EP2675846A2 - Matières polymères durcissables - Google Patents

Matières polymères durcissables

Info

Publication number
EP2675846A2
EP2675846A2 EP12707975.4A EP12707975A EP2675846A2 EP 2675846 A2 EP2675846 A2 EP 2675846A2 EP 12707975 A EP12707975 A EP 12707975A EP 2675846 A2 EP2675846 A2 EP 2675846A2
Authority
EP
European Patent Office
Prior art keywords
chlorine
concentration
polymer material
contained
containing compounds
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Withdrawn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
EP12707975.4A
Other languages
German (de)
English (en)
Inventor
Dieter Rossberg
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.)
ThyssenKrupp Uhde Chlorine Engineers GmbH
Original Assignee
ThyssenKrupp Uhde GmbH
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 ThyssenKrupp Uhde GmbH filed Critical ThyssenKrupp Uhde GmbH
Publication of EP2675846A2 publication Critical patent/EP2675846A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic 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
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/14—Peroxides
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C08L91/08—Mineral waxes

Definitions

  • the invention relates to a curable composition of a formulation according to the invention, a method for producing a polymer material from the curable composition, the resulting polymer material, as well as agents which are made from the polymer material according to the invention and their use.
  • Curable compositions based on, for example, polyester resin,
  • Epoxy resins or polyamide are used to make articles reinforced with fibers such as glass or textile fibers, and are widely used in industry.
  • Such plastic structures are materials made of
  • Reinforcing fibers exist, which are embedded in a plastic matrix. These are used in a variety of applications in the form of short fiber reinforced, long fiber reinforced or continuous fiber reinforced components use.
  • the subgroup of glass fiber reinforced plastics is a composite of a plastic, such as polyester resin, epoxy or polyamide, and glass fibers.
  • a plastic such as polyester resin, epoxy or polyamide
  • Glass fiber reinforced plastics are standard materials in the industry. Tubes of this type are standardized in the DIN and commercially available.
  • thermoplastic material such as e.g. Polypropylene
  • This chemical protective layer is present on those surfaces which come into contact with the alkaline solutions and is intended to protect the glass fiber reinforced plastics. This additional protective layer is required above all when the alkaline solutions have temperatures of> 40 ° C and thus their corrosive effect is enhanced and surfaces are attacked and destroyed.
  • thermoplastic chemical protective layer At temperatures below 40 ° C and low concentrations of the alkaline media can be dispensed with a thermoplastic chemical protective layer and this is instead produced from the plastic matrix itself.
  • the disadvantage of the glass fiber reinforced plastics known in the prior art is that if the chemical protection layer is damaged, the glass fibers are exposed and exposed to a chemical attack by such media directly.
  • Glass is a chemically highly resistant material, which, however, is not alkali-resistant and is massively attacked and destroyed by alkaline media of all kinds. By destroying the reinforcing fiber of the entire composite material is attacked, because the mechanical strength of the composite is due to the
  • a glass fiber reinforced plastic pipe according to the prior art is known for example from DE 10 2008 033 577 A1.
  • this document teaches a plastic tube which has improved properties in terms of tightness, rigidity, dimensional stability and abrasion in comparison to the prior art.
  • the pipe wall is formed by at least one in the spin and / or
  • Centrifugal casting method produced spin coating and at least one in the
  • Winding process produced winding layer. Although such pipes have improved properties, but are very expensive to produce.
  • compositions for such plastic pipes which reduced at least one
  • Compositions generated tubes should have lower removal rates than prior art tubes, which increases the life of such tubes.
  • the object of the present invention is therefore an alternative
  • polymer material itself to provide, the polymer material is a lower erosion rate when exposed to alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are to contain, as conventional polymer materials.
  • the invention has also set itself the task of providing appropriate means and uses of the polymer material. The object is achieved by a cobalt-poor curable composition
  • a catalyst wherein the catalyst is contained in the form of a 6% cobalt solution in a concentration of 0.05 to 0.1%
  • an accelerator wherein the accelerator is contained in the form of dimethylaniline in a concentration of 0 to 0.1%
  • hardener in the form of cumene hydroperoxide in a
  • UV stabilizer wherein the UV stabilizer is contained in a concentration of 0 to 0.5%
  • Paraffin the paraffin being in the form of wax in a concentration of 0 to 1%.
  • concentration data refer to 100% of a total mass to be cured.
  • the object is achieved by a metal-free formulation in which the curable composition comprises
  • an accelerator wherein the accelerator is contained in the form of ⁇ , ⁇ -dimethylaniline in a concentration of 0.05 to 0.2%,
  • a hardener wherein the hardener is contained in the form of dibenzoyl peroxide in a concentration of 2 to 4%,
  • retarder is contained in the form of p-tert-butylcatechol in a concentration of 0 to 0.3%
  • UV stabilizer wherein the UV stabilizer is contained in a concentration of 0 to 0.5%
  • Paraffin the paraffin being present in the form of wax in a concentration of 0 to 1%
  • concentration data refer to 100% of a total mass to be cured.
  • the accelerator can be added via the commercially available product PERGAQUICK A200 or A300 from Pergan. Of the Hardener is added via PEROXAN BP-Paste 50 or PEROXAN CU-80 L, which are also commercially available from Pergan. As retarder, for example, the product Pergaslow BK-10 is used. As UV protection, for example Tinuvin ® 5050 ® from Ciba can be used. The wax is eg BYK ® -S 750 of the Altana Group. These products are to be understood by way of example and may be replaced by others which fall within the scope defined in claim 1 and in claim 2, respectively.
  • Resin and catalyst are subjected to pre-acceleration for a period not exceeding the expiration date of the resin
  • step b) wherein, depending on the formulation, one or more constituents of step b) and / or the catalyst of step a) are omitted,
  • the hardenable mass is brought into a desired shape by standard methods, whereby a workpiece is produced
  • the workpiece is subjected to a heat treatment for 8 hours at 80 ° C and a finished polymer material is generated.
