Classifications

• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C08L23/0869—Acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1397—Single layer [continuous layer]

Definitions

• the present invention relates to copolymers of ethylene and at least one unsaturated carboxylic acid or unsaturated carboxylic acid derivative, wherein the ethylene is at least partly obtained from renewable raw materials.
• the inventors of the present application have implemented a process for the industrial manufacture of ethylene-based copolymers from renewable raw materials.
• the process according to the invention makes it possible to dispense at least partly from raw materials of fossil origin and to replace them with renewable raw materials.
• copolymers based on ethylene obtained according to the process according to the invention are of such quality that they can be used in all the applications in which it is known to use these copolymers, including in the most demanding applications.
• the invention relates to copolymers of ethylene and at least one unsaturated carboxylic acid or unsaturated carboxylic acid derivative in which the ethylene is at least partly obtained from renewable raw materials.
• the copolymer may comprise at least 0.24 10 -10 mass% of 14 C.
• copolymers of ethylene and at least one unsaturated carboxylic acid or unsaturated carboxylic acid derivative means all copolymers comprising at least these two monomers, in particular this definition covers terpolymers comprising ethylene and at least one unsaturated carboxylic acid or unsaturated carboxylic acid derivative.
• At least a portion of the carbon atoms of the unsaturated carboxylic acid or of the unsaturated carboxylic acid derivative is of renewable origin.
• the unsaturated carboxylic acid is acrylic or methacrylic acid (hereinafter (meth) acrylic).
• the unsaturated carboxylic acid derivative is an unsaturated carboxylic acid ester, an unsaturated carboxylic acid anhydride or an unsaturated epoxide.
• the unsaturated carboxylic acid esters are alkyl (meth) acrylates
• the number of carbon atoms of the alkyl part of the alkyl (meth) acrylates is preferably from 1 to 24, in particular ( alkyl (meth) acrylates are selected from methyl acrylate, ethyl acrylate, n - butyl acrylate, isobutyl acrylate and 2 - ethylhexyl acrylate.
• Particularly preferred are methyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
• the anhydrides of unsaturated carboxylic acids are chosen from maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride, in particular maleic anhydride is used.
• the unsaturated epoxides are chosen in particular from:
• aliphatic glycidyl esters and ethers such as glycidyl allyl glycidyl ether, vinyl glycidyl ether, maleate and itaconate, acrylate and glycidyl methacrylate (GMA) and
• alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
• the present application also relates to the copolymer mixtures according to the invention, the compositions comprising these copolymers and the uses of these copolymers.
• the copolymers of ethylene and at least one unsaturated carboxylic acid or carboxylic acid derivative unsaturated according to the present application are obtainable according to the manufacturing process comprising the following steps: a) fermentation of renewable raw materials and optionally, purifying to produce at least one alcohol selected from ethanol and alcohol mixtures comprising ethanol; b) dehydration of the alcohol obtained to produce at least one alkene selected from ethylene and mixtures of alkenes comprising ethylene and, optionally, purification of the alkene to obtain ethylene; c) copolymerization of the alkene; ethylene with at least one comonomer selected from unsaturated carboxylic acid or unsaturated carboxylic acid derivative, d) isolating the obtained copolymer.
• Step a) of the process for producing copolymers of ethylene and at least one unsaturated carboxylic acid or carboxylic acid derivative unsaturated according to the invention comprises the fermentation of renewable raw materials to produce at least one alcohol, said wherein the alcohol is selected from ethanol and mixtures of alcohols comprising ethanol.
• renewable raw material is a natural resource, for example animal or vegetable, whose stock can be reconstituted over a short period on a human scale. In particular, this stock must be renewed as quickly as it is consumed. For example, vegetable matter has the advantage of being able to be cultivated without their consumption leading to an apparent decrease in natural resources.
• renewable raw materials contain 14 C. All carbon samples taken from living organisms (animals or plants) are in fact a mixture of 3 isotopes: 12 C (representing about 98.892%), 13 C (about 1, 108%) and 14 C (traces: 1, 2.10 ⁇ 10 %). The 14 C / 12 C ratio of living tissues is identical to that of the atmosphere.
• 14 C exists in two main forms: in the form of carbon dioxide (CO 2 ), and in organic form, that is to say of carbon integrated in organic molecules.
• CO 2 carbon dioxide
• organic form that is to say of carbon integrated in organic molecules.
• the proportion of 14 C being constant in the atmosphere, it is the same in the body, as long as it is alive, since it absorbs this 14 C in the same way as the 12 C ambient.
• the average ratio of 14 C / 12 C is equal to l, 2x l ⁇ ⁇ 12 .
• 12 C is stable, that is to say that the number of atoms of 12 C in a given sample is constant over time.
• 14 C is radioactive, the number of 14 C atoms in a sample decreases over time (t), its half - life being equal to 5730 years.
