EP2004699A1 - Procédé de coagulation de dispersions polymères aqueuses - Google Patents

Procédé de coagulation de dispersions polymères aqueuses

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Publication number
EP2004699A1
EP2004699A1 EP07727707A EP07727707A EP2004699A1 EP 2004699 A1 EP2004699 A1 EP 2004699A1 EP 07727707 A EP07727707 A EP 07727707A EP 07727707 A EP07727707 A EP 07727707A EP 2004699 A1 EP2004699 A1 EP 2004699A1
Authority
EP
European Patent Office
Prior art keywords
coagulation
salt
polymer
polymer dispersion
coagulated
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Withdrawn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
EP07727707A
Other languages
German (de)
English (en)
Inventor
Chris De Armitt
Graham Edmund Mc Kee
Konrad Mitulla
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.)
Ineos Styrolution Europe GmbH
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP07727707A priority Critical patent/EP2004699A1/fr
Publication of EP2004699A1 publication Critical patent/EP2004699A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C08C1/15—Coagulation characterised by the coagulants used
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation

Definitions

  • the invention relates to a process for the coagulation of aqueous polymer dispersions stabilized with one or more dispersants with the aid of soluble coagulation salts.
  • the invention relates to molding compositions containing such coagulated polymers.
  • polymers are prepared by homo- or copolymerization of suitable monomers in a liquid medium, for example by emulsion, miniemulsion or microsuspension polymerization.
  • the polymer is obtained in the form of a mostly aqueous solid dispersion, from which the polymer must be separated, unless the dispersion is to be used as such.
  • the separation of the polymers from the dispersion is usually done by coagulation. For this purpose, a number of different methods are known.
  • dispersions can be coagulated by the addition of strong electrolytes.
  • salts are mostly used which contain polyvalent cations such as Ca 2+ , Mg 2+ or Al 3+ .
  • the further processing of the coagulated polymer dispersion takes place by partial removal of the water, for example by means of sieving, filtration, centrifuging or decanting, after which the water content of the polymer dispersion is up to 60%.
  • the water content can be further reduced by various drying methods, for example by hot air, heating in vacuo or extrusion drying.
  • a disadvantage of this method is the burden of water to be separated with the salts added to bring about the coagulation, so that the separated water must then be cleaned consuming.
  • Coagulation methods which initiate coagulation of polymer dispersions without the addition of salts, for example the use of high shear forces (shear precipitation) or freezing (freeze coagulation), are known to the person skilled in the art. However, these methods are complex in terms of apparatus and cost-intensive.
  • the solution consists in a process for coagulating an aqueous polymer dispersion stabilized by one or more dispersants with the aid of coagulation salts, characterized in that during or after coagulation the coagulation salts are converted from a dissolved to an insoluble form.
  • the dissolved coagulation salt By transferring the dissolved coagulation salt into an insoluble salt, it is finely dispersed in the coagulated dispersion. This also avoids the possible formation of larger particles of precipitated, possibly water-soluble and hygroscopic coagulation salt in the subsequent and subsequent processing of the dispersion following the coagulation.
  • the coagulation salt converted into an insoluble salt remains in the separation of the waste water in the polymers, the wastewater does not have to be cleaned from the coagulation salt with difficulty.
  • the salt can also serve as a filler.
  • the salt For the salt to precipitate in aqueous solution, it must have a very low solubility product. This also means that it is not hygroscopic, the end product is thus resistant to water.
  • the polymers of the polymer dispersion are prepared from monomers such as butadiene, isoprene, styrene and its derivatives, vinyl chloride, unsaturated fatty acids and their derivatives (acrylates, methacrylates, epoxides, amides, anhydrides), acrylonitrile, methacrylonitrile, alkyl acrylates, methyl acrylates and mixtures thereof.
  • a polymer in the polymer dispersion of butyl acrylate, ethylhexyl acrylate or butadiene is preferably prepared.
  • the polymers can be crosslinked or linear.
  • the polymer particles may be homogeneous or have a core-shell structure.
