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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
  • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • 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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
  • B29B2009/125—Micropellets, microgranules, microparticles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

• the present invention relates to a shock modifier, a device and a method for manufacturing said impact modifier, and to a method for preparing a thermoset material, or a precursor of thermoset material, from said modifier. shock.
• the invention will advantageously find application in the field of the preparation of thermoset materials and in particular thermoset materials with improved impact strength. These materials can be used in various fields such as aeronautics, electronics, automotive or industry, including as structural adhesives, matrices for composite materials or as protection elements for electronic components .
• impact modifier in the present application, a compound which, mixed with a thermosetting material improves the mechanical properties of the polymerized thermosetting material. This can be reflected, for example, in improving elongation at break, impact resistance or fatigue resistance.
• thermoset material in the present application, a material formed of polymeric chains of variable lengths interconnected by covalent bonds so as to form a three-dimensional network.
• thermosets epoxy, (metha) crylic, cyanoacrylate, bismaleimide, unsaturated polyesters, vinyl ester, phenolic and polyurethane.
• thermosets can be obtained by mixing a first so-called resin part with a second so-called hardener part.
• Shock modifiers can be in one or both parts or in both parts.
• thermosetting resins there may be mentioned, for example, impact modifiers that are solubilized in the precursor of thermosetting agents before polymerization. These shock modifiers are distinguished from shock modifiers type heart-bark particles that are dispersed in the precursor before polymerization.
• the first range of impact modifiers has the great advantage of not requiring expensive dispersing tools and is not subject to effects of segregation or destabilization of the dispersion.
• block copolymers that can be found in the form of granules or powder such as those described in patents EP 1 866 369 and EP 1 290 088.
• the dissolution of the impact modifier in the form of granules is not desirable for industrial constraints. Indeed, for a simple reason of exchange surface area on volume, one is automatically in a case of very unfavorable figure. Also, in order to dissolve the impact modifier more rapidly, the use of a shock modifier in the form of a powder is preferred. This powder can be dissolved in the precursor liquid solution (thermosetting material or hardener); however, the handling of the powder remains delicate and the dissolution difficult.
• precursor liquid solution thermosetting material or hardener
• the grains when poured into the liquid precursor solution, tend to agglomerate with each other on the surface of the liquid creating agglomerates very difficult to lubricate. To limit this phenomenon, it is necessary to pour very slowly the grains to ensure optimal dispersion in the liquid solution. However, a slow payment does not always prevent the formation of agglomerates because the powder, even before payment, may tend to form in the form of lumps given the high percentage of the order of 30 to 60% of soft phase of the impact modifier in powder form and the presence of fine particles.
• these particles in powder form are characterized by a ratio between the standard deviation and the median particle size high, greater than 15%.
• This very wide particle size distribution makes the process of solubilization of these impact modifiers in the form of a powder in the thermosetting precursor random.
• the object of the present invention is to provide a shock modifier whose structure limits the risk of agglomeration both during its storage and during the mixing step in the precursor liquid solution.
• the present invention also aims to provide a shock modifier whose structure facilitates the preparation of a thermoset material and more precisely its precursors.
• the present invention also aims to provide a device and a reliable manufacturing process of this impact modifier.
• the invention relates to an impact modifier for a thermosetting resin comprising at least one copolymer chosen from block copolymers of type A-B-A, A-B and A-B-C, in which:
• each block is connected to the other by means of a covalent bond or an intermediate molecule connected to one of the blocks by a covalent bond and to the other block by another covalent bond,
• A is a PMMA homopolymer or a copolymer of methyl methacrylate
• C is either (i) a homopolymeric PMMA or a methyl methacrylate copolymer (MMA) or (ii) a polymer based on monomers or a mixture of vinyl monomers; blocks A and C may be identical;
• said shock modifier is in the form of microgranules of diameter between 400 and 1500 ⁇ , preferably between 400 and 1000 ⁇ , and advantageously between 500 and 800 ⁇ .
