WO2013029295A1 - Base de chicane spécifique aux chemins de fer pour élément de fixation du type barre élastique réalisé en résine époxy modifiée thermodurcissable de masse moléculaire ultra élevée - Google Patents

Base de chicane spécifique aux chemins de fer pour élément de fixation du type barre élastique réalisé en résine époxy modifiée thermodurcissable de masse moléculaire ultra élevée Download PDF

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Publication number
WO2013029295A1
WO2013029295A1 PCT/CN2011/080964 CN2011080964W WO2013029295A1 WO 2013029295 A1 WO2013029295 A1 WO 2013029295A1 CN 2011080964 W CN2011080964 W CN 2011080964W WO 2013029295 A1 WO2013029295 A1 WO 2013029295A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
modified
reinforcing material
thermosetting
ultra
Prior art date
Application number
PCT/CN2011/080964
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English (en)
Chinese (zh)
Inventor
高原
Original Assignee
杭州大固铁路配件有限公司
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Publication of WO2013029295A1 publication Critical patent/WO2013029295A1/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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
    • E01B9/00—Fastening rails on sleepers, or the like

Definitions

  • the invention relates to a modified thermosetting ultra-high molecular epoxy resin railway special elastic strip type buckle baffle seat for replacing the elastic strip type I and type II fastener baffle seats specified in TB-T1495.5-2003
  • the molding method belongs to the field of manufacture of railway special elastic strip type I and type II fastener baffle seats.
  • the raw materials used in the rail brace I and II fastener baffle seats are metal carbon steel, nylon 6 (polyamide 6) and modified nylon 66 (modified polyamide 66).
  • Metal material baffle seat Not resistant to rust, rusted workpieces quickly lose their proper performance; nylon 6 baffle seat and modified nylon 66 due to its structural characteristics (resistance to fatigue strength and low temperature resistance) in small radius, cold regions, poles The use of cracks is widespread in arid areas and their service life is greatly limited.
  • thermoplastic resin composite materials and thermosetting resin composite materials which mainly use a thermoplastic resin or an epoxy resin as a bonding material. Since the thermoplastic resin has a chain molecular structure, many molecular chains are combined by physical action. The process limitation, in which the amount of residual low molecular solvent is uncontrollable, makes the molecular chain structure unevenly arranged in the later molding and solidification, the residual solvent cannot completely escape, resulting in uneven strength per unit area, and the consistency of material strength and quality cannot be guaranteed. .
  • Epoxy resin is a network structure of molecules. The cured epoxy resin and the curing agent form a three-dimensional crosslinked structure, and the molecular chain has strong rigidity and relatively little sliding.
  • the epoxy resin has strong rigidity after curing, it does not reach the metal strength, and the toughness is not good, especially the impact resistance. To limit its application.
  • These two types of composite materials cannot replace existing metal materials in some special high-demand products (rigid rigidity and certain toughness requirements) such as railway rail fasteners.
  • the modified thermosetting ultra-high molecular weight epoxy resin railway special elastic bar type buckle baffle seat designed by the invention is composed of a network structure thermosetting modified epoxy resin, hyperbranched curing crosslinking agent, fibrous reinforcing material and granular reinforcement Material additive composition.
  • the modified thermosetting ultra-high molecular epoxy resin and curing cross-linking agent are used as the main bonding materials to avoid the disadvantages of the chain-like molecular thermoplastic resin being susceptible to heat softening and cooling hardening, and also avoiding ordinary epoxy resin.
  • After solidification, a three-dimensional crosslinked structure is formed, although the molecular chain rigidity is strong, but the metal strength, the toughness are not good, and the impact defects are not tolerated, and the modified thermosetting ultra-high molecular epoxy resin and the curing crosslinking agent are well utilized to pass the chemical bond.
  • Cross-linking, and branching into a tree-like rigid network-like stable structure provides mechanical properties such as tensile strength, yield strength and elongation of high-strength composite materials.
  • the fibrous reinforcing material for controlling the wetting amount is defoamed into a thick paste or paste prepreg having a viscosity of 50000-100000 Pa.S, so that the prepreg can effectively discharge air under the action of the antifoaming agent.
  • the foaming without affecting the curing of the material forming, adopts pre-curing, internal demoulding and Teflon demoulding and other technical means to effectively control the consistency of the prepreg, so that the final composite material has uniform density and perfect size. With excellent mechanical properties.
  • thermosetting ultra-high polymer composite material is used for the production of railway fasteners standard of the Ministry of railways.
  • This application can effectively utilize the composite material of the invention with high strength and modulus, precise and stable molding size, uniform density and high insulation grade.
  • the small friction coefficient not only reduces the workload of railway work maintenance, but also provides a better solution for saving metal, improving the service life of fasteners and improving railway traffic safety.
  • thermosetting modified epoxy resin is The bisphenol A epoxy resin is combined with the polyether modified methyltetrahydrophthalic anhydride and the epoxy-terminated active toughening agent.
  • the preparation method comprises the following steps: vacuum dehydrating the polyether at 120 ° C for 1 hour, and then Polyether and methyltetrahydrophthalic anhydride by 3:1 The ratio was reacted under the action of a catalyst at 130-140 ° C for 3 hours, and the temperature was lowered to 120 ° C to add an epoxy resin for 2 hours to obtain an epoxy-terminated endughening active toughening agent.
