WO2010036243A1 - Greffage direct sans peroxyde de monomères polaires sur des polyoléfines insaturées - Google Patents

Greffage direct sans peroxyde de monomères polaires sur des polyoléfines insaturées Download PDF

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Publication number
WO2010036243A1
WO2010036243A1 PCT/US2008/077485 US2008077485W WO2010036243A1 WO 2010036243 A1 WO2010036243 A1 WO 2010036243A1 US 2008077485 W US2008077485 W US 2008077485W WO 2010036243 A1 WO2010036243 A1 WO 2010036243A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin
free
oxidized
polar monomer
graftable
Prior art date
Application number
PCT/US2008/077485
Other languages
English (en)
Inventor
Chunxia Costeau
Anthony Neubauer
Nathan Wiker
Timothy Pope
William Michie
Original Assignee
Dow Global Technologies Inc.
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 Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Priority to EP08823416A priority Critical patent/EP2328946A1/fr
Priority to PCT/US2008/077485 priority patent/WO2010036243A1/fr
Priority to CN2008801320688A priority patent/CN102224178A/zh
Publication of WO2010036243A1 publication Critical patent/WO2010036243A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/06—Oxidation
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

Definitions

  • This invention relates to processes for grafting polyolefins. Specifically, it relates to a process for peroxide-free direct grafting of polar monomers onto unsaturated polyolefins.
  • Grafting polar groups such as maleic anhydride, acrylic acid, or silane onto non-polar polymeric chains is a common way to modify polymers, which is usually called functionalization of polymers.
  • the coexistence of polar and non-polar groups in the functionalized polymers makes them useful as a compatibilizing agent to improve the compatibility of two substances, which are originally incompatible such as polyethylene and nylon.
  • maleic anhydride is grafted to saturated polymer chains under which produce macro-polymer radicals and maleic radicals.
  • One way to produce these radicals is using high energy such as gamma radiation, UV radiation, or shock waves.
  • Another radical initiator mechanism uses organic peroxides. First, the peroxide decomposes into free radicals. Then, the peroxide free radicals react with polymer chains to produce polymer macro-radicals and convert the polar monomer to an excited dimer. Finally, the polymer macro-radical reacts with the excited dimer and forms grafted polymer chains.
  • the present invention is a peroxide-free process for preparing a direct grafted polyolefin.
  • the process has the steps of (a) selecting an antioxidant-free, unsaturated polyolefin, (b) oxidizing the polyolefin, (c) selecting a graftable, polar monomer, (d) combining the polyolefin and the graftable, polar monomer, (e) forming free radicals on the oxidized polyolefin, and (f) grafting the graftable, polar monomer onto the polyolefin at the free-radical sites.
  • Figure 1 shows the Time Lapsed Changes in Mass Due to Moisture for non- talc containing compositions, including comparative examples and the examples of the present invention.
  • Figure 2 shows the Time Lapsed Changes in Thickness Due to Moisture for non-talc containing compositions, including comparative examples and the examples of the present invention.
  • Figure 3 shows the Time Lapsed Changes in Mass Due to Moisture for medium-talc containing compositions, including comparative examples and the examples of the present invention.
  • Figure 4 shows the Time Lapsed Changes in Thickness Due to Moisture for medium-talc containing compositions, including comparative examples and the examples of the present invention.
  • Figure 5 shows the Time Lapsed Changes in Mass Due to Moisture for high- talc containing compositions, including comparative examples and the examples of the present invention.
  • Figure 6 shows the Time Lapsed Changes in Thickness Due to Moisture for high-talc containing compositions, including comparative examples and the examples of the present invention.
  • the invented peroxide-free process for preparing a direct-grafted polyolefin comprises the steps of (a) selecting a polyolefin having unsaturation and being substantially free of antioxidants, (b) oxidizing the polyolefin, (c) selecting a graftable, polar monomer, (d) combining the polyolefin and the graftable, polar monomer, (e) forming free radicals on the oxidized polyolefin, and (f) grafting the graftable, polar monomer onto the polyolefin at the free-radical sites.
  • the process is substantially free of organic peroxides. Preferably, there are no organic peroxides present.
  • Suitable polyolefins include ethylene polymers prepared with alkyl chromate catalysts, their variants, silyl chromate catalysts, their variants, chromium oxide catalysts, and their variants. More preferably, when the catalyst is a variant of silyl chromate, the catalyst will be bis(triphenylsilyl)chromate catalyst chemically reduced with diethyl aluminum ethoxide in various molar ratios to give 0.5 to 12 AlCr molar ratios.
  • the ethylene polymer may be a high density polyethylene, medium density polyethylene, and low density polyethylene, having vinyl, trans vinyl, and/or vinylidene groups.