• the 14 C content is substantially constant from the extraction of the renewable raw materials, until the manufacture of the copolymer according to the invention according to the invention and even until the end of life of the object manufactured in said copolymer. Therefore, the presence of 14 C in any material, whatever the quantity, gives an indication of the origin of the molecules constituting it, namely that they come from renewable raw materials and not from fossil materials .
• the amount of 14 C in a material can be determined by one of the methods described in ASTM D6866-06 (Standard
• This standard contains three methods for measuring organic carbon derived from renewable raw materials, referred to in English as "biobased carbon”.
• the proportions indicated for the copolymer of the invention are preferably measured according to the mass spectrometry method or the liquid scintillation spectrometry method described in this standard, and most preferably by mass spectrometry.
• the copolymer according to the invention comprises a quantity of carbon derived from renewable raw materials greater than 20%, preferably greater than 50% by weight relative to the total carbon mass of the copolymer.
• the copolymer may comprise at least 0.24 ⁇ 10 "10% by weight of 14 C, and preferably at least 0.6 10" 10% by weight
• the amount of carbon derived from renewable raw materials is greater than 75%, preferably equal to 100% by weight relative to the total carbon mass of the copolymer.
• renewable raw materials plant materials can be used; materials of animal origin or materials of plant or animal origin from recovered materials (recycled materials).
• the materials of plant origin contain at least sugars and / or starches.
• Vegetable materials containing sugars are essentially sugar cane and sugar beet, and maple, date palm, sugar palm, sorghum, American agave; plant materials containing starches are mainly cereals and legumes such as maize, wheat, barley, sorghum, wheat, rice, potato, cassava, sweet potato, or seaweed.
• materials from recovered materials include plant or organic waste including sugars and / or starches.
• renewable raw materials are plant materials.
• Fermentation of renewable materials is carried out in the presence of one or more suitable microorganisms, this microorganism may possibly have been modified naturally by a chemical or physical constraint, or genetically mutant.
• the microorganism used is Saccharomyces cerevisiae or a mutant thereof.
• materials comprising cellulose or hemicellulose, or even lignin which, in the presence of the appropriate microorganisms, can be converted into materials comprising sugar.
• These renewable materials include straw, wood and paper. These materials can advantageously come from recovered materials.
• the fermentation step is followed by a purification step for separating the ethanol from the other alcohols.
• step b) is carried out the dehydration of the alcohol or alcohols obtained to produce, in a first reactor, at least one alkene chosen from ethylene and mixtures of alkenes comprising ethylene, the secondary product of dehydration being water.
• the dehydration of the alcohol is carried out using an alpha-alumina catalyst such as the catalyst marketed by EUROSUPPORT under the trade name ESM 1 10 ® (undoped trilobal alumina containing little -about 0, 04% - residual Na 2 O).
• ESM 1 10 ® undoped trilobal alumina containing little -about 0, 04% - residual Na 2 O.
• the operating conditions of dehydration are part of the general knowledge of those skilled in the art, as an indication, the dehydration is generally carried out at a temperature of the order of 400 ° C.
• Another advantage of the process according to the invention is its energy saving: the fermentation and dehydration steps of the method according to the invention are carried out at relatively low temperatures, below 500 0 C, preferably below 400 0 C, in The step of cracking and steam - cracking of the oil in ethylene is carried out at a temperature of the order of 800 ° C. This energy saving is also accompanied by a reduction in the CO 2 content emitted in the reactor. atmosphere.
• a purification step is carried out during step a) or during step b).
• the alkene obtained in step b) is ethylene. If the alcohol obtained in step a) has not been purified, at the end of step b), a mixture of alkenes comprising ethylene is obtained.
• At least one purification step is carried out during step a) and / or step b) in order to obtain ethylene with a degree of purity sufficient to carry out a copolymerization.
• the alcohol obtained in step a) is purified so as to isolate the ethanol, therefore the alkene obtained in step b) is ethylene.
• the main impurities present in the ethylene resulting from the dehydration of ethanol are ethanol, propane and acetaldehyde.
• the ethylene will have to be purified, that is to say that the ethanol, propane and acetaldehyde will have to be removed, in order to easily copolymerize in step c).
• Ethylene, ethanol, propane and acetaldehyde can be separated by one or more low temperature distillations.
• Ethylene, ethanol, propane and acetaldehyde are cooled to about -105 ° C., preferably -103.7 ° C. and then distilled to extract ethylene.
• Another advantage of the process according to the present invention relates to impurities.
• the impurities present in the ethylene resulting from the dehydration of ethanol are totally different from those present in the ethylene resulting from steam cracking.
• the separation of dihydrogen and methane is carried out after compression at 36 bar and cooling to about -120 ° C. Under these conditions, dihydrogen and methane, liquid, are separated in the demethanizer; then the ethylene is recovered at 19 bar and -33 ° C.