  • Typical dispersions can be prepared by all polymerization mechanisms such as radical or controlled free radical polymerization (ATRP, RAFT, CRP), anionic or cationic polymerization, group transfer, metathesis or
  • the dispersion medium is in the present process
  • Water that may contain other substances such as methanol, ethanol or propanol.
  • the dispersions can be prepared by emulsion, miniemulsion, suspension or dispersion polymerization.
  • the polymer dispersions are stabilized sterically or electrostatically. It is possible to use anionic, cationic, nonionic and amphoteric surfactants to stabilize the
  • Polymer dispersion can be used.
  • anionic and Mischun ⁇ en anionic and nonionic surfactants are preferred.
  • Typical examples of Surfactants can be found in the literature (for example, Surfactant Science and Technology, Second Edition, Drew Meyers, 1992 VCH Publishers Inc. New York, USA, pages 27-79).
  • salt-like coagulants can the intro duction to Colloid and Surface Chemistry, 4 th Edition, Duncan J. Shaw, Butterworth Heinemann Ltd. Oxford UK, 1991, page 211.
  • the coagulation salt and optionally further reaction products thereof are to be converted into insoluble forms.
  • the conversion of the soluble coagulation salt into its insoluble form can be done by the action of heat, electromagnetic radiation, sound or chemicals.
  • the solubility in water of the insoluble forms should be less than 6% by weight, preferably less than 1% by weight and more preferably less than 0.25% by weight.
  • insoluble forms should preferably not be hygroscopic and contain no transition metals, since these lead to oxidative degradation of organic polymers.
  • the cation of the coagulation salt is selected from group IIa and IMa of the periodic table. Particularly preferred are calcium and magnesium.
  • the coagulant should preferably contain no organic amines, such as primary, secondary or tertiary amines, as these tend to cause problems in color and oxidative stability.
  • the coagulation is carried out at temperatures of -5 ° C to 130 ° C, preferably from 10 ° C to 1 10 ° C, more preferably from 15 ° C to 100 ° C.
  • "Sintering" in the context of the present invention means that the coagulated polymer dispersion is kept at the coagulation temperature for a longer period of time or the coagulated polymer dispersion is heated to a higher temperature than the coagulation temperature and held at this temperature for a longer period of time. This period is usually minutes to hours.
  • the purpose of this measure is the complete transfer of the coagulation salt in an insoluble form and the influence on the nature of the polymer, in particular the grain size.
  • the anion of the coagulation salt is preferably HCO3 " .
  • Typical examples of coagulants that meet these requirements are Mg (HCOs) 2 or Ca (HCO 3 ) 2 .
  • Mg (HCOs) 2 -LOSU ng is prepared by introducing CO 2 -GaS in an aqueous suspension of Mg (OH) 2 :
  • This solution is used directly for coagulation of the polymer dispersion. Subsequently, the coagulated polymer dispersion is heated to above 60 ° C. and the magnesium hydrogencarbonate is converted into an insoluble salt.
  • the Mg (CO 3 H) 2 solution may be stored for coagulation prior to use. Storage should take place at temperatures below 70 ° C, preferably below 60 ° C and especially below 30 ° C, to prevent possible degradation.
  • complexing agents such as EDTA (ethylenediaminetetraacetic acid) can be added before the CO 2 gas is passed through the salt solution.
  • the amount of coagulation salt is less than 10 wt .-%, preferably less than 7 wt .-% and particularly preferably less than 5 wt .-%, each based on the polymer to be coagulated.
  • Mg (HCO 3 ) 2 concentration will depend on the particular dispersion to be coagulated, the amount and type of emulsifier, the temperature and the desired end use.
  • the preferred amount of Mg (HCO 3) 2 is the minimum concentration that is required to complete coagulation 7I I rr p p p n irh .ledoch can also other aspects, such as deposits conditions on the reactor wall, be important to select the most suitable coagulation salt concentration.
  • the Mg 2+ concentration in the aqueous phase is usually above 10 mmol / l, preferably 30 mmol / l to 300 mmol / l, particularly preferably 25 to 150 mmol / l.
  • other concentrations may prove to be particularly suitable.
  • more than one coagulating salt may be used.
  • a coagulating salt which is converted into an insoluble form during or after coagulation may be used in conjunction with at least one other coagulating salt which remains soluble during and after coagulation.
  • the amount of coagulating salt which is converted into an insoluble form during or after coagulation can be reduced. This may be necessary in certain circumstances if the coagulant salt converted into its insoluble form remaining in the polymer dispersion results in a deterioration of mechanical properties (such as toughness and elongation at break) when used as a toughener modifier.
