WO2013029295A1 - Railway-specific baffle base for elastic bar-type fastener made of modified, thermosetting, ultra-high molecular epoxy resin - Google Patents
Railway-specific baffle base for elastic bar-type fastener made of modified, thermosetting, ultra-high molecular epoxy resin Download PDFInfo
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- 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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- 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
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- 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
Abstract
A railway-specific baffle base for a elastic bar-type fastener made of a modified, thermosetting, ultra-high molecular epoxy resin and method for forming same, the baffle base consisting of a thermosetting epoxy resin, a fibrous reinforcing material, a granular rigid reinforcing material additive and a hyperbranching curing crosslinker, wherein the content 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 content of the hyperbranching curing crosslinker is 5 - 10 parts by weight.
Description
本发明涉及一种用于替代TB-T1495.5-2003规定的弹条I型、II型扣件挡板座的改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座及成型方法，属铁路专用弹条I型、II型扣件挡板座制造领域。
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.
目前铁路弹条Ⅰ、Ⅱ型扣件挡板座所使用原材料有金属碳素钢、尼龙6(聚酰胺6)和改性尼龙66（改性聚酰胺66）三大类，金属材料挡板座不耐锈蚀，锈蚀的工件很快失去应有的性能；尼龙6挡板座和改性尼龙66由于其结构特性（抗疲劳强度损失和耐低温差等原因）在小半径区间、寒冷地区、极干旱地区使用普遍发生脆裂，其使用寿命受到了极大地限制。
At present, 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.
现有技术中也有一些热塑性树脂复合材料和热固性树脂复合材料，其主要采用热塑性树脂或环氧树脂为粘接材料，由于热塑性树脂为链状分子结构，许多分子链通过物理作用组合在一起，受其工艺限制，其中残余低分子溶剂量无法控制，使得后期成型固化时，分子链状结构排列不均匀，残余溶剂无法完全逸出，导致单位面积的强度不均匀，无法保证材料强度质量的一致性。环氧树脂为网状分子结构，
固化后的环氧树脂与固化剂形成三维交联结构，分子链刚性强，相对滑动少，因此环氧树脂固化后刚性虽强但达不到金属强度，而且韧性不好，特别是不耐冲击，使其应用受到限制。使得这两类复合材料无法在一些特殊的高要求产品（刚性强且有一定的韧性要求）如铁路铁轨紧固件等替代现有的金属材料。
In the prior art, there are also some 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. Therefore, although 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.
设计目的：避免背景技术中的不足之处，设计一种耐腐蚀、耐候性好，强
度高，可达到现有的Q235钢（GB/T700-1988
Q235）工件强度要求和普通碳纤维复合材料的弹条I型、II型扣件挡板座的一种改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座及成型方法。 Design purpose: to avoid the deficiencies in the background technology, design a corrosion resistance, weather resistance, strong
High degree, can reach the existing Q235 steel (GB/T700-1988
Q235) A modified thermosetting super-polymer epoxy resin railway special elastic strip type baffle seat and forming method for workpiece strength requirements and elastic carbon fiber composite material elastic strip type I and type II fastener baffle seats.
设计方案：为了实现上述设计目的。本发明所设计的改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座由网状结构的热固性改性环氧树脂、超支化固化交联剂、纤维状增强材料和粒状增强材料添加剂组成。
Design plan: In order to achieve the above design goals. 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.
1
、采用改性热固性超高分子环氧树脂、固化交联剂为主要粘结材料，避免链状分子热塑性树脂容易受热软化、冷却硬化的弊端，同时也避免了普通环氧树脂
固化后形成三维交联结构，分子链刚性虽强但达不到金属强度、韧性不好、不耐冲击缺陷，很好的利用了改性热固性超高分子环氧树脂和固化交联剂通过化学键交联，并且枝化为树杈状刚性网状稳定结构提供了高强度复合材料的抗张强度、屈服强度和伸长率等机械性能。 1
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.
2
、控制浸润定量的纤维状增强材料经过消泡处理成粘度为50000-100000Pa.S的厚浆状或膏状预浸料，使得预浸料在消泡剂的作用下能有效的排出空气杜绝暗泡，又不会影响的材料成型的固化，采取预固化、内脱模和特氟龙脱模等技术手段，有效的控制了预浸料的稠度，使得最终的得到复合材料密度均匀，尺寸完美，具有优良的机械性能。 2
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.
