EP2152804A1 - Résines de réaction contenant des particules de type c ur-écorce et procédé pour leur production et leur utilisation - Google Patents

Résines de réaction contenant des particules de type c ur-écorce et procédé pour leur production et leur utilisation

Info

Publication number
EP2152804A1
EP2152804A1 EP08759723A EP08759723A EP2152804A1 EP 2152804 A1 EP2152804 A1 EP 2152804A1 EP 08759723 A EP08759723 A EP 08759723A EP 08759723 A EP08759723 A EP 08759723A EP 2152804 A1 EP2152804 A1 EP 2152804A1
Authority
EP
European Patent Office
Prior art keywords
mol
weight
shell
reaction resin
core
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.)
Ceased
Application number
EP08759723A
Other languages
German (de)
English (en)
Inventor
Oliver SCHÄFER
Helmut Oswaldbauer
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.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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 Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP2152804A1 publication Critical patent/EP2152804A1/fr
Ceased legal-status Critical Current

Links

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
    • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08L51/04—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 rubbers
    • 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
    • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes

Definitions

  • the invention relates to a core-shell particle-containing reaction resin and a process for its preparation and its use for the production of thermosetting plastics having improved mechanical properties such as fracture toughness and impact resistance.
  • crosslinked reaction resins Due to the usually very high crosslinking density crosslinked reaction resins have some valuable properties, so that they are among the thermoplastics among the most widely used polymers. These properties include their hardness, strength, chemical resistance and temperature resistance. As a result, these reaction resins for applications in a variety of fields, eg for the production of fiber-reinforced plastics, electrical insulators, for the production of structural adhesives, laminates, stoving, etc. In addition, the thermosets have a serious drawback, which in many cases an application opposes. As a result of the highly crosslinked state, they have a very low impact strength.
  • thermosetting plastic e.g., thermosetting plastic
  • thermoplastic polymers are normally preferred. with associated disadvantages such as lower heat resistance and chemical resistance must be taken into account.
  • thermosets To improve this behavior, several methods have been developed to improve the impact resistance or flexibility of thermosets. Most of these methods aim to introduce elastic components as impact modifiers into the reaction resins.
  • powdered, soft fillers such as rubber powder or soft elastic plastic powder
  • the particle size of such powdered additives is in the range of about 0.04 to 1 mm, which is obviously not sufficient to improve such reaction resins in the desired manner, and which is also associated with disadvantages for other important performance properties of such modified thermosets.
  • plasticizers attempts to improve the impact resistance of crosslinked reaction resins. As a result, an improvement in the impact resistance can be achieved, but unfortunately causes a deterioration of other essential properties of the thermosets. In addition, the use of plasticizers is a latent risk of bleeding after crosslinking of the reaction resin with the associated negative consequences for the surface properties of the
  • NBR liquid or solid but uncrosslinked butadiene-acrylonitrile rubbers
  • siloxane-polyester copolymers as toughening additives in reaction resins.
  • These elastomers contain functional groups that can be reacted with the reaction resin in the crosslinking process or in an upstream reaction.
  • the peculiarity of these modifiers compared to the previously mentioned is that although they are miscible with the uncrosslinked reaction resin, during the crosslinking of the reaction resin, however, a phase separation takes place, in which the rubber phase precipitates in the form of fine droplets.
  • thermosets have significant shortcomings. For example, the thermal stability of nitrile rubber-modified thermosets deteriorates, questioning their usability at high temperatures. The same applies to many electrical properties, e.g. the dielectric strength. Due to the relatively good compatibility of the nitrile rubber with most reaction resins, in particular with epoxy resins, a certain proportion of the rubber in the phase separation at
