourced vinylidene difluoride
• the VDF homopolymer according to the invention comprises VDF monomers coming from renewable resources, and optionally monomers coming from fossil resources.
• PVDF is synthesized from a mixture of monomers (biobased and of fossil origin), at least 20% by weight of the mixture is represented by the units of biobased monomer.
• the PVDF homomolymer only comprises units of VDF of renewable origin determined according to standard EN 16640: 2017.
• the invention also relates to biobased fluorinated copolymers comprising biobased vinylidene difluoride units and one or more types of co-monomer units compatible with vinylidene difluoride.
• These comonomers can be halogenated (fluorinated, chlorinated or brominated) or non-halogenated.
• fluorinated comonomers examples include vinyl fluoride (VF), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluoropropenes and in particular
• the fluorinated monomer may contain a chlorine or bromine atom.
• Chlorofluoroethylene can denote either l-chloro-l-fluoroethylene or l-chloro-2-fluoroethylene.
• the 1-chloro-1-fluoroethylene isomer is preferred.
• the chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
• the biobased fluorinated copolymer can also comprise non-halogenated monomers such as ethylene, in particular biobased ethylene, and / or acrylic or methacrylic comonomers.
• the present invention also relates to the use of biobased PVDF and / or biobased fluorinated copolymers in accordance with those defined above in various applications where the appearance of these polymers is essential and / or their properties depend on their degree of purity; these are applications in chemical engineering, the automotive industry, filtration of fluids, in particular drinking water, offshore, medical, transportation of drinking water, the semiconductor market, cables, Li-ion batteries, photovoltaics, sporting goods and sports textiles.
• Preferred applications are in electronics, in particular for the manufacture of consumer electronics: audio and video equipment for domestic and commercial use, electronic games and entertainment equipment, bowling and billiard equipment, cable and communication equipment. satellite, electronic components used in audio and video equipment, closed circuit television equipment and musical instruments.
• any polymer containing it will advantageously have a higher degree of purity, which makes it possible during the transformation at high temperature to avoid yellowing of the PVDF.
• biobased PVDF and / or biobased fluorinated copolymer of the invention are used alone or in admixture with other polymers, said biobased fluoropolymers representing by mass from 5 to 100%, preferably from 5 to 70%, preferably from 5 to 30%.

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