  • Mg (HCO 3 ) 2 can be used as coagulation salt, which is converted into its insoluble form before or during coagulation, in combination with the coagulation salts MgSO 4 or CaCl 2 , which remain in solution.
  • the coagulation according to the present invention can be carried out with more than one coagulating salt which is converted into an insoluble form during or after the coagulation.
  • mixtures of one or more coagulating salts, which are converted into an insoluble form during or after coagulation, and one or more coagulating salts, which remain in dissolved form can also be used for coagulation.
  • the coagulation can be carried out batchwise or continuously.
  • coagulation can be carried out in a first reactor, followed by "sintering" of the coagulated polymer dispersion in a second reactor, if appropriate.
  • the solid portions of the dispersion are partially dewatered mechanically, for example, by centrifugation, extrusion, optionally in a mechanical press or screw extruder, by heating or heating with vacuum. In the last two cases, the solids can be completely dewatered.
  • the coagulated polymer dispersion is not completely drained.
  • the coagulated polymer dispersion particularly preferably contains 5 to 40% by weight, very particularly preferably 10 to 40% by weight, of water.
  • the completely or partially dried polymer can then be mixed in an extruder or kneader with a polymer melt of a second or more further polymers to produce molding compositions.
  • part of the water in the extruder can be removed before the coagulated product comes into contact with the polymer melt. After mixing with the polymer melt, the water is removed by evaporation in the extruder.
  • PSAN, PMMA or PVC is used as the second polymer.
  • the coagulation salt (s) converted to an insoluble form during or after coagulation may be used as a bulking agent. In this case significantly more coagulation salt is used.
  • the amount of coagulation salt to be chosen depends on the desired end uses. When used as a filler usually more than 2 wt .-%, preferably more than 5 wt .-% and particularly preferably more than 10 wt .-% coagulum salt in its insoluble form, based on the total weight of the final product needed in the final product.
  • This end product may be either the coagulated polymer dispersion or a mixture of the coagulated polymer dispersion with one or more polymers. This is the case, for example, when the coagulated polymer dispersion is used as impact modifier.
  • the polymer dispersions coagulated by the process according to the invention are usually used in conjunction with PSAN, PMMA, PVC, PS, PSAN-MMA and other thermoplastics.
  • a Mg (HCO3) 2 containing the coagulation according to the present invention preferred that the coagulated polymer dispersion with polyvinyl chloride to be processed together because the MgCO formed during the coagulation ß in this case can serve as an HCI scavenger.
  • the coagulated polymer dispersion can also be used to make rubber articles with fillers, for example for tires. Again, MgCO3 can be used as filler.
  • the coagulation salt converted to an insoluble form during or after coagulation may be used as a pigment or as a UV stabilizer.
  • the optimum amount of coagulation salt is 0.1 to 5 wt .-% based on the final product.
  • the invention also provides the molding compositions prepared by the process described above. Surprisingly, the molding compositions prepared by the process according to the invention show a lower yellowness index, a lower water absorption and, in the case of transparent products, a lower tendency to opacification in use, in particular at high atmospheric humidity or in the presence of water.
  • the molding compositions according to the invention can be processed by the known methods of thermoplastic processing such as extrusion, injection molding, rolling, calendering, blow molding, pressing or sintering into moldings, semi-finished products, films, foams or fibers.
  • Example A Demonstration of the underlying principle
  • aqueous polymer dispersion of graft copolymers was prepared.
  • the graft copolymer particles consisted of 60% by weight of a crosslinked n-butyl acrylate rubber as core and 40% by weight of a shell of polystyrene and poly (styrene-co-acrylonitrile) with a ratio of styrene: acrylonitrile of 75:25 Solids content of the dispersion was 35 wt .-%.
  • the emulsifier used was a sodium salt of a Cio-Ci6-Alkylsulfonklagemischs (Emulsifier K30 ® from Bayer).
  • the polymerization was carried out with K 2 S 2 O 8 as initiator.
  • the K 2 S 2 O 8 is reduced to K 2 SO 4 in the course of the reaction.
