EP2117797A2 - Verfahren zur herstellung von dünnfilmobjekten - Google Patents

Verfahren zur herstellung von dünnfilmobjekten

Info

Publication number
EP2117797A2
EP2117797A2 EP08762076A EP08762076A EP2117797A2 EP 2117797 A2 EP2117797 A2 EP 2117797A2 EP 08762076 A EP08762076 A EP 08762076A EP 08762076 A EP08762076 A EP 08762076A EP 2117797 A2 EP2117797 A2 EP 2117797A2
Authority
EP
European Patent Office
Prior art keywords
copolymer
film
preform
weight
central block
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08762076A
Other languages
English (en)
French (fr)
Inventor
Jean-Pierre Disson
Pierre Gerard
Stéphanie Magnet
Christophe Navarro
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2117797A2 publication Critical patent/EP2117797A2/de
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the invention relates to an elastomeric composition based on block terpolymers whose monomer conferring on the assembly its elastomeric property is an acrylate, and to its use for the manufacture of objects with elastic films, thin impervious by means of preforms.
  • Elastic membrane-type objects such as gloves, condoms, balloons, some medical instruments, etc. have long been made from natural rubber.
  • this natural rubber is used in the form of latex, that is to say a natural emulsion of water and rubber to which are added the agents necessary for stabilization and vulcanization.
  • a shape of the object to be manufactured is then immersed in the latex bath the number of times necessary to make a layer of the desired thickness. After evaporation of the water, a solid rubber film is obtained which is then vulcanized to give it the proper properties.
  • Natural rubber has many advantages in this type of application because of its strength, elasticity and pleasant "feel".
  • natural rubber has a number of disadvantages due to the presence of tiny holes due to imperfections of the natural latex. These holes have the disadvantage of letting the small molecules pass and make them unusable in some medical applications in particular.
  • These natural rubbers also have a susceptibility to ozone causing cracking, as well as an oxidative attack resulting in loss of storage properties.
  • the natural rubber thus treated is not hypoallergenic and its regular use often causes allergic reactions.
  • the second consists of ABu and MMA in substantially equivalent amounts in the presence of 2-hydroxyethyl acrylate.
  • the copolymerization of the monomers is carried out in the presence of a persulfate as initiator.
  • This type of polymerization leads to a random copolymer, that is to say that the monomers are distributed randomly or according to their respective reactivities throughout the polymer chain. These are not block copolymers.
  • the block copolymers are copolymers in which part of the molecular chain has a composition A, and at least one other part a composition B.
  • the structures may be of the ABA type, or of the ABC type.
  • An ABC type polymer will typically be obtained by reacting a first monomer or a monomer mixture of selected composition to obtain block A, then reacting a second monomer or a second comonomer composition to obtain block B, and finally a third monomer or third comonomer composition to obtain block C. If the compositions of blocks A and C are identical, an ABA block polymer is obtained.
  • the anionic, cationic or controlled radical polymerization processes make it possible to obtain this type of structure.
  • An ABA type structure can also be obtained by first forming a block B keeping a reactivity at its two ends, then coming to form the two blocks A simultaneously. Controlled radical polymerization allows this type of process.
  • SBS polystyrene / polybutadiene / polyStyrene
  • SIS polyStyrene / polylsoprene / polyStyrene
  • Today many products such as synthetic gloves are made of S-EB-S block copolymers (polystyrene / polyethylene-butylene / polystyrene), copolymers that seem to have the best properties especially with regard to their mechanical and physical properties and their resistance to ozone and oxidation. These polymers are obtained by anionic polymerization.
  • the US'900 patent describes an elastomeric composition formed from several triblock copolymers S-EB-S having different characteristics and which are dissolved in an organic solvent, generally toluene. It is in this solution, which may include other agents, a plasticizer for example, that the preform is dipped. It is then removed after formation of the copolymer film. Evaporation of the solvent then makes it possible to obtain the final elastic copolymer film.
  • US 452 discloses the use in the manufacture of thin-film articles of an elastomeric composition based on S-EB-S triblock copolymers which are not dissolved in the organic solvent as in US Pat. 900, but dispersed in an aqueous phase in the presence of a surfactant, in the form of particles of small dimensions (about 2 microns). The rest of the process is the same as before with evaporation of the aqueous phase.
  • the diagram of FIG. 1 illustrates the process with these different steps and in particular those of the mixture with high shearing coefficient (34) and the elimination (36) of the organic solvent associated with the copolymer.
  • US'007 discloses the use in the manufacture of thin-film articles of an elastomeric composition based on a triblock copolymer S-EB-S which is dissolved in the organic solvent, toluene, as in the US'900 patent.
  • the contribution to the state of the art of this patent lies in the selection of the block copolymers to be used and in particular the respective molecular weights of the various blocks, styrene and ethylene-butylene, of the block copolymer.
  • the problem to be solved is to find for the manufacture of thin-film articles a block copolymer elastomer having at least the same performance as S-EB-S but available in the form of a stable latex similar to the latex of natural rubber and not not including the defects of the latter.