3
、热固性超高分子复合材料用于制作铁道部标准的铁路紧固件的应用，这种应用能有效的利用本发明复合材料产品强度及模量高，成型尺寸精确稳定，密度均一，绝缘等级高，摩擦系数小的特点，不但减轻了铁路工务检修维护工作量，对节约金属、提高紧固件的使用寿命和提高铁路行车安全提供了更好的解决方案。 3
The 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.
4 、热固性改性环氧树脂是
以双酚A环氧树脂配以聚醚改性甲基四氢苯酐再用环氧基封端的活性增韧剂，其制作方法：先将聚醚在120°C下真空脱水1小时，再将聚醚和甲基四氢苯酐按 3:1
比例在催化剂的作用下在130-140°C下反应3小时，降温至120°C加入环氧树脂反应2小时，得到环氧基封端的内增韧活性增韧剂。其
增韧剂在本申请中所带来的好的技术效果是：
环氧树脂的脆性直接影响其进一步使用，绝大多数配方都需要进行增韧改性，以提高制品的耐冲击性和缓解固化时的内应力，降低环氧固化物的脆性。我们自己合成的活性环氧增韧剂，它的分子结构中既包含了大量的柔性链段来缓解环氧树脂的脆硬性，又包含了封端的环氧基团，能参与固化反应，增韧效果明显，不但提高了体系的粘接强度，也大大提高了材料的压缩强度和剪切强度。 4, 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. its
The good technical effects of the toughening agent in this application are:
The brittleness of epoxy resin directly affects its further use. Most formulations require toughening modification to improve the impact resistance of the product and to relieve the internal stress during curing and reduce the brittleness of the epoxy cured product. Our own synthetic active epoxy toughening agent, its molecular structure contains a large number of flexible segments to alleviate the brittle hardness of epoxy resin, and also contains blocked epoxy groups, can participate in the curing reaction, toughen The effect is obvious, which not only improves the bonding strength of the system, but also greatly improves the compressive strength and shear strength of the material.
技术方案1：一种改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座，由改性热固性环氧树脂、纤维状增强材料和粒状刚性增强材料添加剂和超支化固化交联剂组成；其所述改性热固性环氧树脂含量为10-20重量份、纤维状增强材料含量为70-80重量份、粒状增强材料添加剂的含量为5-10重量份、超支化固化交联剂含量为5-10重量份。
Technical Solution 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 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, and the hyperbranched curing cross-linking The agent content is 5 to 10 parts by weight.
技术方案2：一种改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座的成型方法，将改性热固性环氧树脂和粒状增强材料添加剂混合研磨细度为45微米以下的均匀浆状，按比例加入超支化固化交联剂搅拌均匀，然后浸润定量的纤维状增强材料经过消泡处理成粘度为50000-100000Pa.S的厚浆状或膏状预浸料，再将预浸料置于加热后的模具中，排气后施加600-900KN的压力，在155-165℃的温度范围内，经10-15分钟固化得到成品改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座。
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.
技术方案3：改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座，浸润定量的纤维状增强材料经过消泡处理成粘度为50000-100000Pa.S的厚浆状或膏状预浸料通过拉挤、模压、层压、传递模塑、浇铸、注射的成型方法制作替代TB-T1495.5-2003规定的弹条I型、II型扣件挡板座。
Technical Solution 3: Modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat, infiltrated quantitative fibrous reinforcing material is defoamed into a thick paste or paste with a viscosity of 50000-100000Pa.S The prepreg is formed by the pultrusion, molding, laminating, transfer molding, casting, and injection molding methods to replace the elastic strip type I and type II fastener baffle seats specified in TB-T1495.5-2003.