  • Example A-V1 (Prior Art: Coagulation with Coagulation Salt)
  • the polymer dispersion 1 was coagulated by the addition of 2 parts of an aqueous magnesium sulfate solution (0.5% by weight). The coagulated polymer dispersion was then filtered and the solids content of the filtrate determined by heating to 200 ° C to constant weight. The solids content in the filtrate was 0.56 wt .-%.
  • Example A-V2 (Prior Art: Coagulation by Shearing (Without Coagulation Salt))
  • the polymer dispersion 1 was coagulated by the application of high shear in a mixer Ultraturrax ® T50 of the Janke & Kunkel IKA laboratory technology at 10,000 rpm without the addition of salt.
  • the coagulated polymer dispersion was filtered and the solids content of the filtrate was determined by heating at 200 ° C to constant weight.
  • the solids content of the filtrate here was 0.11 wt .-%.
  • Example A-1 (Process according to the invention: coagulation with coagulation salt and conversion of the coagulation salt into an insoluble derivative)
  • Polymer dispersion 1 was coagulated by addition of an aqueous solution of 0.6% by weight Mg (HCO 3 ) 2 at 60 ° C., and then heated to 95 ° C.
  • the coagulated dispersion was filtered and the solids content of the filtrate was determined by heating to 200 ° C. to constant weight.
  • the solids content of the water was 0.11% by weight. (0.6 wt .-% magnesium bicarbonate give the same Mg 2+ concentration as 0.5 wt .-% magnesium sulfate).
  • the calculated theoretical value for the minimum salt concentration in the filtrate is 0.1 1 wt .-% (emulsifier, buffer salts and initiator). This agrees with the experimentally determined value for the sample without the addition of coagulation salt and in the case of the coagulated sample according to the invention. This shows that all magnesium bicarbonate was actually converted into an insoluble derivative by the process according to the invention.
  • Example B Influence of Temperature and Stirring Speed: (Inventive and Prior Art)
  • An aqueous polymer dispersion was prepared from a graft copolymer having a solids content of 35% by weight.
  • the graft copolymer particles consisted of 60% by weight of a crosslinked n-butyl acrylate rubber core having a first grafted shell of polystyrene constituting 13% by weight of the graft copolymer, and
  • the proportion of the second shell in the total weight of the polymer was 27% by weight.
  • the emulsifier used was a sodium salt of a Cio-Ci6-Alkylsulfonklagemischs (Emulsifier K30 ® from Bayer).
  • the concentration of the emulsifier was 1% by weight, based on the graft copolymer.
  • the distribution of the polymer dispersion was monodisperse with an average of 500 nm.
  • the Mg 2+ concentration in the water phase after separation of the coagulated graft copolymer by filtration was determined by titration with Na-EDTA (ethylenediaminetetraacetic acid di-sodium salt) solution. To this was titrated 25 g of the filtered water phase with 25 ml of a 0.5% strength by weight ammonium hydroxide solution and an indicator buffer tablet (ammonium chloride + hexamethylenetetramine) with a 0.1 molar Na-EDTA solution until the color changes from red to green capsized.
  • Na-EDTA ethylenediaminetetraacetic acid di-sodium salt
  • Experiments B-1 to B-12 were carried out using Mg (HCOs) 2 as a coagulation salt and Polymer Dispersion 2.
  • Experiments B-V1 to B-V9 were carried out in comparison in the absence of the polymer dispersion and the experiments B-V10 to B-V21 were also carried out with MgSO 4 in the presence of the polymer dispersion for comparison.
  • the amount of Mg in the filtrate about 8 x is lower than with the use of MgSO 4 as coagulation.
  • the soluble Mg (HCO3) 2 is completely converted to the insoluble product Mg (COs).
  • the size of those in experiments B-V1 to B-V9 in the absence of the polymer dispersion resulting MgC ⁇ 3 particles is in the range of 30 to 50 microns.
  • the sizes of the MgCO 3 particles formed in the presence of the polymer dispersion during coagulation (B1-B12) are significantly smaller.
  • the Mg 2+ concentration in the aqueous phase after coagulation and centrifugation was 0.16 wt%.
  • Example C-1 (Inventive method)
  • the Mg 2+ concentration in the aqueous phase after coagulation and centrifugation was 0.003 wt%.
  • Example D Coagulation of a polybutadiene dispersion
  • Polymer Dispersion 3 An aqueous dispersion of a graft copolymer of 62% by weight of butadiene as the core and poly (styrene-co-acrylonitrile) having a styrene: acrylonitrile ratio of 75:25 as a shell was prepared.
  • the emulsifier used was 1% by weight of K stearate, based on the content of graft copolymer.
  • the particle size distribution was polydispersed with an average particle size of 0.35 ⁇ m.