  • EP 0266513 Bl describes modified reaction resins, processes for their preparation and their use. It is limited to compositions which in addition to a reaction resin max. 2-50 wt.% Contain three-dimensionally crosslinked polyorganosiloxane rubbers having particle sizes of 0.01 to 50 microns in amounts of 2-50 wt.%, The properties of the composition described therein in terms of impact resistance and impact strength are insufficient. Furthermore, the processes described in EP 0266513 Bl have a disadvantage insofar as it is necessary to develop different procedures and formulations for each reaction resin and thus also obtain different property profiles. Furthermore, in the described formulations the Presence of unreacted components such as free silicone oils are not excluded, which can lead to deterioration in the adhesion characteristic.
  • WO2006037559 describes modified reaction resins and processes for their preparation.
  • solutions of preformed particles in organic solutions are mixed with reaction resins and the reaction resins according to the invention can be obtained by subsequent removal of the solvent.
  • Disadvantages of this process are the sometimes large amounts of solvent which can be removed again only with great difficulty and, if not completely removed during curing of the reaction resins, can lead to defects in the material.
  • Another disadvantage is the use of inorganic salts, which are always found in the organic solutions of the siloxane even after extraction, as these partially absorb water and so saline water traces are always included, whereby saline impurities are introduced into the reaction resin, which for electronic applications of Reaction resins are undesirable.
  • the object of the invention is to improve the state of the art and to produce a homogeneous reaction resin, which has improved properties in terms of impact resistance and impact strength after curing and shaping, and possibly only shows low conductivity values.
  • the invention relates to a composition
  • a composition comprising (A) 50 to 99.5 wt .-% of a processable to thermosets, at temperatures in the range of 15 to 100 0 C liquid Reaction resin or reaction resin mixture having an average molecular weight of 200 to 500,000 and sufficient for the curing process number of reactive groups and (B) 0.5 to 50 wt .-% of one or more three-dimensionally crosslinked redispersed Polyorganosiloxankautschuke in the reaction resin or reaction resin mixture homogeneous in finely divided form as polyorganosiloxane rubber particles having a diameter of 0.001 to 0.4 microns, wherein the polyorganosiloxane rubber particles are composed of a core (a) consisting of an organosilicon polymer and an organopolymer shell (d) and optionally two inner shells (b) and (c), wherein the inner shell (c) is an organic polymer and the inner shell (b) is an organosilicon polymer consisting of
  • the radicals R are preferably alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, hexyl radical; Alkenyl radicals such as the vinyl and allyl radical and butenyl radical; Aryl radicals, such as the phenyl radical; or substituted hydrocarbon radicals.
  • halogenated hydrocarbon radicals such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl radical, and the chlorophenyl radical
  • Mercaptoalkyl radicals such as the 2-mercaptoethyl and 3-
  • Cyanoalkyl radicals such as the 2-cyanoethyl and 3-cyanopropyl radicals
  • Aminoalkyl radicals such as the 3-aminopropyl radical
  • Acyloxyalkyl radicals such as 3-acryloxypropyl and 3-methacryloxypropyl
  • Hydroxyalkyl radicals such as the hydroxypropyl radical.
  • radicals methyl, ethyl, propyl, phenyl, vinyl, 3-methacryloxypropyl, 1-methacryloxymethyl, 1-acryloxymethyl and 3-mercaptopropyl where less than 30 mol% of the radicals in the siloxane polymer vinyl, 3-methacryloxypropyl or 3- Mercaptopropyl groups are.
  • monomers for the organic polymer portion d) are preferably acrylic or methacrylic esters of aliphatic alcohols having 1 to 10 carbon atoms, acrylonitrile, styrene, p-methylstyrene, alpha-methylstyrene, vinyl acetate, vinyl propionate, maleimide, vinyl chloride, ethylene, butadiene, isoprene and Chloroprene or difunctional radicals such as allyl methacrylate used.
  • styrene and acrylic acid esters and methacrylic acid esters of aliphatic Alcohols having 1 to 4 carbon atoms for example methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl methacrylate or butyl (meth) acrylate. Both homopolymers and copolymers of said monomers are suitable as the organic polymer fraction.
  • the finely divided elastomeric graft copolymers have an average particle size (diameter) of 10 to 400 nm, preferably 40 to 300 nm, measured with the transmission electron microscope.
  • the particle size distribution is preferably very uniform, the graft copolymers are preferably monomodal, ie the particles have a maximum in the particle size distribution and a polydispersity factor sigma 2 of at most 0.2, measured by the transmission electron microscope.
  • the polyorganosiloxane rubber particles may have reactive groups on their surface which, if appropriate in the presence of reaction auxiliaries, react chemically with the reaction resin before or during further processing of the modified reaction resin, optionally together with small amounts of auxiliaries, in particular crosslinking agents , Catalysts, dispersants and / or curing agents.