  • the good technical effects of the toughening agent in this application are: The brittleness of epoxy resin directly affects its further use.
  • thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat modified by thermosetting epoxy resin, fibrous reinforcing material and granular rigidity reinforcing material additive and hyperbranched curing cross-linking
  • the composition of the modified thermosetting epoxy resin is 10-20 parts by weight
  • the content of the fibrous reinforcing material is 70-80 parts by weight
  • the content of the granular reinforcing material additive is 5-10 parts by weight
  • the agent content is 5 to 10 parts by weight.
  • Technical Solution 2 A method for molding a modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat, wherein the modified thermosetting epoxy resin and the granular reinforcing material additive are mixed and ground fineness is less than 45 micrometers.
  • Uniform slurry proportionally adding hyperbranched curing crosslinker to stir evenly, and then infiltrating the quantitative fibrous reinforcing material by defoaming into a thick paste or paste prepreg with a viscosity of 50000-100000Pa.S, and then pre-precipitating
  • the immersion material is placed in a heated mold, and after being exhausted, a pressure of 600-900 KN is applied, and in a temperature range of 155-165 ° C, curing is performed for 10-15 minutes to obtain a modified modified thermosetting ultra-high molecular weight epoxy resin railway special bomb. Strip fastener baffle seat.
  • the present invention abandons the technical solution of a high-strength composite material of a composite or ordinary epoxy resin composite material bonded with an insulating material such as metal and non-metal, thereby fundamentally avoiding the metal material and The linear expansion coefficient between non-metallic insulating materials, the adverse effects of tensile strength, yield strength and elongation, while avoiding the disadvantages of unsatisfactory rigidity and poor toughness of ordinary epoxy resin; secondly, thermosetting modification is adopted.
  • Epoxy epoxy resin and hyperbranched curing cross-linking agent are the main bonding materials, which avoids the disadvantages of the chain-chain thermoplastic resin being easily softened by heat and cooled and hardened, and also avoids ordinary epoxy resin.
  • the railway fastener strip I is produced.
  • Type and Type II fastener baffle seats have the characteristics of accurate and stable forming dimensions, uniform density, high insulation grade and low friction coefficient, which not only reduces the workload of railway work maintenance, but also saves metal and improves the use of fasteners. Life and improve the safety of railway driving provide a better solution; fourth is the system Elastic strip I, II type fastener baffle seat, with high strength (bending strength up to 966 MPa), good toughness (compressive strength up to 966) MPa), impact resistance, corrosion resistance, low temperature resistance (at normal temperature and minus 50 degrees, the impact strength loss is small), long service life, etc., especially with high and low temperature resistance and good insulation and flame retardant properties, is the public works The system is updated with new products. For specific test indicators, see the 'National Testing Center Inspection Report'.
  • Example 1 A modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat, modified by thermosetting epoxy resin, fibrous reinforcing material and granular rigid reinforcing material additive and hyperbranched curing cross-linking
  • the composition of the modified thermosetting epoxy resin is 10-20 parts by weight, the content of the fibrous reinforcing material is 70-80 parts by weight, the content of the granular reinforcing material additive is 5-10 parts by weight, and the hyperbranched curing cross-linking
  • the agent content is 5 to 10 parts by weight.
  • the modified thermosetting epoxy resin is The bisphenol A epoxy resin is combined with the polyether modified methyltetrahydrophthalic anhydride and the epoxy-terminated active toughening agent.
  • the preparation method comprises the following steps: vacuum dehydrating the polyether at 120 ° C for 1 hour, and then Polyether and methyltetrahydrophthalic anhydride by 3:1 The ratio is reacted under the action of a catalyst at 130-140 ° C for 3 hours, and the temperature is lowered to 120 ° C to add an epoxy resin for 2 hours to obtain an epoxy-terminated endughening active toughening agent.
  • the curing property and the optimum blending ratio of the toughening agent are added to 100 parts by weight of the bisphenol A epoxy resin in the range of 9-11 (ie 9, 10, 11) parts by weight of the toughening agent.
  • the hyperbranched curing crosslinking agent is a different terminal carboxyl hyperbranched polyester synthesized by using methyltetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride and glycidol as raw materials, and using the terminal carboxylate overrun Any one or a combination of two or more of a polyester and a fatty polyamine, an alicyclic polyamine, an aromatic amine, a polyamide, a modified amine, an acid anhydride, an imidazole, a resin or a tertiary amine; the fibrous reinforcing material is Refers to any one or two of glass fiber, carbon fiber, boron fiber, whisker, asbestos fiber, aramid fiber, aramid fiber, polyester fiber, nylon fiber, vinyl nylon fiber, polypropylene fiber, polyimide fiber.
  • the granular reinforcing material refers to a combination of carbon black, glass hollow microbeads, clay, sand, glass powder, fly ash, wood powder, mica powder, asbestos, silica gel and short glass fiber, or a combination of two or more .
  • Example 2 On the basis of Example 1, the modified thermosetting epoxy resin content was 10 parts by weight, the fibrous reinforcing material content was 80 parts by weight, the content of the particulate reinforcing material additive was 5 parts by weight, and hyperbranching was carried out. The curing crosslinking agent content was 5 parts by weight.
  • Embodiment 3 On the basis of Example 1, the modified thermosetting epoxy resin content is 20 parts by weight, the fibrous reinforcing material content is 70 parts by weight, the content of the particulate reinforcing material additive is 5 parts by weight, and hyperbranched The curing crosslinking agent content was 5 parts by weight.