  • Example D-V1 (Prior Art: Coagulation with Coagulation Salt) 9.6 kg of a 1.48 wt% MgSO 4 solution was added to a 40 l stainless steel reactor.
  • the Mg 2+ concentration in the aqueous phase after coagulation and centrifugation was 0.16 wt%.
  • Example D-1 (Inventive method)
  • the Mg 2+ concentration in the aqueous phase after coagulation and centrifugation was 0.003 wt%.
  • aqueous dispersion having a graft copolymer content of 36% by weight was prepared.
  • the graft copolymer consisted of 80% by weight of a butadiene-co-styrene copolymer having a butadiene: styrene ratio of 73:27 as the core.
  • a second sleeve of methyl methacrylate and butyl acrylate at a weight ratio of 85:15 was grafted onto the graft copolymer.
  • the weight fraction of both the first and the second shell in the total weight of the graft copolymer was in each case 10% by weight.
  • the polymer dispersion was treated with Na stearate at a concentration of 1% by weight, based on the graft copolymer stabilized.
  • the polymer dispersion showed a monodisperse particle size distribution with an average particle size of 140 nm.
  • Example E-V1 (Prior Art: Coagulation with Coagulation Salt) 13.2 kg of a 1.1% by weight MgSO 4 solution was placed in a stainless steel reactor and heated to 50 ° C. This was followed by the addition of 11.0 kg of polymer dispersion 4. The reactor was heated to 99 ° C and held at this temperature for 25 minutes. Thereafter, the reactor was cooled and the solids separated from the aqueous phase by centrifugation.
  • Example E-1 (Method according to the invention: coagulation with coagulation salt and conversion of the coagulation salt into an insoluble derivative) The experiment was repeated according to the procedure described under E-V1, with the difference that instead of the MgSO 4, Mg (HCO 3 ) 2 was used as coagulation salt - was set. The concentration of the Mg (HCO 3 ) 2 solution used was adjusted so that the same Mg 2 + concentration was present in experiments E-V1 and E-1.
  • test specimens of mixtures of the coagulated polymers with SAN were prepared.
  • SAN was used, which was prepared as follows:
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions known to the person skilled in the art.
  • the resulting styrene / acrylonitrile copolymer SAN had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number VZ of 80 ml / g.
  • the granules were molded at 260 ° C by injection molding at a mold temperature of 60 ° C in plates.
  • the plates were stored after cooling for five days in a heated water bath at 60 ° C.
  • the water uptake of the polymers was determined by weighing the plates before and after storage in a water bath.
  • the polymer mixture (state of the art) prepared from the polymer dispersion C-V1 has absorbed 1.7% by weight of the original weight of water.
  • the polymer mixture prepared from the polymer dispersion C-1 (according to the invention) has absorbed only 1.1% by weight of its original weight of water.
  • the water absorption is important for a possible warping of the polymers as well as for electrical properties.
  • the coagulated polymer dispersions E-V1 (prior art) and E-1 (according to the invention) were after centrifugation with polystyrene-co-acrylonitrile in a weight ratio of 30 wt .-% polymer from the coagulated polymer dispersion to 70 wt .-% polystyrene-co Acrylonitrile (S / AN 81/19 wt .-%) and polymethyl methacrylate (Plexiglas 6N) mixed.
  • the ratio of polystyrene-co-acrylonitrile to polymethyl methacrylate was 1. 04: 1.
  • the ratio of PMMA to SAN was chosen such that the matrix is iso-refractive with the graft copolymer, the polymer mixture is transparent at room temperature. Subsequently, the two mixtures were stored overnight at 60 ° C in water. The polymer blend prepared from the polymer dispersion E-V1 had become significantly cloudy, whereas the polymer blend of E-1 remained transparent.
  • the yellowness value of the polymer blends described under 4. was determined.
  • the blends containing Mg (HCO 3 ) 2 coagulated graft copolymer according to the process of the present invention they exhibited a lower yellowness than polymer blends prepared from MgSO 4 coagulated polymer dispersions as shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de coagulation d'une dispersion polymère aqueuse, caractérisé en ce qu'au cours de la coagulation ou après la coagulation, le sel de coagulation dissous est transformé de manière à prendre sa forme non soluble.
EP07727707A 2006-04-06 2007-04-03 Procédé de coagulation de dispersions polymères aqueuses Withdrawn EP2004699A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07727707A EP2004699A1 (fr) 2006-04-06 2007-04-03 Procédé de coagulation de dispersions polymères aqueuses