  • the modified reaction resin is preferably further characterized in that the content of sodium, magnesium or calcium ions is below 50 ppm and the content of chloride, sulfate ions is also below 50 ppm.
  • the content of residual solvent is preferably less than 0.3% by weight, very particularly preferably less than 0.1% by weight.
  • the core rubbery phase is a silicone rubber or the mixture of a silicone rubber with an organic rubber such as a diene rubber, fluororubber, acrylate rubber or wherein the core must consist of at least 40 wt.% Of a rubber phase.
  • Particularly preferred is a core which consists of at least 50 wt.% Of a silicone rubber.
  • Particularly preferred core-shell particles contain a core of at least 20% by weight of a crosslinked silicone core and a
  • Particularly preferred organopolymers are polymers based on
  • the glass transition temperature of the shell is preferably between 60 0 C and 150 0 C, most preferably 80 ° and
  • Reaction resin preferably 1 to 60 wt.%, Preferably 1 to 15 wt .-%, particularly preferably 2 to 5 wt.% Of one or more three-dimensionally crosslinked polyorganosiloxane rubbers.
  • Suitable reaction resins according to the invention are all polymeric or oligomeric organic compounds which are provided with a sufficient number of suitable reactive groups for a curing reaction.
  • all reactive resins are generally suitable which can be processed to thermosets, regardless of the respective
  • Crosslinking mechanism which takes place in the curing of the respective reaction resin.
  • the reaction resins which can be used as starting materials can be divided into three groups according to the type of crosslinking by addition, condensation or polymerization.
  • Epoxy and urethane resins are usually crosslinked by addition of stoichiometric amounts of a hydroxyl, amino, carboxyl or carboxylic anhydride curing agent, wherein the curing reaction takes place by addition of the oxirane or isocyanate groups of the resin to the corresponding groups of the curing agent.
  • epoxy resins the so-called catalytic curing by polyaddition of the oxirane groups themselves is also possible.
  • Air-drying alkyd resins crosslink by autoxidation with atmospheric oxygen.
  • addition-curing silicone resins are known, preferably those with the proviso that no further free silanes are included.
  • Examples of the second group of crosslinked by polycondensation reaction resins are condensation products of aldehydes, such as formaldehyde, with amine group-containing aliphatic or aromatic compounds, such as urea or melamine, or with aromatic compounds such as phenol, resorcinol, cresol, etc., furan resins, saturated polyester resins and condensation-curing silicone resins. Curing is usually carried out by increasing the temperature with elimination of water, low molecular weight alcohols or other low molecular weight compounds.
  • Preferred starting materials for the reaction resins modified according to the invention are one or more phenolic resins, resorcinol resins and / or cresol resins, both resoles and novolaks, and also urea, formaldehyde and melamine resins.
  • Formaldehyde precondensates, furan resins and saturated polyester resins and / or silicone resins selected.
  • the three-dimensional crosslinking is effected.
  • initiators compounds capable of forming free radicals, e.g. Peroxides, peroxo compounds or azo group-containing compounds.
  • thermosetting resins not only the above-mentioned reactive resins, but also all others used for the production of thermosetting resins
  • Plastics are suitable, can be modified in the manner proposed according to the invention and yield after curing and curing thermosets with significantly improved fracture and impact resistance, with other essential properties, such as strength, heat resistance and chemical resistance, which are characteristic of the thermoset, remain substantially unaffected , It does not matter if the reaction resins are solid or liquid at room temperature. The molecular weight of the reaction resins is practically irrelevant. Compounds often called
  • Hardener components for reactive resins are used, such as phenolic resins or anhydride can also be considered as reactive resins.
  • reactive resins in the composition according to the invention epoxy resins, such as the bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, novolak epoxy resins, biphenyl unit-containing epoxy resins, aliphatic or cycloaliphatic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. All epoxy resins may deviate more or less from the monomeric structure, depending on the degree of condensation in the preparation. Furthermore, acrylate resins can be used for the compositions according to the invention.
  • acrylate resins examples include triethylene glycol dimethacrylate, urethane dimethacrylate, glycidyl methacrylate. Also, phenolic resins, urethane resins, silicone resins, the latter preferably those with the proviso that no further free silanes are included.