  • Embodiment 4 On the basis of Example 1, the modified thermosetting epoxy resin content is 10 parts by weight, the fibrous reinforcing material content is 70 parts by weight, the content of the particulate reinforcing material additive is 10 parts by weight, and hyperbranched The curing crosslinking agent content was 10 parts by weight.
  • Example 5 On the basis of Example 1, the modified thermosetting epoxy resin content was 10 parts by weight, the fibrous reinforcing material content was 75 parts by weight, the content of the particulate reinforcing material additive was 7.5 parts by weight, and hyperbranching was carried out.
  • the curing crosslinking agent content was 7.5 parts by weight.
  • Example 6 On the basis of Example 1, the content of the modified thermosetting epoxy resin was 13 parts by weight, the content of the fibrous reinforcing material was 75 parts by weight, and the content of the particulate reinforcing material additive was 6 parts by weight, hyperbranched. The curing crosslinking agent content was 6 parts by weight.
  • Embodiment 7 On the basis of Embodiment 1-6, a method for molding a modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat, firstly thermosetting modified epoxy resin and granular reinforcement The material additive is mixed and ground to a uniform slurry of 45 micron or less, and the hyperbranched curing crosslinking agent is added in proportion to stir evenly, and then the infiltrated quantitative fibrous reinforcing material is defoamed in a temperature range of 100-120 ° C and includes the end value.
  • Pre-cured for 20-30 minutes and including the end value to obtain a thick paste or paste prepreg having a viscosity of 50000-100000Pa.S, and then placing the prepreg in the heated mold, and applying 1000KN after exhausting.
  • the above pressure, control temperature in the range of 165-175 ° C and including the end value, after 3-8 minutes and including the end value, secondary curing to obtain the finished modified thermosetting ultra-high molecular epoxy resin railway special elastic bar type fasteners Board seat.
  • the application of the above-mentioned strength new modified thermosetting ultra-high molecular weight epoxy resin composite material designed by the invention is to make the standard of the Ministry of Railways of China by pultrusion, molding, laminating, transfer molding, casting and injection molding.
  • the viscosity of the composite prepreg of the modified thermosetting ultra-high molecular epoxy resin railway special elastic strip baffle seat is controlled to 50000-100000Pa.S, which makes the prepreg effective under the action of defoaming agent. Exhaust air to eliminate dark foam, and will not affect the curing of the material forming, adopt pre-curing, internal demoulding and Teflon demoulding and other technical means to effectively control the consistency of the prepreg, so that the final composite density Uniform, perfect size and excellent mechanical properties.
  • Example 1 The modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat composite material prepared by the die casting method described in the present embodiment is prepared by preparing a thermosetting modified epoxy resin and a granular reinforcing material according to a prescribed ratio.
  • the fibrous reinforcing material is 80 parts by weight
  • the thermosetting hyperbranched modified epoxy resin is 9 parts
  • the curing crosslinking agent is 6 parts
  • the granular reinforcing material additive is 5 parts.
  • Example 2 The modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat composite material described in this embodiment is prepared by preparing a thermosetting modified epoxy resin and a granular reinforcing material additive according to a prescribed ratio. Black, silica, mica powder mixed, grinding fineness of 45 microns or less uniform slurry, after stirring evenly, according to the thermosetting modified epoxy resin and curing crosslinker in a weight ratio of 3:2 added to the curing crosslinker, at 80 After pre-curing at -100 ° C, the quantitative fibrous reinforcing material - the combination of alkali-free glass fiber and carbon fiber through the pultrusion equipment latitudinal heating mold (control temperature 165-175 ° C, tensile force 80-120 KN) continuous uniform pultrusion (effective curing time 3-6 minutes), after the heat-hardening, the strips with the uniform weft size are obtained, cut according to a certain size, and then the baffle seat is added to form the ears,
  • Example 3 This embodiment describes a novel modified thermosetting ultra-high molecular weight epoxy resin composite material obtained by pultrusion.
  • the novel modified thermosetting ultra-high molecular weight epoxy resin composite material is: 12 parts of thermosetting modified epoxy resin.
  • the hyperbranched curing crosslinking agent is 8 parts of a combination of methyltetrahydrophthalic anhydride and a promoter, the fibrous reinforcing material is: 75 parts of a combination of glass fiber and carbon fiber; the granular reinforcing material is: carbon black, dioxide A total of 5 combinations of silicon and mica powder.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention porte sur une base de chicane spécifique aux chemins de fer pour un élément de fixation du type barre élastique réalisé en une résine époxy modifiée thermodurcissable de masse moléculaire ultra élevée et sur un procédé pour sa formation, laquelle base de chicane est constituée par une résine époxy thermodurcissable, un matériau de renfort fibreux, un additif de matériau de renfort rigide granulaire et un agent réticulant à durcissement à hyper-ramification, la teneur en résine époxy modifiée thermodurcissable étant de 10 à 20 parties en poids, la teneur en matériau de renfort fibreux étant de 70 à 80 parties en poids, la teneur en additif de matériau de renfort granulaire étant de 5 à 10 parties en poids, et la teneur en agent réticulant à durcissement à hyper-ramification étant de 5 à 10 parties en poids.
PCT/CN2011/080964 2011-08-26 2011-10-19 Base de chicane spécifique aux chemins de fer pour élément de fixation du type barre élastique réalisé en résine époxy modifiée thermodurcissable de masse moléculaire ultra élevée WO2013029295A1 (fr)