• the process according to the present application makes it possible to avoid the step of separating dihydrogen and methane, and also makes it possible to cool the mixture to -105 ° C. at atmospheric pressure instead of
• the cooling of this separation step can also be done under pressure to increase the boiling temperature of the compounds to be separated (for example to 20 bar and -35 ° C). These differences also contribute to making the process according to the invention more economical (saving material and saving energy which is also accompanied by a decrease in the amount of CO 2 emitted into the atmosphere).
• step b) of the process according to the invention does not comprise acetylene, unlike the ethylene obtained by cracking or steam-cracking. Since acetylene is very reactive and causes oligomerization side reactions, obtaining ethylene without acetylene is therefore particularly advantageous.
• the process according to the invention can be implemented in production units located at the place of production of the raw materials.
• the size of the production units of the process according to the invention is much smaller than the size of a refinery: the refineries are in fact large plants generally located far from the centers of production of raw materials and fed by pipelines. .
• step c) the ethylene is copolymerized with at least one unsaturated carboxylic acid or unsaturated carboxylic acid derivative generally by a high pressure radical copolymerization.
• the polymerization of step c) can be carried out in an autoclave or tubular reactor, preferably this process is carried out in a tubular reactor.
• step c) the ethylene is copolymerized with at least one unsaturated carboxylic acid and / or carboxylic acid derivative unsaturated generally by a high pressure radical copolymerization.
• High pressure radical copolymerization is generally carried out by introducing ethylene, the comonomer (s) (the comonomers comprise at least one of the unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative) and a high pressure polymerization initiator. in an autoclave or tubular reactor at a temperature of between 80 ° C. and 325 ° C. in a tubular reactor and between 150 ° and 290 ° C. in an autoclave reactor.
• the amount of comonomers introduced may be up to 20% by weight relative to the total amount of ethylene and comonomers introduced into the reactor, which makes it possible to obtain a copolymer containing up to 50% by weight of comonomers.
• the pressure is regulated by means of an expansion valve located at the outlet of the reactor.
• the polymer formed is recovered at the outlet of the reactor and the monomer that has not reacted is preferably recycled at the beginning of the reactor.
• the pressure inside the reactor is advantageously between 500 and 3000 bar, preferably between 1000 and 2500 bar.
• this transfer agent may for example be one or more alkanes such as butane, pentane, one or more alkenes such as propylene, butene or one or more aldehydes such as as propionaldehyde, acetaldehyde or one or more ketones such as acetone, methyl ethyl ketone).
• this transfer agent it is possible to limit the molar mass of the polymer produced.
• all the organic and inorganic compounds which liberate free radicals under the reaction conditions may be used, preferably compounds or mixtures of compounds comprising a peroxide group, for example the following compounds: tertio butyl Ip eroxyneodecanoate, tert-butylperoxypivalate, tert-amylperoxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxybenzoate, tert-butylperoxyacetate or ditertioamyl peroxide.
• the mass quantity of polymerization initiator is between 1 and 1000 ppm.
• the introduction of the mixture of ethylene and comonomers is preferably carried out at the top of the tubular reactor.
• the initiator or the mixture of initiators is injected by means of a high pressure pump at the top of the reactor, after the place of introduction of the mixture of ethylene and comonomers.
• the mixture of ethylene and comonomers can be injected at least at another point of the reactor, this injection is itself followed by a new injection of initiator or a mixture of initiators, this is called multipoint injection technique.
• the mixture is preferably injected in such a way that the weight ratio of the injected mixture at the reactor inlet to the totality of the injected mixture is between 10 and 90%.
• Examples of processes which can be used to prepare an ethylene copolymer with an unsaturated acrylic acid ester are, for example, those described in US 4,788,265, US2006 / 0149004 A1, or in US2007 / 0032614 A1.
• An autoclave reactor generally consists of a cylindrical reactor in which is placed a stirrer.
• the residence time in the reactor is between 30 and 120 seconds.
• the length / diameter ratio of the reactor is between 3 and 25.
• the reactor can be separated into several interconnected zones in series.
• the ethylene alone and the comonomer or comonomers are injected into the first zone of the reactor at a temperature of between 20 and 120 ° C., preferably between 50 and 80 ° C.
• An initiator is also injected into this first reaction zone.
• the reactor is a multizone reactor, the flow of ethylene and comonomers unreacted as well as the polymer formed then pass into the following reaction zones.
• comonomers and initiators can be injected.
• the temperature of the zones is between 150 ° C. and 290 ° C. and preferably between 160 ° C. and 280 ° C.
• the reactor pressure is between 500 and 3000 bar, preferably between 1200 and 2200 bar.