本发明与背景技术相比，一是摒弃了用金属与非金属等绝缘材料粘接的复合制作或普通环氧树脂复合材料的高强度的复合材料的技术方案，从根本上避免了金属材料与非金属绝缘材料之间存在的线膨胀系数，抗张强度、屈服强度和伸长率带来的不利影响，同时也避免了普通环氧树脂刚性不理想且韧性差的缺点；二是采用了热固性改性环氧树脂、超支化固化交联剂为主要粘结材料，避免链状分子热塑性树脂容易受热软化、冷却硬化的弊端，同时也避免了普通环氧树脂
固化后形成三维交联结构，分子链刚性虽强但达不到金属强度，而且韧性不好，特别是不耐冲击的缺陷，很好的利用了热固性改性环氧树脂和超支化固化交联剂通过化学键交联并且枝化为树杈状刚性网状稳定结构，提供了高强度复合材料的抗张强度、屈服强度和伸长率等机械性能；三是所制作的铁路紧固件弹条I型、II型扣件挡板座，具有成型尺寸精确稳定，密度均一，绝缘等级高，摩擦系数小的特点，不但减轻了铁路工务检修维护工作量，而且对节约金属、提高紧固件的使用寿命和提高铁路行车安全提供了更好的解决方案；四是所制的
弹条Ⅰ、Ⅱ型扣件挡板座，具有强度高（弯曲强度可达966 MPa）、韧性好(压缩强度可达966
MPa)、抗冲击、耐腐蚀、耐低温（常温及零下50度时，冲击强度损失很小）、使用寿命长等特点，尤其具有耐高、低温性能和良好的绝缘、阻燃性能，是工务系统更新换代产品，具体检测指标见'国家检测中心检验报告'。
Compared with the background art, 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.
After solidification, a three-dimensional crosslinked structure is formed, although the molecular chain rigidity is strong, but the metal strength is not obtained, and the toughness is not good, especially the defect that is not resistant to impact, and the thermosetting modified epoxy resin and the hyperbranched curing cross-linking are well utilized. The agent is crosslinked by chemical bonds and branched into a tree-like rigid network-like stable structure, which provides mechanical properties such as tensile strength, yield strength and elongation of the high-strength composite material. Third, 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'.
实施例1：一种改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座，由改性热固性环氧树脂、纤维状增强材料和粒状刚性增强材料添加剂和超支化固化交联剂组成；其所述改性热固性环氧树脂含量为10-20重量份、纤维状增强材料含量为70-80重量份、粒状增强材料添加剂的含量为5-10重量份、超支化固化交联剂含量为5-10重量份。所述改性热固性环氧树脂是
以双酚A环氧树脂配以聚醚改性甲基四氢苯酐再用环氧基封端的活性增韧剂，其制作方法：先将聚醚在120°C下真空脱水1小时，再将聚醚和甲基四氢苯酐按 3:1
比例在催化剂的作用下在130-140°C下反应3小时，降温至120°C加入环氧树脂反应2小时，得到环氧基封端的内增韧活性增韧剂，
该增韧剂的固化特性和最佳掺合比例，在100重量份双酚A环氧树脂中加入9-11范围内（即9、10、11）重量份这种增韧剂
；所述超支化固化交联剂是以甲基四氢苯酐、邻苯二甲酸酐、六氢苯酐和环氧丙醇为原料，合成的不同端羧基超支化聚酯，并用这种端羧基超支化聚酯与脂肪多元胺、脂环多元胺、芳香胺、聚酰胺、改性胺、酸酐类、咪唑、树脂类或叔胺任意一种或两种以上的组合；所述纤维状增强材料是指玻璃纤维、碳纤维、硼纤维、晶须、石棉纤维、芳香族聚酰胺纤维、奥纶纤维、聚酯纤维、尼龙纤维、维尼龙纤维、聚丙烯纤维、聚酰亚胺纤维任意一种或两种组合；所述粒状增强材料是指炭黑、玻璃空心微珠、粘土、砂、玻璃粉、粉煤灰、木粉、云母粉、石棉、硅胶和短玻璃纤维一种或两种以上的组合。
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 .
实施例2：在实施例1的基础上，其所述改性热固性环氧树脂含量为10重量份、纤维状增强材料含量为80重量份、粒状增强材料添加剂的含量为5重量份、超支化固化交联剂含量为5重量份。
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.
实施例3：在实施例1的基础上，其所述改性热固性环氧树脂含量为20重量份、纤维状增强材料含量为70重量份、粒状增强材料添加剂的含量为5重量份、超支化固化交联剂含量为5重量份。
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.