  • the level of unsaturation relates to the grafting reaction of the present invention. It is believed that the theoretical grafting limit can be calculated according to equal mole criterion. Furthermore, the number of carbon double bonds per 1000 carbon of a polymer can be measured using a nuclear magnetic resonance method.
  • an appropriate polyolefin can be selected based upon the desired level of polar monomer grafting. It is further contemplated that the level of grafting may be controlled based upon the amount of polar monomer added during the invented process.
  • the polyolefin should be at least substantially free of any antioxidants. Preferably, the polyolefin would have no antioxidant present.
  • Antioxidants would inhibit the oxidization of the unsaturated polyolefin. It is believed that several methods are known for oxidizing unsaturated polyolefins. For example, the combination of the carbon double bonds, absorbed oxygen (air), and purging/storage temperature will introduce oxidation reactions to the polymer and result in incorporating some peroxide groups.
  • the unsaturated polyolefin can be oxidized by subjecting the polyolefin to an oxygen-containing environment, for an amount of time and at a suitable temperature to yield oxidation of the polyolefin.
  • the efficiency of oxidizing the polyolefin may be improved when residual catalyst or other promoters are present.
  • the temperature of oxidation it is preferable to manage the temperature of oxidation to avoid certain side reactions.
  • it is preferable to perform the oxidizing step occurs at a temperature that permits the polyolefin to remain substantially free of crosslinking bonds or chain scissioning.
  • air purging following combination of the polyolefin and the graftable, polar monomer in the reactive extruder should be avoided.
  • the air purging can promote the competitive side reaction of crosslinking rather than introducing additional peroxide groups for grafting.
  • Suitable graftable, polar monomers may be ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides, including derivatives of such acids, and mixtures thereof, and vinyl trialkoxy silanes.
  • acids and anhydrides which may be mono-, di- or polycarboxylic acids, are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, itaconic anhydride, maleic anhydride and substituted maleic anhydride, e.g., dimethyl maleic anhydride or citraconic anhydride, nadic anhydride, nadic methyl anhydride and tetrahydro phthalic anhydride.
  • Examples of derivatives of the unsaturated acids are salts, imides, amides and esters, e.g., mono- and disodium maleate, acrylamide, maleimide, glycidyl methacrylate and diethyl fumarte.
  • Examples of the vinyl trialkoxy silanes are vinyl trimethoxy silane and vinyl triethoxy silane.
  • the free radicals can be formed on the oxidized polyolefin by heating the oxidized polyolefin.
  • the present invention is a process for preparing a grafted polyolefin comprising the steps (a) selecting an oxidized polyolefin; (b) selecting a graftable, polar monomer; (c) combining the oxidized polyolefin and the graftable, polar monomer; (d) forming free radicals on the oxidized polyolefin; and (e) grafting the graftable, polar monomer onto the oxidized polyolefin at the free-radical sites.
  • Suitable oxidized polyolefins are derived from the oxidization of unsaturated ethylene polymers prepared with alkyl chromate catalysts, their variants, silyl chromate catalysts, their variants, chromium oxide catalysts, and their variants.
  • WO 2005/116091 teaches a method for preparing a polyolefin with enriched peroxide content via reactivation. That reference is incorporated herein by reference.
  • the present invention is a peroxide-free process for preparing a direct-grafted polyolefin comprising the steps of (a) selecting an oxidized polyolefin, (b) selecting a graftable, polar monomer, (c) admixing in an extruder the oxidized polyolefin and the graftable, polar monomer, (d) heating the mixture to a temperature suitable for free -radically activating the oxidized sites on the polyolefin, (e) grafting the polar monomer onto the polyolefin at the oxidized sites, and (f) extruding direct-grafted polyolefin from the extruder.
  • the present invention is a direct-grafted polyolefin prepared by any of the described methods.
  • the present invention is a polyolefin-based composition made from or containing the direct-grafted polyolefin and at least one additive.
  • the composition may contain more than one direct-grafted polyolefin and/or more than one additive.
  • the present invention is a bio-fiber-plastic composite formulation containing or made from the direct-grafted polyolefin and a bio-fiber component.
  • Suitable bio-fiber components include wood, hemp, kenaf, rice hulls, wheat straw, and other cellulosic materials.
  • the bio-fiber component may be present any amount up to about 90 weight percent.