  • the invention aims to overcome these drawbacks by proposing the use of novel triblock copolymers which, in addition, may be either in the form of a solution in an organic solvent, or in the form of a latex consisting of a stable emulsion, and which therefore, in this case, make it possible to dispense with the use of the organic solvent.
  • the invention relates to a process for the manufacture of thin-film articles comprising the following steps: - preparation of a liquid phase containing, homogeneously dispersed, a polymer fraction comprising a majority of a triblock copolymer with a central block representing from 30 to 85% by weight of the copolymer, comprising a majority of an acrylate monomer having a low Tg conferring on this copolymer its elastomeric character, and identical or different side blocks having a Tg greater than that of the central block, depositing this phase liquid in the form of a film on a preform of the object to be manufactured, elimination of the liquid phase by evaporation, and solidification of the film to obtain a solid elastic film on the preform.
  • the liquid phase will be in the form of a true solution of the polymer fraction in an organic solvent.
  • This organic solvent should have good solubilization properties of the copolymers and homopolymers of the polymer fraction retained in the process. It will be chosen from aromatic derivatives such as toluene, ethylbenzene, chlorobenzene, xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone. Toluene is the preferred solvent for the process of the invention.
  • the liquid phase will be in the form of a stable aqueous emulsion of the polymer fraction (latex).
  • the subject of the invention is a process for the manufacture of thin-film articles comprising the following steps: preparation of a liquid phase, consisting of a solution in an organic solvent, of a polymer fraction comprising at least 75 % by weight of a triblock copolymer with a central block representing from 30% to 85% by weight of the copolymer comprising a majority of an acrylate monomer having a low Tg conferring on this copolymer its elastomeric character, and identical or different side blocks having a Tg higher than that of the central block, immersion of a preform of the object to be manufactured in a bath of the liquid phase, removal of the bath from the preform on which the liquid phase, containing the block copolymer to constitute the film, is deposited, evaporation of the solvent, and solidification of the film to obtain a solid elastic film on the
  • the solidification of the film can be obtained by heating the latter.
  • the invention also relates to a process for the manufacture of thin-film articles comprising the following steps: preparation of a liquid phase, consisting of an aqueous emulsion, of a polymer fraction comprising at least 75% by weight of a triblock copolymer with a central block representing from 30 to 85% by weight of the copolymer comprising a majority of an acrylate monomer having a low Tg conferring on this copolymer its elastomeric character, and identical or different side blocks having a Tg greater than that of the central block, immersing a preform of the object to be manufactured in a bath of the liquid phase, removing the bath from the preform on which the liquid phase, containing the block copolymer to form the film, is deposited, - evaporation of the solvent, and solidification of the film to obtain a solid elastic film on the preform.
  • the solidification of the film can be obtained by heating the latter.
  • the solidification can also be obtained by local destabilization of the latex by coagulation by means of a coagulating agent, such as divalent cation salts or mineral acids, previously deposited on the surface of the preform.
  • the operation can be repeated several times if it is desired to obtain a multilayer film with the same latex or the same solution, or a latex or a solution containing different grades and / or comprising complementary components capable of conferring additional properties to the final product.
  • the following steps can be carried out: preparation of a liquid phase containing either as a solution within the an organic solvent, either in the form of a stable aqueous emulsion, a polymer fraction comprising at least 75% by weight of a triblock copolymer with a central block representing from 30% to 85% by weight of the copolymer comprising a majority of an acrylate monomer having a low Tg conferring on this copolymer its elastomeric character, and identical or different lateral blocks having a Tg higher than that of the central block, and - spraying of this liquid phase on a heated preform resulting in the evaporation of the solvent and the solidification of the movie.
  • the triblock copolymer used in the process of the invention comprises, as a central block, an elastomeric polymer with an acrylate unit which gives the assembly its performance in elasticity.
  • the polymer of this central block has a glass transition (Tv) generally between (limits included) - 60 and 20 0 C and preferably between - 50 and 10 0 C.
  • Tv glass transition
  • the other blocks of the copolymer which are identical or different, are polymers conferring on the triblock its mechanical strength and have a glass transition (Tg) that is higher than that of the acrylate central block, generally between (limits included) 60 and 150 ° C. and preferably between 80 and 130 ° C.
  • These other lateral blocks will be for example polystyrene (PS), polymethylmethacrylate (PMMA), or combinations; polystyrene is generally chosen mainly for cost reasons.
  • the Tg of butyl polyacrylate is -45 ° C., that of PS about 100 ° C. and that of PMMA 115 ° C.
  • the acrylate central block content of the triblock copolymer will be between (inclusive) 30 and 85% by weight and preferably between 60 and 80% by weight.