  • pre-acceleration is dispensed with in step a. of
  • further additional components such as fillers and / or fiber materials, in particular glass fibers and / or glass fleeces and / or synthetic nonwovens are embedded in the curable composition.
  • Such glass webs are known from the prior art and standardized, and commercially under the name Textilgllasmatten for
  • Plastic reinforcement commercially available. It is advantageous to an aluminum borosilicate glass with a mass fraction of alkali ⁇ 1% of the glass type E or to alkali-lime glasses with increased addition and special chemical
  • the invention further comprises a polymeric material comprising the ingredients of the curable composition of the invention based on the resin epoxy novolac vinyl ester, wherein the polymer material is prepared by the process according to the invention.
  • the polymer material further additional components, such as fillers and / or fiber materials, in particular glass fibers and / or glass fleeces and / or synthetic nonwovens, embedded, which give the material its strength.
  • the polymer material is preferably resistant to media in which chlorine or chlorine-containing compounds are present in the liquid or gaseous state, in particular to chlorine gas, bleach, anolyte, chlorine exhaust, moist chlorine and brine condensate resistant.
  • chlorine gas chlorine gas
  • bleach anolyte
  • chlorine exhaust moist chlorine and brine condensate resistant.
  • anolyte is meant, for example, brine with free chlorine gas.
  • Brine condensate is understood as meaning a brine solution which also contains chlorine. In particular, meets the
  • chlorine-containing compounds in this disclosure are understood as meaning compounds of the formula R-Cl-X, where R is an arbitrary reaction partner and X is the number of chlorine atoms.
  • the present invention claims means for receiving and / or transporting alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are contained, comprising the polymer material according to the invention.
  • this is a pipe or a container, wherein preferably a tube type E or D is used.
  • tube type E the mass content of the glass is maximally 40% and evenly distributed over the circumference.
  • the inner layer of this tube type consists of a C-glass fiber reinforced resin layer of approximately 0.4 mm thickness.
  • the outer layer consists of a layer of C-glass or synthetic fleece and a weather-resistant resin layer of maximum 0.2 mm thickness.
  • the pipe type D is replaced by a
  • the chemical protection layer of at least 2.5 mm thickness and a laminate structure characterized.
  • the chemical protection layer is a resin-rich inner layer of at least 2.5 mm thickness. It consists of a C-glass non-woven reinforced
  • Reinharz Anlagen includes in the further structure textile glass mats made of e-glass.
  • the mass content of the glass in the chemical protective layer is between 25 and 30% and increases from the inside to the outside.
  • Laminate construction is 60 ⁇ 5% and consists of textile glass fabric, textile glass mats and / or textile glass rovings made of e-glass.
  • the outer layer consists of a layer C Glass or synthetic fleece and a weather-resistant resin layer of maximum 0.2 mm thickness. This information is all known and accessible to the person skilled in the art, as stipulated in DIN 16 965 for pipes.
  • the pipe class to be used advantageously is the pipe class PX or PW, wherein in the pipe class PW on glass fleeces and / or synthetic nonwovens in the range, with the alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state of aggregation, come into contact, is omitted. It has been found that such glass webs leach under load with alkaline media such as chlorine gas, bleach, anolyte, chlorine exhaust air, humid chlorine and brine condensate and lead to clogging of the pipes.
  • alkaline media such as chlorine gas, bleach, anolyte, chlorine exhaust air, humid chlorine and brine condensate and lead to clogging of the pipes.
  • the designations of the pipe classes PX or PW are familiar to the person skilled in the art.
  • the pipe class PX is designed for a temperature up to and including 80 ° C
  • the pipe class PW is designed for a temperature up to and including 95 ° C.
  • the means for receiving and / or transport of alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous state are contained via a filler comprising the ingredients of the curable composition of the invention based on the carrier Combine pyrogenic silica.
  • the invention finds above all use in
  • Apparatus of processes in which alkaline media in which chlorine or chlorine-containing compounds in the liquid or gaseous state are supplied and / or used finds use in devices and / or in piping and / or container construction of a chlorine plant, in the alkaline media in which chlorine or chlorine-containing compounds in liquid or gaseous
  • the devices are devices of an electrolysis process by alkaline media in which chlorine or chlorine-containing compounds are prepared in liquid or gaseous state and / or supplied.
  • the invention will be explained in detail below by way of example with reference to two exemplary embodiments. These examples include studies on removal rates of polymer materials flowed through by alkaline media containing chlorine or chlorine-containing compounds in the liquid or gaseous state.
  • a prior art tubing and tubing material of the present invention has been over a period of more than 4 years with an anolyte solution, i. flows through with brine loaded with free chorgas.
  • the exact composition of the pipe materials is shown in the following table:
  • Pipe materials is shown in Table 4. Above all, different resins were used as a basis.
  • A resins
  • B catalyst
  • C accelerator
  • D hardener
  • E retarder
  • stabilizer
  • G paraffin
  • H solvent UV protection in all pipelines Tinuvin ® 5050 ® from Ciba was used, and as wax throughout BYK-S 750 of Atlana group was used.
  • Pipes (sample 1 - 13) passed an anolyte solution and measured the removal over time. The result is shown in FIG.
  • the unshaded bars indicate the average removal rate in mm over a period of 4 years, while the shaded bars indicate the maximum removal rate, which was determined by determining a single value.
  • sample 7 which corresponds to the composition according to the invention in a metal-poor formulation, has by far the lowest removal rate.
  • the metal-free formulation reflects sample 12, which gives somewhat better results than sample 13, which is based on the same resin but has a prior art formulation. Sample 12 also gives comparable results to Sample 11, which also
  • Polymer material is resistant even at high temperatures in the presence of alkaline media containing chlorine or chlorine-containing compounds in the liquid or gaseous state
  • Polymer material has extended life by reducing erosion