实施例4：在实施例1的基础上，其所述改性热固性环氧树脂含量为10重量份、纤维状增强材料含量为70重量份、粒状增强材料添加剂的含量为10重量份、超支化固化交联剂含量为10重量份。
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.
实施例5：在实施例1的基础上，其所述改性热固性环氧树脂含量为10重量份、纤维状增强材料含量为75重量份、粒状增强材料添加剂的含量为7.5重量份、超支化固化交联剂含量为7.5重量份。
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.
实施例6：在实施例1的基础上，其所述改性热固性环氧树脂含量为13重量份、纤维状增强材料含量为75重量份、粒状增强材料添加剂的含量为6重量份、超支化固化交联剂含量为6重量份。
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.
实施例7：在实施例1-6的基础上，一种改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座的成型方法，首先将热固性改性环氧树脂和粒状增强材料添加剂混合研磨细度为45微米以下均匀浆状，按比例加入超支化固化交联剂搅拌均匀，然后浸润定量的纤维状增强材料经过消泡处理在100-120℃温度范围内且包括端值，预固化20-30分钟且包括端值，制得粘度为50000-100000Pa.S的厚浆状或膏状预浸料，再将预浸料置于加热后的模具中，排气后施加1000KN以上的压力，控制温度在165-175℃范围内且包括端值，经3-8分钟且包括端值，二次固化得到成品改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座。
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.
本发明所设计的上述强度新型改性热固性超高分子环氧树脂复合材料的应用，是将其通过拉挤、模压、层压、传递模塑、浇铸、注射的成型方法制作中国铁道部标准的铁路轨道紧固件弹条I型、II型扣件挡板座。
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. Railway track fasteners, type I, type II fasteners, baffle seats .
同时控制了改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座复合材料预浸料的粘度为50000-100000Pa.S，使得预浸料在消泡剂的作用下能有效的排出空气杜绝暗泡，又不会影响的材料成型的固化，采取预固化、内脱模和特氟龙脱模等技术手段，有效的控制了预浸料的稠度，使得最终的得到复合材料密度均匀，尺寸完美，具有优良的机械性能。
At the same time, 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.
例1：本实施例描述的压铸法制得的改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座复合材料，是将按规定比例配制热固性改性环氧树脂和粒状增强材料添加剂--炭黑、粉煤灰、云母粉混合，研磨细度为45微米以
下均匀浆状，搅拌均匀后按热固性改性环氧树脂与超支化固化交联剂3:2比例加入超支化固化交联剂，浸润定量的纤维状增强材料--无碱玻璃纤维，在80-100℃预固化20-30分钟后制得预浸料，将预浸料定量置于加热后的铁路弹条I型、II型扣件挡板座模具中，排气后加压1000KN，控制温度165-175℃，经3-8分钟二次固化成型后，即采用模压工艺制成所述紧固件。其中按重量份数，所述纤维状增强材料为为80份，热固性超支化改性环氧树脂为9份，固化交联剂为6份，粒状增强材料添加剂为5份。
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. Additives - carbon black, fly ash, mica powder mixed, grinding fineness of 45 microns
Uniform slurry, stir evenly, add hyperbranched curing crosslinker in a ratio of 3:2 of thermosetting modified epoxy resin and hyperbranched curing crosslinker, infiltrate quantitative fibrous reinforcing material--alkali-free glass fiber, at 80 After pre-curing at -100 °C for 20-30 minutes, the prepreg is prepared, and the prepreg is quantitatively placed in the mold of the rail spring type I and type II fasteners after heating, and the pressure is 1000KN after being exhausted, and the control is controlled. The temperature is 165-175 ° C, and after 3-8 minutes of secondary curing molding, the fastener is formed by a molding process. Among them, 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, and the granular reinforcing material additive is 5 parts.
例2：本实施例描述的改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座复合材料，是将按规定比例配制热固性改性环氧树脂和粒状增强材料添加剂--炭黑、二氧化硅、云母粉混合，研磨细度为45微米以下均匀浆状，搅拌均匀后按热固性改性环氧树脂与固化交联剂按3:2重量比加入固化交联剂，在80-100℃浸润预固化后，将定量的纤维状增强材料--无碱玻璃纤维和碳纤维的组合经过拉挤设备纬向加热模具（控制温度165-175℃，拉力80-120
KN）连续匀速拉挤（有效固化时间3-6分钟），保温硬化后制得纬向尺寸一致的条状物，按一定尺寸剪切，然后加装挡板座双耳后成型，即制得采用拉挤工艺制成所述铁路弹条I型、II型扣件挡板座。
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, which is obtained. The railway spring strip type I and type II fastener baffle seats are formed by a pultrusion process.