• copolymerization methods that can be used are, for example, those described in patent applications FR2660660, FR2498609, FR256941 1 and FR2569412.
• a device for carrying out the copolymerization process according to the invention according to a technique of injecting the reagents at several points.
• This device comprises a tubular reactor R comprising five zones Z 1, Z 2, Z 3, Z 4 and Z 5, a medium pressure separator S 1 which constitutes the inlet in a medium pressure recycling circuit and a low pressure separator S 2 which constitutes the inlet in a low pressure recycling circuit.
• the medium pressure recycle circuit comprises the medium pressure separator S l, the pipe 9 provided with the valve V4, the heat exchanger E7, the pipe 10, the separator S3 and the pipe 5, provided with the valve V6.
• the low pressure recycle circuit comprises the low pressure separator S2, the pipe 14, the heat exchanger E8, the pipe 15, the separator S4, the pipe 17, the compressor C, the pipe 2.
• the tubular reactor R is a jacketed tube in which circulates water for supplying or withdrawing calories in order to heat or cool the fluid circulating in the reactor.
• the tubular reactor R comprises five zones Z 1, Z 2, Z 3, Z 4 and Z 5 to which five parts of the double envelope correspond: E 1 is the part of the double envelope located around the zone Z 1, E 2 is the part of the double envelope located around zone Z2, E3 is the part of the double envelope located around zone Z3, E4 is the part of the double envelope located around zone Z4, E5 is the part of the double envelope around zone Z5; the temperature of the water circulating in each of the parts E 1, E 2, E 3, E 4 and E 5 may be different.
• Line 1 is provided with an expansion valve V l.
• this fresh ethylene is mixed with a gas stream (recycling of ethylene and the comonomer or comonomers of the low pressure recycle circuit) from compressor C.
• Line 2 brings the mixture into a Pc precompressor (where the mixture is compressed from 60 bar to 200 bar), then the mixture leaves the precompressor Pc via line 4.
• Fresh comonomers are introduced into line 4 by means of line 3. Downstream of line 3, line 5 introduces into line 4 the mixture of recycled fluids from the medium pressure recycle circuit.
• the mixture circulating in the pipe 4 is introduced into the hypercompressor Hc (where the mixture is compressed by 200 bar at a pressure of between 1200 and 2500 bar, which is the pressure in the reactor), then the mixture leaves the hypercompressor Pc by driving 6.
• the pressure inside the reactor is regulated by the expansion valve V2.
• valve V7 makes it possible to regulate the pressure of the mixture in line 6.
• the reactor used comprises 5 zones: the mixture comprising ethylene and the comonomer (s) and optionally a transfer agent is admitted in zone Z1 of the reactor (at the reactor inlet) using line 6.
• zone Z1 the mixture is heated up to the initiation temperature of the polymerization reaction (between 90 and 170 ° C.).
• a mixture of ethylene and comonomers can be introduced by means of line M2 and a polymerization initiator (generally at least one peroxide and / or molecular oxygen) can be introduced via line 12.
• a polymerization initiator generally at least one peroxide and / or molecular oxygen
• the polymerization reaction is strongly exothermic, the temperature of the mixture which passes into the tubular reactor increases gradually.
• the mixture comprising the polymer Before leaving the reactor, the mixture comprising the polymer is cooled to a temperature of between 140 ° C. and 240 ° C.
• the mixture comprising the polymer exits the reactor through line 7 provided with a valve V3 which allows the mixture to be relaxed at approximately 260 bar. Then the mixture enters the heat exchanger E6 where it is cooled and leaves it via line 8.
• Line 8 brings the mixture into the medium pressure separator S 1.
• the copolymer formed is separated from the mixture by unreacted products: ethylene, comonomer and transfer agent.
• the mixture of the unreacted products is brought into the heat exchanger E7 via line 9 where it is cooled and then leaves the the heat exchanger E7 through the pipe 10.
• the pipe 10 brings the products into the separator S3 where the polymer waxes (having a low mass and which have not been separated in the separator S 1) are isolated and extracted from the device via line 1 1.
• Line 5, equipped with valve V6, supplies the ethylene, comonomer and transfer agent mixture of separator S3 in line 4.
• the copolymer exits the separator S 1 through line 12 provided with a valve V5 and is introduced into the low-pressure separator S2.
• the valve V5 makes it possible to relax the copolymer at a pressure of approximately 2 to 5 bars.
• the copolymer is removed from the device via line 13 and is then conveyed to an extruder to be converted into granules.
• the pipe 14 makes it possible to evacuate the gas mixture (ethylene / comonomers, transfer agent which have not been separated in the separator S 1), this mixture is fed into the heat exchanger E 8 via the pipe 14 where it is cooled to about 35 ° C and then exits the heat exchanger E8 through line 15.