  • the mass molecular weight Mw of the triblock copolymer will generally be between (limits included) 50,000 and 500,000 and preferably between 50,000 and 300,000.
  • block copolymers such as S-Abu-S, that is to say a copolymer having the polystyrene / biylyl polyacrylate / polystyrene block, or MAM, that is, say a copolymer having the sequence polymethacrylate methyl / poly Butyl acrylate / poly methacrylate methyl.
  • S-Abu-S that is to say a copolymer having the polystyrene / biylyl polyacrylate / polystyrene block
  • MAM that is, say a copolymer having the sequence polymethacrylate methyl / poly Butyl acrylate / poly methacrylate methyl.
  • S-Abu-M the manufacturing costs of these are naturally higher.
  • the monomers described above can also be “functionalized” by incorporating subsequently reactive monomers into the structure, such as, for example, acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate, diallyl methacrylate etc.
  • the triblock copolymer In the liquid phase, organic solution or aqueous emulsion, the triblock copolymer represents at least 75% by weight of all the polymers present. Alongside the constituents of the triblock copolymer itself, there may be found, for example, homopolymers, random copolymers.
  • the liquid phase has a polymer fraction content of between 30 and 70% and preferably between 35 and 60% by weight.
  • the triblock copolymers of the process of the invention will advantageously be synthesized by controlled radical polymerization (PRC).
  • Controlled radical polymerization makes it possible to reduce the reactions of the growing radical species, in particular the termination stage, reactions which in the conventional polymerization interrupt the growth of the polymer chain irreversibly and without control of the termination reactions.
  • "dormant" radical species in the form of a low dissociation energy bond, capable of blocking and restarting the polymerization at will.
  • periods of growth of active radical species and periods of growth arrest are obtained as required. This alternation leads to an increase in the average molecular weight according to the progress of the reaction while controlling its progress.
  • This control can result in a narrower molecular weight distribution (lower polymolecularity index) than in a conventional radical and, above all, in synthesizing block copolymers by restarting the polymerization with a new monomer from a species. dormant polymer.
  • the films manufactured according to the process do not have all the physical characteristics necessary for the intended application, it will be possible to add to the liquid phase the compounds capable of conferring on it these characteristics.
  • a plasticizer such as mineral oils compatible with the triblock copolymer of the process.
  • plasticizers include trimellitates, naphthenic oils or phthalates.
  • Butyl Acrylate / Methacrylate is 60/40 using these agents and Poly (styrene) -
  • Example 1 B Preparation of a dialkoxyamine from the monoalkoxyamine obtained in 1A
  • Example 2 Preparation in emulsion of a block copolymer latex Poly (methyl methacrylate) - Poly (butyl acrylate) - Poly (methyl methacrylate) whose weight ratio Acrylate Acrylate / Methacrylate is 60/40.
  • the reactor temperature is lowered to 80 ° C.
  • the temperature of the reactor is then brought to 105 ° C. and 2342.1 g of methyl methacrylate, degassed beforehand, are added continuously for a period of 2 hours at
  • the temperature is maintained by thermal regulation additional two hours after the end of the addition.
  • the conversion of methyl methacrylate reaches 50%.
  • the reactor temperature is then lowered to 8O 0 C.
  • step Cooking residual methyl methacrylate by a conventional radical polymerization process. At 80 ° C., 23.4 g of n-dodecyl mercaptan, 17.6 g of sodium formaldehyde sulfoxylate and 17.6 g of potassium persulfate are added and the temperature is maintained by thermal regulation for 2 hours, followed by temperature of the reaction medium is then lowered to room temperature.
  • the final latex which has the following composition:
  • Example 3 Preparation in emulsion of a copolymer latex block Poly (styrene) - Poly (butyl acrylate) - Poly (styrene) whose weight ratio Acrylate Butyl / Styrene is 60/40.
  • n-dodecyl mercaptan At 80 ° C., 4.48 g of n-dodecyl mercaptan, 33.6 g of a 10% by weight aqueous sodium formaldehyde sulfoxylate solution and 67.2 g of 5% aqueous potassium persulfate solution are used. are added and the temperature is maintained by thermal regulation for 2 hours.
  • the temperature of the reactor is then brought to 120 ° C. and 2342.1 g of pre-degassed styrene are added continuously over a period of 2 hours at 120 ° C.
  • the temperature is maintained by thermal regulation for two more hours after the end of the period. 'addition.
  • the conversion of styrene reaches 50%.
  • the reactor temperature is then lowered to 8O 0 C.
  • step Styrene residual cooking by a conventional radical polymerization process.
  • 80 ° C. 23.4 g of n-dodecyl mercaptan, 17.6 g of sodium formaldehyde sulfoxylate and 17.6 g of potassium persulfate are added and the temperature is maintained by thermal regulation for 2 hours, followed by temperature of the reaction medium is then lowered to room temperature.
  • the final latex which has the following composition:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Moulding By Coating Moulds (AREA)
  • Materials For Medical Uses (AREA)
EP08762076A 2007-02-13 2008-02-13 Verfahren zur herstellung von dünnfilmobjekten Withdrawn EP2117797A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0753209A FR2912411B1 (fr) 2007-02-13 2007-02-13 Procede pour la fabrication d'objets a films minces.
PCT/FR2008/050226 WO2008104705A2 (fr) 2007-02-13 2008-02-13 Procede pour la fabrication d'objets a films minces