例3：本实施例描述拉挤法制得的新型改性热固性超高分子环氧树脂复合材料，所述的新型改性热固性超高分子环氧树脂复合材料是：热固性改性环氧树脂12份，超支化固化交联剂为甲基四氢苯酐与促进剂的组合8份，所述纤维状增强材料是：玻璃纤维和碳纤维组合共75份；所述粒状增强材料是：炭黑、二氧化硅、云母粉的组合共5份。
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.
需要理解到的是：上述实施例虽然对本发明的设计思路作了比较详细的文字描述，但是这些文字描述，只是对本发明设计思路的简单文字描述，而不是对本发明设计思路的限制，任何不超出本发明设计思路的组合、增加或修改，均落入本发明的保护范围内。
It should be understood that although the above embodiment has a relatively detailed text description of the design idea of the present invention, these text descriptions are merely a simple text description of the design idea of the present invention, and are not limited to the design idea of the present invention, and may not exceed any Combinations, additions or modifications of the inventive design are all within the scope of the invention.
Claims (5)
1、一种改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座，其特征是：由改性热固性环氧树脂、纤维状增强材料和粒状刚性增强材料添加剂和超支化固化交联剂组成；其所述改性热固性环氧树脂含量为10-20重量份、纤维状增强材料含量为70-80重量份、粒状增强材料添加剂的含量为5-10重量份、超支化固化交联剂含量为5-10重量份。1. A modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat, which is characterized by: modified thermosetting epoxy resin, fibrous reinforcing material and granular rigidity reinforcing material additive and hyperbranched curing a crosslinking agent composition; the modified thermosetting epoxy resin content is 10-20 parts by weight, the fibrous reinforcing material content is 70-80 parts by weight, the granular reinforcing material additive is 5-10 parts by weight, and hyperbranched curing The crosslinking agent content is 5 to 10 parts by weight.
2、根据权利要求1所述的改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座，其特征是： 2 . The modified thermosetting ultra-high molecular weight epoxy resin railway special elastic bar type buckle baffle seat according to claim 1 , wherein:
所述改性热固性环氧树脂是以双酚A环氧树脂配以聚醚改性甲基四氢苯酐再用环氧基封端的活性增韧剂；The modified thermosetting epoxy resin is an active toughening agent which is terminated with a bisphenol A epoxy resin and a polyether modified methyltetrahydrophthalic anhydride and an epoxy group;
所述超支化固化交联剂是以甲基四氢苯酐、邻苯二甲酸酐、六氢苯酐和环氧丙醇为原料，合成的不同端羧基超支化聚酯，并用这种端羧基超支化聚酯与脂肪多元胺、脂环多元胺、芳香胺、聚酰胺、改性胺、酸酐类、咪唑、树脂类或叔胺任意一种或两种以上的组合；The hyperbranched curing crosslinking agent is a different terminal carboxyl group hyperbranched polyester synthesized by using methyltetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride and glycidyl alcohol as raw materials, and the terminal carboxyl group is hyperbranched. a combination 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, or a combination of two or more;
所述纤维状增强材料是指玻璃纤维、碳纤维、硼纤维、晶须、石棉纤维、芳香族聚酰胺纤维、奥纶纤维、聚酯纤维、尼龙纤维、维尼龙纤维、聚丙烯纤维、聚酰亚胺纤维任意一种或两种组合；The fibrous reinforcing material refers to glass fiber, carbon fiber, boron fiber, whisker, asbestos fiber, aramid fiber, aramid fiber, polyester fiber, nylon fiber, vinyl nylon fiber, polypropylene fiber, polyacryl Any one or two combinations of amine fibers;
所述粒状增强材料是指炭黑、玻璃空心微珠、粘土、砂、玻璃粉、粉煤灰、木粉、云母粉、石棉、硅胶和短玻璃纤维一种或两种以上的组合。The granular reinforcing material refers to a combination of carbon black, glass hollow microbeads, clay, sand, glass powder, fly ash, wood flour, mica powder, asbestos, silica gel and short glass fibers, or a combination of two or more thereof.