• Line 15 brings the products into separator S4 where the monomers are condensed. Part of the monomers is extracted from the device via line 16, the other part of the monomers is introduced via line 17 into compressor C (where they are compressed at 60 bar).
• the monomers leave the compressor via the pipe 2.
• the pipe 18 makes it possible to introduce the transfer agent into the pipe 2.
• step d) the copolymer obtained is isolated and optionally purified, according to a conventional technique, depending on the application for which it is intended.
• the copolymer according to the invention comprises maleic anhydride
• maleic anhydride comprising carbon atoms of renewable origin.
• the maleic anhydride may be obtained according to the process described in the application FR 0854896 of the Applicant, comprising the following steps: a) fermentation of renewable raw materials and optionally purification to produce a mixture comprising at least butanol; b) oxidation of butanol to maleic anhydride at a temperature generally of between 300 and 600 ° C., by means of a catalyst based on vanadium and / or molybdenum oxides; c) isolation of the maleic anhydride obtained at the end of step b).
• the copolymer according to the invention comprises acrylic acid
• acrylic acid comprising carbon atoms of renewable origin
• the acrylic acid can be obtained according to the process described in application FR 2,884,817 of Arkema SA by dehydration of glycerol in the presence of molecular oxygen.
• the copolymer according to the invention comprises methyl methacrylate
• methyl methacrylate comprising carbon atoms of renewable origin.
• methyl methacrylate can be obtained according to the teaching of the application FR 0853588 from Arkema FRANCE.
• This application essentially describes two processes for manufacturing methyl methacrylate: a first process comprising the following steps:
• hydrocyanic acid is condensed on acetone via basic catalysis to obtain acetone cyanohydrin;
• acetone cyanohydrin is reacted in a concentrated sulfuric medium to obtain ⁇ -oxyisobutyramide monosulfate, which is converted into sulfuric methacrylamide by the action of the heat of the reaction, which is highly exothermic;
• a third step the methacrylamide is hydrolyzed and esterified with methanol to form the methacrylate of methyl and ammonium sulphate and the desired methyl methacrylate is recovered;
• hydrocyanic acid is condensed on acetone via basic catalysis to obtain acetone cyanohydrin;
• the methyl hydroxymethacrylate is dehydrated to recover the desired methyl methacrylate.
• the acetone, hydrocyanic acid and / or methanol used in these processes can be obtained from renewable materials.
• the acetone can be obtained according to one of the following three processes: 1. Acetobutyl fermentation of C 6 and C 5 sugars, resulting in an acetone-butanol mixture optionally comprising ethanol, acetone separation, by example by distillation, in particular azeotropic distillation or by membrane separation or separation on silicalite; 2. hydrothermal liquefaction at 573 K of sewage sludge to obtain black water containing hydrocarbons, and catalytic cracking of said black water in a water vapor atmosphere on a zirconia or zirconia / alumina catalyst supported on an iron oxide, and then separation of the acetone, for example by distillation, in particular azeotropic distillation or by membrane separation or separation on silicalite;
• Hydrocyanic acid can be obtained by one of the following methods: Methane ammoxidation, the methane having been obtained by fermentation in the absence of oxygen of animal and / or vegetable organic matter, such as pig slurry, garbage, industrial waste, leading to a biogas composed essentially of methane and methane. carbon dioxide, the carbon dioxide having been removed by washing the biogas with a basic aqueous solution of sodium hydroxide, potassium hydroxide or amine, or by water under pressure, or by absorption in a solvent such as methanol ;
• methanol ammoxidation the methanol having been obtained by pyrolysis of the wood or by gasification of all materials of animal and / or vegetable origin, leading to a synthesis gas consisting essentially of carbon monoxide and hydrogen which is made react with water, or by fermentation from crops such as wheat, sugar cane or beetroot, giving fermentable products and therefore alcohol.
• Methanol can be obtained by pyrolysis of wood or by gasification of any material of animal or vegetable origin, leading to a synthesis gas consisting essentially of carbon monoxide and hydrogen that is reacted with water, or by fermentation from crops such as wheat, sugar cane or beet, giving fermentable products and therefore alcohol.
• the copolymers according to the invention are chosen from: random copolymers of ethylene and of methacrylic acid, random copolymers of ethylene and of acrylic acid, random copolymers of ethylene and of methyl acrylate , random copolymers of ethylene and butyl acrylate, copolymers of ethylene and 2 - ethylhexyl acrylate, random copolymers of ethylene and maleic anhydride, random copolymers of ethylene and methacrylate. glycidyl.
• random terpolymers of ethylene, butyl acrylate and maleic anhydride random terpolymers of ethylene, methyl acrylate and maleic anhydride, and terpolymers statistics of ethylene, methyl acrylate and glycidyl methacrylate.