• the dissolution rate of the impact modifier in the form of microgranules is greater than or equal to that of the impact modifier in powder form conventionally used.
• the handling of these microgranules is also facilitated by the absence of fines generated by the associated manufacturing process.
• the ratio of the standard deviation / average particle size is less than 10%, preferably less than 5%, and advantageously less than 3%. This very narrow particle size distribution for the impact modifier according to the invention enables it to provide better control of the solubilization process in the precursor during the preparation of thermoset materials.
• the present invention also relates to a method for manufacturing an impact modifier as mentioned above, by a solvent route, said process comprising an extrusion step, an underwater cutting step and a drying step.
• the extrusion step is carried out through a die having at least one orifice having a diameter of between 0.3 and 0.5 mm at a die temperature depending on the nature of the impact modifier and, the step of cutting under water is carried out in a granulator at a cutting water temperature to obtain a shock modifier in the form of microgranules of diameter between 400 and 1500 ⁇ , and preferably between 400 and 1000 ⁇ .
• extrusion means in the cradle of the invention the extrusion bi-screw, single screw, BUSS, LIST or any other method for melting the impact modifier and pass through a die.
• the invention also relates to a device for manufacturing an impact modifier, as mentioned above, in which the extruder comprises a die with at least one orifice of between 0.3 and 0.5 mm and preferably between 0.35 and 0.37 mm.
• the invention finally relates to a method for preparing a thermoset material from said impact modifier.
• FIG. 1 represents an exemplary embodiment, in front view, of a die made according to the invention
• FIG. 2 represents an embodiment detail referenced I in FIG. 1 according to the sectional view A-A,
• FIG. 3 is a front view of an exemplary embodiment of a separation grid made according to the invention.
• FIG. 4 represents a 4a) image of the conventional granules of copolymer 1, for example, lifted in Example 1, whereas FIG. 4b) represents the microgranules according to the invention obtained at the end of the manufacturing process of the Example No. 1,
• FIG. 5 is a diagram illustrating the continuous measurement over time of the viscosity of two resin mixtures obtained by mixing a precursor and a powder or microgranules.
• the present invention relates to an impact modifier for thermosetting resin comprising at least one copolymer chosen from block copolymers of type A-B-A, A-B and A-B-C, in which:
• each block is connected to the other by means of a covalent bond or an intermediate molecule connected to one of the blocks by a covalent bond and to the other block by another covalent bond,
• A is a PMMA homopolymer or a copolymer of methyl methacrylate
• A is preferably compatible with said resin
• AB, ABA or ABC block copolymers may be manufactured by any means of polymerization.
• the controlled radical polymerization or anionic polymerization processes implemented using the solvent, emulsion, suspension or other method are used.
• A is a PMMA homopolymer or a copolymer of methyl methacrylate.
• the comonomers used are preferably those based on alkyl methacrylate for forming a block A compatible with the thermoset resin.
• alkyl methacrylates in which the alkyl group contains from 1 to 18 carbons: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and methacrylate.
• n-hexyl cyclohexyl methacrylate, ethyl hexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate stearyl methacrylate, isobornyl methacrylate.
• PEG polyethylene glycol
• vinyl monomers such as N-vinyl pyrrolidone or any other monomer soluble in water.
• reactive monomer is meant a chemical group capable of reacting with the functions of thermosetting resins.
• Block A can be formed of only one of these (meth) acrylic monomers or of several.
• Block A may be manufactured by any means of polymerization and in particular by controlled or anionic radical polymerization.
• the Tg of B is less than 0 ° C. and preferably less than -40 ° C.
• Tg is meant the glass transition temperature of a polymer measured by DSC according to the ASTM standard. E1356.
• the monomer used to synthesize the elastomeric B block may be a diene chosen from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 2-phenyl-1,3 butadiene.
• B is advantageously chosen from poly (dienes), especially poly (butadiene), poly (isoprene) and their random copolymers, or else from partially or completely hydrogenated poly (dienes).