3
、根据权利要求1所述的改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座，其特征是：所述聚醚改性甲基四氢苯酐再用环氧基封端的活性增韧剂的制作方法是先将聚醚在120°C下真空脱水1小时，再将聚醚和甲基四氢苯酐按3:1比例在催化剂的作用下在130-140°C下反应3小时，降温至120°C加入环氧树脂反应2小时，得到环氧基封端的内增韧活性增韧剂。
3
The modified thermosetting ultra-high molecular weight epoxy resin railway special elastic bar type buckle baffle seat according to claim 1, wherein the polyether modified methyltetrahydrophthalic anhydride is further terminated with an epoxy group. The active toughening agent is prepared by vacuum dehydrating the polyether at 120 ° C for 1 hour, and then reacting the polyether and methyltetrahydrophthalic anhydride in a ratio of 3:1 under the action of a catalyst at 130-140 ° C. After 3 hours, the epoxy resin was reacted for 2 hours by cooling to 120 ° C to obtain an epoxy-terminated internal toughening active toughening agent.
4
、一种改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座的成型方法，其特征是：将改性热固性环氧树脂和粒状增强材料添加剂混合研磨细度为45微米以下的均匀浆状，按比例加入超支化固化交联剂搅拌均匀，然后浸润定量的纤维状增强材料经过消泡处理成粘度为50000-100000Pa.S的厚浆状或膏状预浸料，再将预浸料置于加热后的模具中，排气后施加600-900KN的压力，在155-165℃的温度范围内，经10-15分钟固化得到成品改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座。4
A method for molding a modified thermosetting ultra-high molecular weight epoxy resin railway special elastic strip type buckle baffle seat, characterized in that the modified thermosetting epoxy resin and the granular reinforcing material additive are mixed and ground fineness is 45 micrometers or less. 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 The prepreg 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. Spring-type fastener baffle seat.
5
、一种如权利要求1-4所述的改性热固性超高分子环氧树脂铁路专用弹条型扣件挡板座，其特征是：浸润定量的纤维状增强材料经过消泡处理成粘度为50000-100000Pa.S的厚浆状或膏状预浸料通过拉挤、模压、层压、传递模塑、浇铸、注射的成型方法制作替代TB-T1495.5-2003规定的弹条I型、II型扣件挡板座。
5
The modified thermosetting ultra-high molecular weight epoxy resin railway special elastic bar type buckle baffle seat according to any one of claims 1-4, characterized in that: the infiltrated quantitative fibrous reinforcing material is defoamed to a viscosity of 50000-100000Pa.S thick paste or paste prepreg is made by pultrusion, molding, lamination, transfer molding, casting, injection molding method instead of the elastic type I specified in TB-T1495.5-2003, Type II fastener bezel seat.
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| CN112552486A (en) * | 2020-04-22 | 2021-03-26 | 普氢(上海)新材料科技有限公司 | Pre-accelerated toughening anhydride curing agent, preparation method thereof and epoxy resin composition for producing pultrusion composite material |
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| CN102206325B (en) * | 2010-03-31 | 2012-09-05 | 朱瑞澄 | Modification method of heat-resistant toughened methyl tetrahydrophthalic anhydride |
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| CN101250322A (en) * | 2008-04-11 | 2008-08-27 | 南京聚隆化学实业有限责任公司 | Nylon engineering plastic for high-speed railway rail fastening and method for manufacturing same |
| CN102079881A (en) * | 2010-12-16 | 2011-06-01 | 嘉兴安普铁路配件有限公司 | High intensity thermosetting molecule based composite material and application thereof |
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| CN108797231A (en) * | 2018-09-25 | 2018-11-13 | 浙江三维橡胶制品股份有限公司 | The anti-winged device of spring and its application |
| CN112552486A (en) * | 2020-04-22 | 2021-03-26 | 普氢(上海)新材料科技有限公司 | Pre-accelerated toughening anhydride curing agent, preparation method thereof and epoxy resin composition for producing pultrusion composite material |
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