• the invention also relates to a composition comprising at least one copolymer according to the invention, said composition comprising:
• a terpolymer of ethylene, an unsaturated carboxylic acid ester and a monomer selected from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and unsaturated epoxides or "a mixture of a copolymer of ethylene and an unsaturated carboxylic acid ester and a copolymer of ethylene and at least one monomer selected from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and unsaturated epoxides.
• copolymers according to the invention are preferably obtained from 40 to 99% of ethylene by weight and from 1 to
• the terpolymers according to the invention are preferably obtained from 40 to 99.99% of ethylene by weight, from 0 to
• maleic anhydride or glycidyl methacrylate 15% maleic anhydride or glycidyl methacrylate; more preferably from 55% to 94.9% ethylene by weight, from 5 to 35% unsaturated carboxylic acid or its derivatives by weight and from 0.1 to 10% maleic anhydride or glycidyl methacrylate.
• the melt flow index MFI (English MeIt Fluid Index) of these copolymers is advantageously in the range of 0.1 to 1000 g / l Omin (ASTM D 1238, 190 0 C, 2, 16kg ), preferably from 1 to 500 g / l Omin.
• the copolymer or terpolymer may be amorphous or semi-crystalline. When semi-crystalline, its melting point of the polymer may be between 45 ° C and 115 ° C.
• the present invention also relates to the copolymers according to the invention grafted with polyamide blocks or with polyether blocks. having at least one amino terminal function.
• These polymers consist of a backbone (trunk) which is a copolymer or terpolymer of ethylene and at least one unsaturated carboxylic acid or unsaturated carboxylic acid derivative according to the invention and at least one graft which is a polyamide or a polyether block having at least one amine terminal function, the graft (s) being attached to the backbone by the residues of the unsaturated monomers. Indeed the remains of the unsaturated monomers are capable of reacting with polyamides / ethers having an amino end.
• the copolymers according to the invention grafted with polyamides correspond to those described in application FR 2 912 150.
• the backbone preferably consists of a copolymer chosen from random copolymers of ethylene and of maleic anhydride and the random terpolymers of ethylene, alkyl (meth) acrylate and anhydride maleic.
• the graft When the graft is of polyamide type, it may be homopolyamides such as for example polyamide 6 monoNH 2, polyamide 1 1 monoNH 2, polyamide 12 monoNH 2, polyamide 6-6 monoNH 2 or copolyamides, for example copolyamide 6/1 1 monoNH 2 or copolyamide 6/12 monoNH2, preferably they are polyamide 6 monoNH2, polyamide 1 1 monoNH2 or copolyamide 6/1 1 monoNH2.
• homopolyamides such as for example polyamide 6 monoNH 2, polyamide 1 1 monoNH 2, polyamide 12 monoNH 2, polyamide 6-6 monoNH 2 or copolyamides, for example copolyamide 6/1 1 monoNH 2 or copolyamide 6/12 monoNH2, preferably they are polyamide 6 monoNH2, polyamide 1 1 monoNH2 or copolyamide 6/1 1 monoNH2.
• the polyamide may comprise at least partly carbon atoms of renewable origin, in particular the polyamide 11 or 6/1 1 obtained at least in part from castor oil.
• the copolymer grafted with a polyamide according to the invention is advantageously a copolymer of ethylene, alkyl (meth) acrylate and maleic anhydride with PolyamidemonoNH2 grafts.
• copolymers according to the invention grafted with polyamide grafts may advantageously be used as encapsulant in solar panels, as constituent in elastomeric compositions, or for manufacturing parts having properties thermal resistance to oil and hydrolysis allowing them to be used under engine hood, for example in the automobile.
• copolymers according to the invention grafted with polyether blocks having at least one amine terminal function correspond to those described in application FR 2 897 356.
• the backbone is composed of a copolymer selected from copolymers of ethylene and alkyl (meth) acrylate, copolymers of ethylene and carboxylic acid anhydride such as maleic anhydride, and ethylene polymers. and an unsaturated epoxide of the aliphatic glycidyl ester type, such as in particular glycidyl methacrylate (GMA).
• a copolymer selected from copolymers of ethylene and alkyl (meth) acrylate, copolymers of ethylene and carboxylic acid anhydride such as maleic anhydride, and ethylene polymers.
• an unsaturated epoxide of the aliphatic glycidyl ester type such as in particular glycidyl methacrylate (GMA).
• the functionalized polyolefin is a copolymer of ethylene, of ethyl acrylate or of n-butyl acrylate, the content of which is between 2 and 40% by weight of the copolymer, and of maleic anhydride whose content is between 0.2 and 6% by weight of the copolymer.
• the amino-terminated polyether graft is typically a polyoxyalkylene glycol having at least one amine end chain.
• the polyoxyalkylene glycol is selected from polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG) polyoxytetramethylene glycol (PTMG), or copolymers or mixtures thereof.