Publications (1)

Publication Number Publication Date
EP2117797A2 true EP2117797A2 (de) 2009-11-18

Family

ID=38446045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08762076A Withdrawn EP2117797A2 (de) 2007-02-13 2008-02-13 Verfahren zur herstellung von dünnfilmobjekten

Country Status (3)

Country Link
EP (1) EP2117797A2 (de)
FR (1) FR2912411B1 (de)
WO (1) WO2008104705A2 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112900A (en) * 1990-11-28 1992-05-12 Tactyl Technologies, Inc. Elastomeric triblock copolymer compositions and articles made therewith
JP2003213197A (ja) * 2002-01-24 2003-07-30 Nippon Zeon Co Ltd コーティング剤およびディップ成形品
JP2004285220A (ja) * 2003-03-24 2004-10-14 Nippon Zeon Co Ltd コーティング剤組成物およびディップ成形品
FR2866026B1 (fr) * 2004-02-06 2008-05-23 Arkema Procede de polymerisation radicalaire en emulsion mettant en oeuvre des alcoxyamines hydrosolubles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008104705A3 *

Also Published As

Publication number Publication date
FR2912411B1 (fr) 2009-04-10
WO2008104705A2 (fr) 2008-09-04
WO2008104705A3 (fr) 2008-10-16
FR2912411A1 (fr) 2008-08-15

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