  • a further subject matter is a process for the preparation of core-shell particles containing reaction resins, characterized in that (A) 50 to 99.5 wt .-% of a processable to thermosetting, at temperatures in the range of 15 to 100 0 C liquid reaction resin or reaction resin mixture having an average molecular weight of 200 to 500,000 and having a sufficient number of suitable reactive groups for the curing process, and
  • polyorganosiloxane gum Particles are composed of a core (a) consisting of an organosilicon polymer and an organopolymer shell (d) and optionally two inner shells (b) and (c), wherein the inner shell (c) is an organic polymer and the inner shell ( b) an organosilicon polymer consisting of (a) 20 to 95 wt.%, based on the total weight of the polyorganosiloxane rubber particle, a core polymer of the general formula (R 3 SIOI 72) "(R 2 Si0 2/2) x.
  • Organopolymer monoolefinically unsaturated monomers wherein R is the same or different monovalent alkyl or alkenyl radicals having 1 to 6 carbon atoms, aryl radicals or substituted hydrocarbon radicals having, are mixed at temperatures of 0 0 C to 180 0 C, wherein the (B) Polyorganosiloxane rubber particles are homogeneously distributed in the reaction resin.
  • the components are mixed, wherein the polyorganosiloxane rubber particles are homogeneously distributed in the reaction resin.
  • This may include stirrer, dissolver, kneader, roller mills, high-pressure homogenizers, ultrasonic homogenizers u. Dispersers of the type "Ultra-Turrax" are used.
  • the applied temperatures must not lead to a noticeable crosslinking of the reaction resins during the dispersion phase.
  • solvents may optionally be added, preferably dispensing with the use of solvents.
  • the proportion of reaction resin is preferably between 99% by weight and 80% by weight.
  • This mixture of reaction resin and polyorganosiloxane rubber particles according to the invention may optionally contain further siloxane particles, e.g. in EP 744 432 A or EP 0 266 513 Bl.
  • modified reaction resins of the present invention have a number of advantages over comparable known products and can therefore be used to advantage in many fields. These advantages include primarily the improvement of the fracture and
  • thermosetting plastics both at very low temperatures depending on the polyorganosiloxane used up to -50 0 C and at very high temperatures, ie up to the softening temperature of the respective thermosets. It is also important that the modification does not exert a negative influence on the hardness, strength and softening temperature of the crosslinked reaction resin. Due to the elastomer component, the cured according to the invention reaction resin has a high aging, weathering, Light and temperature resistance, without thereby affecting the characteristic properties of the thermoset itself. The electrical properties, in particular the insulating properties of the reaction resin are not affected, especially at higher temperatures.
  • the processing of the impact-modified reaction resins according to the invention can be carried out in a conventional manner.
  • the modified reactive resins according to the invention are suitable for all fields of application in which thermosetting plastics are customarily used. In addition, they are particularly suitable for applications in which pure thermosets could not be used because of their unsatisfactory fracture and impact resistance.
  • Suitable uses of the modified reactive resins according to the invention are, in particular, those for the production of break-resistant and impact-resistant, optionally formed thermosetting plastics, fiber-reinforced plastics, insulating materials in electrical engineering and laminates.
  • Standard deviation sigma be determined. From the curve for the surface distribution, one obtains the mean value for the mean volume V. From the curve for the surface distribution one obtains the mean value for the mean surface A of the particles.
  • Polydispersity index sigma 2 can be calculated using the following formulas:
  • the particle size and the polydispersity index were determined using a transmission electron microscope from Phillips (Phillips CM 12) and an evaluation unit from Zeiss (Zeiss TGA 10).
  • the latex to be measured was diluted with water and applied to a standard copper mesh with a 1 ⁇ 1 seed loop.
  • thermosets significantly improved material toughness or Fracture toughness, especially impact resistance, while the other, advantageous for thermosets properties such as temperature resistance, strength and chemical resistance, are not or only slightly affected.
  • Example 1 (not according to the invention):
  • Methyl methacrylate added and the polymerization by addition of 5.2 g (0.6 wt.% Based on monomer) K2S2O8 and 18 g (2.1
  • NaHSC> 3 37 wt.% In water
  • Methyl methacrylate added, then heated to 65 0 C and polymerized within 3 hours.
  • Methacryloxypropyltrimethoxysilane added and stirred at 90 ° C for 1 hour. A dispersion having a solids content of 23% by weight and an average particle size of 122 nm was obtained.