• compositions comprising the copolymer or the terpolymer according to the invention.
• These compositions may thus comprise, in addition to the copolymer or the terpolymer, at least one additive for improving the properties of the final material and / or at least one other polymer.
• additives include antioxidants; UV protection agents; so - called “implementation” agents whose function is to improve the appearance of the final polymer during its implementation, such as fatty amides, stearic acid and its salts, ethylene bisstearamide or fluoropolymers; anti-fogging agents; anti-blocking agents such as silica or talc; fillers such as calcium carbonate and nanofillers such as clays; coupling agents such as silanes; crosslinking agents such as peroxides; antistatic agents; nucleating agents; pigments; dyes.
• additives are generally used in contents of between 10 ppm and 100,000 ppm by weight relative to the weight of the final copolymer.
• compositions may also comprise additives chosen from plasticizers, plasticizers and flame retardant additives, such as aluminum or magnesium hydroxides (the latter additives may reach amounts well above 100000 ppm). Some of these additives can be introduced into the composition in the form of masterbatches. These compositions may also comprise other polymers, such as polyolefins other than the copolymers according to the invention, polyamide or polyester.
• polyolefins which are different from the polymer according to the invention, mention may be made of homopolymers and copolymers of ethylene, such as very low density polyethylene (LLDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
• LLDPE very low density polyethylene
• LDPE low density polyethylene
• LLDPE medium density polyethylene
• HDPE high density polyethylene
• copolymers comprising ethylene and vinyl acetate or copolymers comprising ethylene and alkyl (meth) acrylate.
• ethylene is not derived from renewable raw materials.
• the present application also relates to the copolymer compositions according to the invention and more particularly to the compositions comprising one or more copolymers according to the invention, this copolymer (s) being:
• composition according to the invention comprises:
• composition according to the invention comprises:
• compositions according to the first variant or according to the second variant described above in which the amount of comonomer chosen from unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and unsaturated epoxides, included in US Pat. copolymer or in the terpolymer, is less than 1% by weight relative to the total weight of the composition.
• copolymers according to the invention can be used in an extrusion - coating process for application on a support or in an extrusion - lamination process for bonding between them several supports of different or different nature, in a wide temperature range.
• the present application also relates to the uses of the copolymers according to the invention and compositions comprising at least one copolymer according to the invention.
• the present application relates in particular to the uses of the copolymers and compositions according to the invention as adhesive or adhesive composition in particular, coextrusion, extrusion coating or extrusion lamination.
• a preferred composition of copolymers according to the invention is: according to a first variant
• LLDPE linear low density polyethylene
• LLDPE very low density polyethylene
• LDPE low density polyethylene
• polyethylene terephthalate
• PP polypropylene
• PVDC polyvinyl chloride
• PVDC polyvinylidene chloride
• PVDF polyvinylidene fluoride
• PA polystyrene
• polymers can thus be used in multilayer structures, in particular between a polyethylene terephthalate (PET) layer and a polyethylene layer or between a polyester layer derived from renewable materials such as poly (lactic acid) and a polymer having barrier properties, such as, for example, the saponified ethylene vinyl acetate copolymer (EVOH) or the PA which have barrier properties. oxygen.
• PET polyethylene terephthalate
• EVOH saponified ethylene vinyl acetate copolymer
• PA which have barrier properties. oxygen.
• the present application also relates to the uses of the copolymers according to the invention as an adhesive or adhesive composition in a multilayer structure.
• the invention relates to a multilayer structure obtained by using the adhesive composition according to the invention in an extrusion-coating process for application on a support, said support being chosen from aluminum, paper or cardboard, cellophane, films based on polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride (PVC), polyvinylidene chloride resins
• PVDC polyacrylonitryl
• PAN polyacrylonitryl
• the invention also relates to a multilayer structure obtained by using the adhesive composition of the invention, in an extrusion-lamination process for bonding several supports of different nature to each other, the supports are generally chosen from aluminum, paper or cardboard, cellophane, film-based polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylonitryl (PAN) resins, these films being oriented or not, metallized or not, whether or not they are treated physically or chemically, and films coated with a thin inorganic barrier layer, such as polyester (PET SiOx or AlOx).
• a thin inorganic barrier layer such as polyester (PET SiOx or AlOx).
• the present application also relates to the use of the compositions according to the invention as a sealing layer, in particular on a material chosen from aluminum, polystyrenes (PS), polypropylenes (PP), polyamines (PA), etc.