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CN201110248613.3 2011-08-26
CN201110248613 2011-08-26

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WO2013029295A1 true WO2013029295A1 (fr) 2013-03-07

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108797231A (zh) * 2018-09-25 2018-11-13 浙江三维橡胶制品股份有限公司 弹条防飞装置及其应用
CN112552486A (zh) * 2020-04-22 2021-03-26 普氢(上海)新材料科技有限公司 一种预促进增韧酸酐固化剂及制备方法、用于生产拉挤复合材料的环氧树脂组合物

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CN101250322A (zh) * 2008-04-11 2008-08-27 南京聚隆化学实业有限责任公司 高速铁路钢轨扣件用尼龙工程塑料及其制造方法
CN102079881A (zh) * 2010-12-16 2011-06-01 嘉兴安普铁路配件有限公司 高强度热固性分子基复合材料及其应用

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JPH0770406A (ja) * 1993-08-31 1995-03-14 Tonen Corp 低温硬化型プリプレグ用エポキシ樹脂組成物及びそれを用いたプリプレグ
CN102206325B (zh) * 2010-03-31 2012-09-05 朱瑞澄 一种耐热增韧甲基四氢苯酐的改性方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101250322A (zh) * 2008-04-11 2008-08-27 南京聚隆化学实业有限责任公司 高速铁路钢轨扣件用尼龙工程塑料及其制造方法
CN102079881A (zh) * 2010-12-16 2011-06-01 嘉兴安普铁路配件有限公司 高强度热固性分子基复合材料及其应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108797231A (zh) * 2018-09-25 2018-11-13 浙江三维橡胶制品股份有限公司 弹条防飞装置及其应用
CN112552486A (zh) * 2020-04-22 2021-03-26 普氢(上海)新材料科技有限公司 一种预促进增韧酸酐固化剂及制备方法、用于生产拉挤复合材料的环氧树脂组合物

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