  • Methyl methacrylate added and the polymerization by addition of 5.2 g (0.6 wt.% Based on monomer) K2S2O8 and 18 g (2.1
  • NaHSC> 3 37 wt% in water
  • Vinyltrimethoxysiloxane added within 2 hrs. And stirred for 3 hrs.
  • Methacryloxypropyltrimethoxysilane metered and 1 hour at 90
  • Methyl methacrylate added and the polymerization by addition of 5.2 g (0.6 wt.% Based on monomer) K2S2O8 and 18 g (2.1
  • the dispersions prepared in Examples 1-3 were sprayed from aqueous dispersion.
  • the dispersion was sprayed through a single-fluid nozzle in a spray-drying tower of the company.
  • Nubilosa (height 12 m, diameter 2.2 m) with a pressure of 33 bar.
  • the inlet temperature was 145 0 C
  • the exit temperature was 75 0 C
  • the dispersions were preheated to 55 0 C.
  • the throughput was 65 1 dispersion per hour and the amount of drying air 2000 m ⁇ / h. Of all 3 dispersions, powdery products were obtained.
  • Rotor-stator mixer (Ultra-Turrax) in varying weight ratios in different reaction resins about 5
  • the white, smooth dispersion of core-shell parts in unsaturated polyester resin obtained in this way was obtained by adding 2 ml peroxide MEKP-HA 2 (peroxide-Chemie GmbH) and 0.4 ml Co-Oct. Solution (1% cobalt in styrene) for 24 h at
  • the glass transition temperature of the homogeneous, cured resin was 92 ° C. and the impact resistance was 27 kJ / m 2 compared to 93 ° C. and only 10 kJ / m 2 of the unmodified resin.
  • the glass transition temperature of the homogeneous cured resin was 128 ° C. and the impact resistance was 82 kJ / m 2 as compared with 130 ° C. and only 28 kJ / m 2 of the unmodified resin.
  • the silicone core-shell materials according to the invention exhibit excellent miscibility with reaction resins, which leads to greatly improved mechanical properties.
  • the translucency of the non-crosslinked mixtures shows that the powder agglomerates decompose into their primary particles as a result of the redispersion.
  • the non-inventive powders generally show a much poorer redispersibility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)
  • Organic Insulating Materials (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne une composition contenant (A) 50 - 99,5 % en poids d'une résine de réaction liquide ou d'un mélange de résines de réaction pouvant être transformées en résines thermodurcissables à des températures de l'ordre de 15 à 100 °C, présentant un poids moléculaire moyen de 200 à 500 000 et comportant un nombre suffisant de groupes réactifs appropriés pour le processus de durcissement ; et (B) 0,5 - 50 % en poids d'un ou plusieurs caoutchoucs de polyorganosiloxane redispersé réticulé de façon tridimensionnelle qui sont contenus de façon homogène dans la résine de réaction ou le mélange de résines de réaction sous forme finement dispersée de particules de caoutchouc de polyorganosiloxane présentant un diamètre de 0,001 à 0,4 µm. Les particules de caoutchouc de polyorganosiloxane sont constituées d'un coer (a) constitué d'un polymère de silicium organique et d'une enveloppe organopolymère (d) et éventuellement, de deux enveloppes internes (b) et (c), l'enveloppe interne (c) étant un polymère organique et l'enveloppe interne (b) étant un polymère de silicium organique, constitué de (a) 20 à 95 % en poids, par rapport au poids total des particules de caoutchouc de polyorganosiloxane, d'un polymère de coer de formule générale (R3SiO1/2)w(R2SiO2/2)x.(RSiO3/2)y.(SiO4/2)z où w = 0 à 20 % en mole, x = 80 à 99,5 % en mole, y = 0,5 à 10 % en mole, z = 0 à 10 % en mole, (b) 0 à 40 % en mole, par rapport au poids total des particules de caoutchouc de polyorganosiloxane, d'une enveloppe de polydialkylsiloxane constituée d'unités de formule (R3SiO1/2)w(R2SiO2/2) x.(RSiO3/2) y.(SiO4/2)z où w = 0 à 20 % en mole, x = 0 à 99,5 % en mole, y = 0,5 à 100 % en mole, z = 0 à 50 % en mole, (c) de 0 à 40 % en poids, par rapport au poids total des particules de caoutchouc de polyorganosiloxane, d'une enveloppe de monomères mono-oléfiniquement ou poly-oléfiniquement insaturés d'organopolymère, et (d) de 5 à 95 % en poids, par rapport au poids total des particules de caoutchouc de polyorganosiloxane, d'une enveloppe de monomères mono-oléfiniquement insaturés d'organopolymère, R présentant des radicaux alkyle ou alcényle monovalents identiques ou différents comportant 1 à 6 atomes de carbone, des radicaux aryle ou des radicaux hydrocarbure substitués.
EP08759723A 2007-05-30 2008-05-19 Résines de réaction contenant des particules de type c ur-écorce et procédé pour leur production et leur utilisation Ceased EP2152804A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007024967A DE102007024967A1 (de) 2007-05-30 2007-05-30 Kern-Schalepartikel enthaltende Reaktionsharze und Verfahren zu ihrer Herstellung und deren Verwendung
PCT/EP2008/056095 WO2008145550A1 (fr) 2007-05-30 2008-05-19 Résines de réaction contenant des particules de type cœur-écorce et procédé pour leur production et leur utilisation