• the copolymers according to the invention can also be used:
• compatibilizer of compounds ie an adjuvant which makes it possible to improve the compatibility with said compounds
• natural fibers ie an adjuvant which makes it possible to improve the compatibility with said compounds
• polyolefin / polyamine alloys ie an adjuvant which makes it possible to improve the compatibility with said compounds
• polymers ie, as an adjuvant in a polymer for improving the impact strength of said polymer
• polymers such as polyethylene terephthalate (PET), polyamide (PA) polymers , polypropylenes (PP), polybutylene terephthalate (PBT), biopolyesters (polylactic acid
• PHA polyhydroxyalkanoates
• the invention relates to an impact modifier comprising polypropylene, an ethylene / alkyl acrylate copolymer, preferably 2-ethylhexyl acrylate or n-octyl acrylate, and optionally a polymer chosen from high density polyethylene.
• This impact modifier is described in detail in application FR 2 828 493.
• a shock modifier comprising:
• a core-shell copolymer (A) a core-shell copolymer (A), (b) a copolymer of ethylene selected from copolymers of ethylene and an unsaturated carboxylic acid anhydride, copolymers of ethylene and an unsaturated epoxide and mixtures thereof, (c) a selected copolymer among the copolymers of ethylene and an alkyl (meth) acrylate, copolymers of ethylene and (meth) acrylic acid, optionally neutralized, and mixtures thereof.
• This impact modifier is described in detail in patent application EP 1 252 234. From the copolymers, it is also possible to form films, such as encapsulating films for solar panels.
• copolymers can also be added in another polymer, such as for example PET, to facilitate recycling. These copolymers can also be used to produce a sound-absorbing mass, that is to say an expandable expandable mass having a sound-insulating function.
• Flexible parts can also be formed from the copolymers of the invention by injection or thermoforming; Tubes or containers such as bottles or reservoirs can also be manufactured by tube extrusion or by blow molding extrusion.
• copolymers according to the invention can also be contained in compositions for producing woven or nonwoven fabrics. Another possible application for the copolymers according to the invention is to manufacture masterbatches.
• the copolymers according to the invention can also be used to manufacture electric cables.
• they can be used to make an electrical cable jacket.
• We can also fabricating compositions by dispersing a conductive compound (e.g., carbon black) to form half-insulating mi- conductive compositions (commonly referred to as semiconductors); these compositions are particularly useful for manufacturing medium or high voltage cables.
• a conductive compound e.g., carbon black
• semiconductors commonly referred to as semiconductors
• copolymers can also be used for the modification of bitumen.
• the copolymer according to the invention can also be used in the composition of a hot-melt adhesive (commonly called hot melt).
• a hot-melt adhesive commonly called hot melt
• a hot-melt adhesive composition can be formulated by mixing the copolymers according to the invention with so-called "tackifying" resins, waxes and antioxidants.
• tackifying resins waxes and antioxidants.
• Other additives such as plasticizers, plasticizers, pigments or fillers can also be added.
• tackifying resins can be solid or liquid, used alone or as a mixture; they allow mainly to bring adhesive power to the composition.
• These include: "Resins based on natural or modified rosin ester, for example polymerized, in particular pentaerythritol or gycerol esters, modified terpene or polyterpene resins,
• resins alpha-methyl-styrene, styrene / terpene, terpene / phenol
• resins of hydrocarbon origins such as aliphatic or aromatic resins, not hydrogenated or totally or partially hydrogenated.
• the waxes which make it possible to regulate the fluidity and the setting time of the adhesive, may be chosen from the following families: paraffins, microcrystalline waxes, polyethylene waxes, Fischer-Tropsch waxes, oxidized or otherwise, functionalized waxes hydroxystearamide type or fatty amides.
• the tubular reactor used is 600 m long and 42 mm in diameter.
• the ethylene was injected at the rate of 12 tons / hour (line 1), and 800 kg / hour of butyl acrylate (line 3), the mixture is compressed in the hypercompressor (Hc) at 2400 bar.
• Hc hypercompressor
• the mixture is preheated to 120 ° C. in zone Z1, then a Lup 1 1/26 mixture (that is to say Luperox 1 1 Tert-butylperoxypivalate / Luperox 26 Tert-butylperoxy-2-ethylhexanoate) is injected by the pipe (12).
• a Lup 1 1/26 mixture that is to say Luperox 1 1 Tert-butylperoxypivalate / Luperox 26 Tert-butylperoxy-2-ethylhexanoate
• zone Z2 the temperature rises to 210 ° C. and then drops to 160 ° C. at the outlet of zone Z2.

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• 2008
  • 2008-11-13 FR FR0857689A patent/FR2938262B1/fr not_active Expired - Fee Related
• 2009
  • 2009-11-10 US US13/129,157 patent/US20120021156A1/en not_active Abandoned
  • 2009-11-10 BR BRPI0922029A patent/BRPI0922029A2/pt not_active IP Right Cessation
  • 2009-11-10 WO PCT/FR2009/052166 patent/WO2010055258A1/fr active Application Filing
  • 2009-11-10 EP EP09768174A patent/EP2365989A1/fr not_active Withdrawn
• 2013
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