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06112319 2006-04-06
EP07727707A EP2004699A1 (fr) 2006-04-06 2007-04-03 Procédé de coagulation de dispersions polymères aqueuses
PCT/EP2007/053236 WO2007113297A1 (fr) 2006-04-06 2007-04-03 Procédé de coagulation de dispersions polymères aqueuses

Publications (1)

Publication Number Publication Date
EP2004699A1 true EP2004699A1 (fr) 2008-12-24

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Application Number Title Priority Date Filing Date
EP07727707A Withdrawn EP2004699A1 (fr) 2006-04-06 2007-04-03 Procédé de coagulation de dispersions polymères aqueuses

Country Status (5)

Country Link
US (1) US8470911B2 (fr)
EP (1) EP2004699A1 (fr)
KR (1) KR101366366B1 (fr)
MX (1) MX2008012190A (fr)
WO (1) WO2007113297A1 (fr)

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FR2969158B1 (fr) * 2010-12-15 2013-01-18 Arkema France Procede pour modifiants chocs et composition thermoplastique modifiee choc ayant une resistance hydrolytique amelioree
EP2607322A1 (fr) * 2011-12-21 2013-06-26 Solvay Sa Procédé pour le traitement des eaux usées
EP2657259A1 (fr) 2012-04-23 2013-10-30 Bayer MaterialScience AG Compositions d'ABS à surface améliorée après stockage humide à chaud

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US3727775A (en) * 1969-08-19 1973-04-17 Farah Mfg Co Inc Pickup and transfer device
US4286081A (en) * 1979-10-15 1981-08-25 The Bf Goodrich Company Electrolyte in the emulsion polymerization process for producing vinyl dispersion resins
JPS58164683A (ja) * 1982-03-25 1983-09-29 Takeda Chem Ind Ltd 安定化された固体組成物
DE3810166A1 (de) * 1988-03-25 1989-10-05 Henkel Kgaa Verwendung eines waessrigen konzentrates, enthaltend ein ethylen-acrylsaeure-copolymerisat, sowie verfahren zur koagulation von lacken und anderen organischen beschichtungsmitteln
AU625002B2 (en) 1989-10-18 1992-06-25 Mitsubishi Rayon Company Limited Production process of particulate polymer
DE4408213B4 (de) * 1994-03-11 2006-06-08 Bayer Ag ABS-Formmassen mit heller Eigenfarbe und verbesserter Thermostabilität sowie Verfahren zu deren Herstellung
US5633220A (en) * 1994-09-02 1997-05-27 Schlumberger Technology Corporation High internal phase ratio water-in-oil emulsion fracturing fluid
DE10058133A1 (de) * 2000-11-22 2002-05-23 Basf Ag Verfahren zur Herstellung kautschukhaltiger thermoplastischer Formmassen
US7585560B2 (en) * 2004-09-30 2009-09-08 Dai Nippon Printing Co., Ltd. Optical laminate
US20060116454A1 (en) 2004-12-01 2006-06-01 Bedri Erdem Stable thermally coaguable polyurethane dispersions

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Also Published As

Publication number Publication date
KR101366366B1 (ko) 2014-02-21
US20090062448A1 (en) 2009-03-05
KR20080112262A (ko) 2008-12-24
MX2008012190A (es) 2008-10-02
US8470911B2 (en) 2013-06-25
WO2007113297A1 (fr) 2007-10-11

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