  • the bio-fiber plastic composite formulation may also contain other polymeric materials such as high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, polyvinyl chloride, acrylonitrile butadiene styrene polymers, or other polymers. These polymeric materials may be present in an amount up to about 90 weight percent. Preferably, they are present in an amount between about 30 and about 70 weight percent.
  • additives include talc and inorganic fillers, processing aids, coupling aids, pigments, antioxidants, microbial additives, and flame retardants.
  • Talc and inorganic fillers may be present in an amount up to about 20 weight percent.
  • the processing aids include metallic stearates, waxes, amides, and other materials, which may be present in an amount up to about 6 weight percent.
  • Coupling agents include, for example, maleic anhydride grafted polymers and silane grafted polymers, which may be present in an amount up to about 6 weight percent.
  • Pigments, antioxidants, and microbial additives are generally present in an amount less than about 5 weight percent.
  • Both the modulus of elasticity and the modulus of rupture were measured according to ASTM D790, "Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials.”
  • the specimens had a width of 1.0 inch (25.4 mm) and a length of 6 inch (152 mm).
  • the thickness of the specimen was targeted at 0.25 inch (6.4 mm), and the support span was set at 4 inch (102 mm), yielding a 16:1 L/D ratio as required by the ASTM testing protocol.
  • the testing was conducted in a standard room temperature of 23 degrees Celsius and 50 percent humidity.
  • the moisture resistance was measured according to ASTM D570-98, "Standard Test Method for Water Absorption of Plastics," by using a rectangular bar in dimensions of 1 inch x 4 inch x 0.25 inch (25.4 mm x 102 mm x 6.4 mm) (W x L x T). As required by the testing method, a set of 3 specimens was prepared for each sample. The weight of each bar was measured and recorded prior to submerging in water. The bars were placed upright in a bucket filled with water. The weight and dimensions of each specimen were recorded at successive intervals of time. The percentage change of mass and volume were recorded and plotted.
  • compositions were evaluated at three different talc levels: (1) none; (2) medium - 5 weight percent; and (3) high - 14 weight percent.
  • the talc used was Luzenac Nicron 403, which had an approximate average particle size of 0.5 micron and was supplied by Rio Tinto Minerals.
  • the following components were used to prepare the compositions: (a) Amplify GR205TM maleic anhydride grafted high density polyethylene, having a melt index of 2.0 gram per 10 minute (measured at 190 degrees Celsius, 2.16 kilogram), a density of 0.965 gram per cubic centimeter, and a maleic anhydride grafting level of 1.2 weight percent.
  • the polymer was commercially available from The Dow Chemical Company.
  • Lotader 3210TM random terpolymer of ethylene, butyl acrylate, and maleic anhydride having a melt index of 5 gram per 10 minute (measured at 190 degrees Celsius and under 2.16 kilogram), a density of 0.94 gram per cubic centimeter, and a maleic anhydride grafting level of 3 weight percent.
  • the butyl acrylate component was present in an amount of 5 weight percent. It was commercially available from Arkema.
  • Wood flour 60-mesh particle- size pine was commercially available from American Wood Fiber.
  • Struktol TPW 113TM processing aid being a blend of a complex, modified fatty acid ester and having a specific gravity of 1.005, was commercially available from Struktol Company of America.
  • Struktol TPW 104TM processing aid being a blend of aliphatic carboxylic acid salts and mono and diamides, was commercially available from Struktol Company of America.
  • the amount of components utilized to make the non-talc formulations are shown in Table 1.
  • Table 1 also recites the values determined for the physical properties of elastic modulus and rupture modulus.
  • Table 2 The amount of components utilized to make the medium talc formulations are shown in Table 2.
  • Table 2 also recites the values determined for the physical properties of elastic modulus and rupture modulus.
  • Table 3 also recites the values determined for the physical properties of elastic modulus and rupture modulus.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé sans peroxyde pour préparer une polyoléfine à greffage direct. Le procédé comprend les étapes de (a) sélection d’une polyoléfine insaturée, sans antioxydant, (b) oxydation de la polyoléfine, (c) sélection d’un monomère polaire greffable, (d) combinaison de la polyoléfine et du monomère polaire greffable, (e) formation de radicaux libres sur la polyoléfine oxydée, et (f) greffage du monomère polaire greffable sur la polyoléfine aux sites de radical libre.
PCT/US2008/077485 2008-09-24 2008-09-24 Greffage direct sans peroxyde de monomères polaires sur des polyoléfines insaturées WO2010036243A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP08823416A EP2328946A1 (fr) 2008-09-24 2008-09-24 Greffage direct sans peroxyde de monomères polaires sur des polyoléfines insaturées
PCT/US2008/077485 WO2010036243A1 (fr) 2008-09-24 2008-09-24 Greffage direct sans peroxyde de monomères polaires sur des polyoléfines insaturées
CN2008801320688A CN102224178A (zh) 2008-09-24 2008-09-24 不含过氧化物直接接枝极性单体到不饱和聚烯烃上