• Blocks B can also be hydrogenated.
• the monomer used to synthesize block B may also be an alkyl (meth) acrylate, in which case the following Tg values are given in parentheses, following the name of the acrylate: ethyl acrylate ( -24 ° C), butyl acrylate (-54 ° C), 2-ethylhexyl acrylate (-85 ° C), hydroxyethyl acrylate (-15 ° C) and methacrylate 2 - ethylhexyl (-10 ° C). Butyl acrylate is advantageously used.
• Block B may also consist of a mixture of monomers. The acrylates are different from those of the block A to respect the condition of incompatibility of the blocks A and B.
• C is either (i) a PMMA homopolymer or a methyl methacrylate copolymer as defined above (ii) a polymer based on monomers or a mixture of vinyl monomers.
• the two blocks A and C of the triblock A-B-C may be identical or different. They can be different in their molar mass but consist of the same monomers. If block C contains a comonomer it may be the same or different from the comonomer of block A.
• Block B consists of the same monomers and possibly comonomers as block B of diblock A-B or triblock ABA.
• the blocks B of the triblock A-B-C and diblock A-B may be identical or different.
• shock modifiers are known for example from the WO document
• Shock modifiers according to the invention are in the form of microgranules of diameter between 400 and 1500 ⁇ , preferably between 400 and 1000 ⁇ , and advantageously between 500 and 800 ⁇ .
• the ratio of the standard deviation / average particle size is less than 10%, preferably less than 5%, and advantageously less than 3%.
• the invention relates to a method of manufacturing the impact modifier described above in the form of microgranules with a diameter of between 400 and 1500 ⁇ , preferably between 400 and 1000 ⁇ , and advantageously between 500 and 800 ⁇ .
• the pellet production line of a few millimeters in diameter comprises a feed system, a granulator with an extruder and a die as well as underwater cutting means, the chain further comprises a conveying line, means for separating and drying the granules.
• microgranules For the production of microgranules, tests have shown that the production line must be modified and that special adaptations were necessary both at the granulator and the dryer. The manufacturing process must also be modified to obtain microgranules of diameter between 400 and 1500 ⁇ , and preferably between 400 and 1000 ⁇ .
• a die 1 is shown for the production of microgranules. This die 1 is intended to be fixed on the axis of the granulator, not shown in the accompanying figures.
• the die 1 comprises at least one orifice 2 comprised between 0.3 and 0.5 mm and preferably between 0.35 and 0.37 mm.
• the die 1 has orifices 2 distributed in cluster 3.
• the die 1 comprises a set of clusters 3, each grouping one number of orifices 2 greater than ten.
• Other configurations are of course conceivable and the number of orifices 2 distributed over the entire die 1 can easily be modified depending on the characteristics desired for the granulator.
• the orifices 2 of one and the same cluster 3 are distributed in a front hole 4. This arrangement is advantageous in that it limits the pressure drops. at the level of the sector 1.
• the die 1 comprises 6 before hole 4, each grouping a cluster 3.
• Each cluster 3 has 15 orifices 2 of diameter 0.36 ⁇ .
• the thickness of the wall at the openings 2 is of the order of 4 mm, while the total thickness of the die being of the order of 55 to 60 mm.
• the diameter of each front hole 4 is of the order of 70 mm.
• this separation grid 5 comprises circularly shaped openings 6 made in a plate 7.
• the openings 6 advantageously have a diameter of between 1.5 and 2 mm and preferably 1.7 mm.
• the separation grid 5 further comprises a square section mesh 8 disposed on the plate 7, the space between the meshes is between 180 and 220 ⁇ .
• Table 1 below makes it possible to compare different orders of quantities between the granules conventionally produced and the microgranules of the present invention.
• the microgranules can quickly plug the orifices of the die 1. To avoid this phenomenon, it was found by the applicant, the need to increase the temperature of the die 1.