Publications (1)

Publication Number Publication Date
EP2152804A1 true EP2152804A1 (fr) 2010-02-17

Family

ID=39672908

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08759723A Ceased EP2152804A1 (fr) 2007-05-30 2008-05-19 Résines de réaction contenant des particules de type c ur-écorce et procédé pour leur production et leur utilisation

Country Status (6)

Country Link
US (1) US20100305273A1 (fr)
EP (1) EP2152804A1 (fr)
JP (1) JP2010528165A (fr)
CN (1) CN101679718B (fr)
DE (1) DE102007024967A1 (fr)
WO (1) WO2008145550A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009025981A1 (de) * 2009-06-16 2011-03-31 Saertex Gmbh & Co. Kg Verfahren zur Herstellung eines textilen Halbzeugs mit verbesserter Zähigkeit und textiles Halbzeug
WO2011005925A1 (fr) * 2009-07-10 2011-01-13 Dow Global Technologies Inc. Caoutchoucs cœur/écorce destinés à être utilisés dans des compositions de stratifié électrique
HUE062902T2 (hu) * 2010-09-02 2023-12-28 Sumitomo Bakelite Co Rögzítõ gyanta készítmény rotorban történõ alkalmazásra
US8663428B2 (en) * 2012-05-25 2014-03-04 Voith Patent Gmbh Roll for a papermaking machine
TWI794401B (zh) * 2018-03-21 2023-03-01 美商陶氏有機矽公司 可室溫固化有機聚矽氧烷組成物及電氣/電子設備
WO2019233557A1 (fr) 2018-06-05 2019-12-12 Wacker Chemie Ag Procédé de revêtement de moyens de soutènement

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3634084A1 (de) 1986-10-07 1988-04-21 Hanse Chemie Gmbh Modifiziertes reaktionsharz, verfahren zu seiner herstellung und seine verwendung
DE4040986A1 (de) * 1990-12-20 1992-06-25 Wacker Chemie Gmbh Elastomere pfropfcopolymerisate mit kern-huelle-struktur
JPH06172490A (ja) * 1992-12-09 1994-06-21 Toto Kasei Kk 塗料用エポキシ樹脂組成物
JPH0725983A (ja) * 1993-07-06 1995-01-27 Shin Etsu Chem Co Ltd エポキシ樹脂組成物
DE19519446A1 (de) 1995-05-26 1996-11-28 Wacker Chemie Gmbh Monodisperse lösliche Organopolysiloxanpartikel
DE19535824A1 (de) * 1995-09-26 1997-03-27 Wacker Chemie Gmbh Vorvernetzte Siliconelastomer-Partikel mit Organopolymerhülle als Formulierungsbestandteil in Pulverlacken
US7015261B1 (en) * 2000-11-17 2006-03-21 Arkema Inc. Impact modifier combination for polymers
DE10204890A1 (de) * 2002-02-06 2003-08-14 Roehm Gmbh Schlagzähe Formmasse und Formkörper
JP4763458B2 (ja) * 2003-04-28 2011-08-31 株式会社カネカ ポリオルガノシロキサン含有樹脂の製造方法
JP2005108449A (ja) * 2003-09-26 2005-04-21 Toyota Central Res & Dev Lab Inc マイクロ波加熱装置
DE102004022406A1 (de) * 2004-05-06 2005-12-15 Wacker-Chemie Gmbh Polysiloxan-Pfropfpolymerisat
DE102004047708A1 (de) * 2004-09-30 2006-04-06 Wacker Chemie Ag Kern-Schalepartikel enthaltende Zusammensetzung und ihre Herstellung
JP2006104328A (ja) * 2004-10-05 2006-04-20 Mitsubishi Rayon Co Ltd 熱硬化性樹脂組成物およびその用途
JP4541186B2 (ja) * 2005-02-28 2010-09-08 ガンツ化成株式会社 液状エポキシ樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008145550A1 *