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2008/077485 WO2010036243A1 (fr) 2008-09-24 2008-09-24 Greffage direct sans peroxyde de monomères polaires sur des polyoléfines insaturées

Publications (1)

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WO2010036243A1 true WO2010036243A1 (fr) 2010-04-01

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EP (1) EP2328946A1 (fr)
CN (1) CN102224178A (fr)
WO (1) WO2010036243A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016083530A1 (fr) 2014-11-26 2016-06-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Polymères modifiés au moyen d'un réactif modificateur et procédé de leur production

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332749A (en) * 1979-05-10 1982-06-01 Hercules Incorporated Process for the production of polyolefine-based fibrids, and the fibrids obtained
EP0081442A2 (fr) * 1981-12-03 1983-06-15 Etablissement Public dit: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS) Nouvelle polyoléfine greffée et procédé pour sa préparation
EP0540026A1 (fr) * 1991-10-31 1993-05-05 Montell North America Inc. Compositions de polyoléfine et procédé pour leur préparation
DE19511579C1 (de) * 1995-03-29 1996-03-07 Leuna Werke Gmbh Verfahren zur Herstellung von thermoplastischen Formmassen aus synthetischen und natürlichen Polymeren und deren Verwendung
EP0806439A2 (fr) 1996-05-06 1997-11-12 Montell North America Inc. Procédé de préparation de polypropylène greffé à l'aide d'un système catalytique redox
WO2004113406A1 (fr) 2003-06-23 2004-12-29 Basell Poliolefine Italia S.R.L. Procede de fabrication de copolymeres greffes a l'etat fondu a l'aide d'un polymere olefinique reactif renfermant un peroxyde
US20060160954A1 (en) 2004-12-14 2006-07-20 Basell Poliolefine Italia S.R.L. Preparation of graft copolymers by sequential polymerization using peroxide-containing polyolefins
US20070141337A1 (en) 2005-12-20 2007-06-21 Mehta Sameer D Cellulosic-reinforced composites having increased resistance to water absorption

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332749A (en) * 1979-05-10 1982-06-01 Hercules Incorporated Process for the production of polyolefine-based fibrids, and the fibrids obtained
EP0081442A2 (fr) * 1981-12-03 1983-06-15 Etablissement Public dit: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS) Nouvelle polyoléfine greffée et procédé pour sa préparation
US4443584A (en) 1981-12-03 1984-04-17 Centre National De La Recherche Scientifique Method for preparing graft polyolefin
EP0540026A1 (fr) * 1991-10-31 1993-05-05 Montell North America Inc. Compositions de polyoléfine et procédé pour leur préparation
DE19511579C1 (de) * 1995-03-29 1996-03-07 Leuna Werke Gmbh Verfahren zur Herstellung von thermoplastischen Formmassen aus synthetischen und natürlichen Polymeren und deren Verwendung
EP0806439A2 (fr) 1996-05-06 1997-11-12 Montell North America Inc. Procédé de préparation de polypropylène greffé à l'aide d'un système catalytique redox
WO2004113406A1 (fr) 2003-06-23 2004-12-29 Basell Poliolefine Italia S.R.L. Procede de fabrication de copolymeres greffes a l'etat fondu a l'aide d'un polymere olefinique reactif renfermant un peroxyde
US20060160954A1 (en) 2004-12-14 2006-07-20 Basell Poliolefine Italia S.R.L. Preparation of graft copolymers by sequential polymerization using peroxide-containing polyolefins
US20070141337A1 (en) 2005-12-20 2007-06-21 Mehta Sameer D Cellulosic-reinforced composites having increased resistance to water absorption

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016083530A1 (fr) 2014-11-26 2016-06-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Polymères modifiés au moyen d'un réactif modificateur et procédé de leur production
DE102014117307A1 (de) 2014-11-26 2016-06-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Mittels eines Modifizierungsreagenzes modifizierte Polymere und Verfahren zu deren Herstellung

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CN102224178A (zh) 2011-10-19
EP2328946A1 (fr) 2011-06-08

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