• the extrusion step is performed through a die 1 having at least one orifice 2 having a diameter of between 0.3 and 0.5 mm at a die temperature sufficiently high to maintain the microgranules in the liquid state.
• the underwater cutting step is performed in a granulator at a cutting water temperature above 70 ° C.
• Pulse air output pellet blowing 3 seconds / pause 3 seconds
• the impact modifier "copolymer 1" corresponds to the triblock copolymer A-B-A in which A is a copolymer of methyl methacrylate (MMA) and dimethyl acrylamide (DMA) and the block B is a homopolymer of butyl acrylate.
• A is a copolymer of methyl methacrylate (MMA) and dimethyl acrylamide (DMA) and the block B is a homopolymer of butyl acrylate.
• microgranules 45 ° C
• FIG. 4b represents a photograph of the microgranules obtained by this first example of microgranulation. It can be seen from this FIG. 4b that the method implemented in this example makes it possible to obtain good control of the section and homogeneous microgranules between them. Conventional granules obtained from the same copolymer 1 are presented for comparison in Figure 4a.
• the impact modifier "copolymer 2" corresponds to the polystyrene-polybutadiene-polymethyl methacrylate copolymer.
• This second example made it possible to obtain microgranules of sizes below one micrometer.
• the particle size distribution by weight of the microgranules of the copolymer 2 is shown in Table 3. These results are obtained during a passage through the vibrating screen.
• the impact modifier in the form of microgranules obtained in Examples 1 and 2 can then be used for the preparation of a thermoset material.
• the impact modifier in the form of microgranules can thus be used in a process for preparing a thermosetting material or a hardener.
• the process for preparing the thermosetting material comprises a step of dissolution in the precursor of a composition comprising a shock modifier comprising at least one copolymer chosen from AB, ABA, ABC block copolymers in the form of microgranules with a diameter of between 400 and 1500. Dm, preferably between 400 and 1000 ⁇ , and advantageously between 500 and 800 ⁇ .
• the impact modifier is chosen from block copolymers A-B, ABA or ABC.
• thermosetting material It has been found that the use of a shock modifier for the manufacture of the thermosetting material considerably improves the preparation of the thermosetting material.
• the problems related to the agglomeration and the manipulation of the impact modifier in the form of powder are eliminated and, on the other hand, the dissolution of the impact modifier in the form of microgranules makes it possible surprisingly to dissolve faster than under the shape of a powder.
• thermosetting material obtained from an impact modifier in the form of microgranules are also very close to those of a material obtained from an impact modifier in the form of powder.
• Comparative tests have made it possible to compare the characteristics of resins obtained by mixing a precursor and a powder or microgranules. Referring to the appended FIG. 5, it is also possible to measure the viscosity of the two mixtures continuously over time.
• the viscosity of the mixture having used the impact modifier in the form of microgranules is of the same order of magnitude as that with the powder, the viscosities of each mixture remaining stable over time.
• thermoset material from a shock modifier in the form of microgranules.
• the grades have an average particle size:
• the size distribution shows a polydispersity 5 to 6 times higher for NP powder grades than for MG microgranules.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Mechanical Engineering (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Graft Or Block Polymers (AREA)

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• 2011
  • 2011-03-25 FR FR1152489A patent/FR2973033A1/fr not_active Withdrawn
• 2012
  • 2012-03-23 JP JP2014500459A patent/JP2014508845A/ja active Pending
  • 2012-03-23 CN CN201280025246.3A patent/CN103562244A/zh active Pending
  • 2012-03-23 US US14/007,020 patent/US20140018504A1/en not_active Abandoned
  • 2012-03-23 EP EP12717369.8A patent/EP2688928A1/de not_active Withdrawn
  • 2012-03-23 WO PCT/FR2012/050612 patent/WO2012131242A1/fr active Application Filing
  • 2012-03-23 KR KR1020137028022A patent/KR20140019408A/ko not_active Application Discontinuation

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