Also Published As

Publication number Publication date
US20100305273A1 (en) 2010-12-02
CN101679718A (zh) 2010-03-24
DE102007024967A1 (de) 2008-12-04
CN101679718B (zh) 2012-09-05
WO2008145550A1 (fr) 2008-12-04
JP2010528165A (ja) 2010-08-19

Similar Documents

Publication Publication Date Title
EP2352793B1 (fr) Résines époxyde renfermant des mélanges de siloxane, procédé pour leur production et leur utilisation
EP0266513B1 (fr) Résine réactive modifiée, procédé pour sa préparation et son utilisation
EP3502054A1 (fr) Formulations durcissables fonctionnalisées d'oxyde de graphène
EP1786866B1 (fr) Composition de resine polymere
EP3080175B1 (fr) Utilisation d'une dispersion polymérique pour la production d'un matériau absorbeur de vibrations
EP0296403B1 (fr) Polymères greffés thermoplastiques silicone-caoutchouc
EP2118157B1 (fr) Polymères coeur-écorce redispersibles et procédé de production
EP2152804A1 (fr) Résines de réaction contenant des particules de type c ur-écorce et procédé pour leur production et leur utilisation
EP1794232A1 (fr) Composition contenant des particules a noyau et enveloppe et son mode de production
EP2869855B1 (fr) Composition de mélange polymérisable, utilisation de cette composition de mélange polymérisable et prothèse dentaire
EP2265650A1 (fr) Matière polymérisable comprenant des nanoparticules réticulantes
EP0296402B1 (fr) Polymères greffés thermoplastiques en silicone-caoutchouc (I)
EP3538400A1 (fr) Matière insonorisante contenant un polymère en émulsion à chaînes latérales alkylène-imine
EP3436545B1 (fr) Procédé de revêtement d'agents de soutènement à l'aide de compositions de résine réactive modifiées, agents de soutènement ainsi revêtus et utilisation desdits agents de soutènement revêtus dans des procédés d'extraction par fracturation hydraulique
DE2658118A1 (de) Waessrige harzdispersionen und daraus hergestellte hitzehaertbare ueberzugsmittel
EP3560980A1 (fr) Polyester à chaîne allongée, dérivés prépolymérisés dudit polyester et leur utilisation ainsi que masses de résine époxyde
EP3408347B1 (fr) Compositions de résine active modifiées et leur utilisation pour le revêtement d'agents de soutènement
EP0322632A2 (fr) Mélanges de polymères flexibles
JP5208003B2 (ja) ポリマー微粒子分散組成物、及びその製造方法
KR20170038373A (ko) Mbs계 충격 보강제, 이의 제조방법 및 이를 포함하는 폴리카보네이트 조성물
DE2127912C3 (de) Hitzehärtbares pulverförmiges Gemisch
KR20220004474A (ko) 그라프트 공중합체, 이의 제조방법 및 이를 포함하는 수지 조성물
EP3535337A1 (fr) Compositions de résine active modifiées et leur utilisation pour le revêtement d'agents de soutènement
WO2006037558A1 (fr) Composition contenant des particules d'organosiloxane et sa preparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091116

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17Q First examination report despatched

Effective date: 20100505

DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20130711