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Reinforced Plastic Materials (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une matière durcissable préparée d'après une recette selon l'invention, un procédé de préparation d'un matériau polymère à partir de la matière durcissable, le matériau polymère ainsi préparé, des agents préparés à partir du matériau polymère et leur utilisation.
EP12707975.4A 2011-02-17 2012-01-25 Matières polymères durcissables Withdrawn EP2675846A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011011609A DE102011011609A1 (de) 2011-02-17 2011-02-17 Härtbare polymere Massen
PCT/EP2012/000313 WO2012110193A2 (fr) 2011-02-17 2012-01-25 Matières polymères durcissables

Publications (1)

Publication Number Publication Date
EP2675846A2 true EP2675846A2 (fr) 2013-12-25

Family

ID=45812744

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12707975.4A Withdrawn EP2675846A2 (fr) 2011-02-17 2012-01-25 Matières polymères durcissables

Country Status (9)

Country Link
US (1) US20130324642A1 (fr)
EP (1) EP2675846A2 (fr)
JP (1) JP2014513199A (fr)
KR (1) KR20140037053A (fr)
CN (1) CN103380160A (fr)
CA (1) CA2823064A1 (fr)
DE (1) DE102011011609A1 (fr)
RU (1) RU2013134620A (fr)
WO (1) WO2012110193A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013003505B4 (de) * 2013-03-04 2021-08-12 Thyssenkrupp Uhde Chlorine Engineers Gmbh Verfahren zum Herstellen eines Rohres
WO2017121607A1 (fr) 2016-01-12 2017-07-20 Thyssenkrupp Uhde Chlorine Engineers Gmbh Matériau composite

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4406646A1 (de) * 1994-03-01 1995-09-07 Basf Ag Eingedickte härtbare Formmassen aus einem Vinylester- oder Vinylesterurethanharz
US5486580A (en) * 1994-11-02 1996-01-23 The Dow Chemical Company Mesogenic novolacs and resins
CH691126A5 (de) * 1995-12-21 2001-04-30 Mbt Holding Ag Novolakvinylesterzusammensetzungen.
US6287992B1 (en) * 1998-04-20 2001-09-11 The Dow Chemical Company Polymer composite and a method for its preparation
US6774193B2 (en) * 2000-06-14 2004-08-10 Albemarle Corporation Stabilized unsaturated polymer resin compositions and methods of using the same
DE102008033577A1 (de) 2008-07-17 2010-01-21 Hobas Engineering Gmbh Faserverstärktes Kunststoffrohr

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012110193A2 *

Also Published As

Publication number Publication date
US20130324642A1 (en) 2013-12-05
WO2012110193A4 (fr) 2013-03-07
CN103380160A (zh) 2013-10-30
CA2823064A1 (fr) 2012-08-23
WO2012110193A3 (fr) 2013-01-10
WO2012110193A2 (fr) 2012-08-23
JP2014513199A (ja) 2014-05-29
KR20140037053A (ko) 2014-03-26
DE102011011609A1 (de) 2012-08-23
RU2013134620A (ru) 2015-04-10

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