WO2018033042A1 - 高纤维含量纤维增强聚氨酯硬泡复合板材及其制作方法 - Google Patents

高纤维含量纤维增强聚氨酯硬泡复合板材及其制作方法 Download PDF

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WO2018033042A1
WO2018033042A1 PCT/CN2017/097347 CN2017097347W WO2018033042A1 WO 2018033042 A1 WO2018033042 A1 WO 2018033042A1 CN 2017097347 W CN2017097347 W CN 2017097347W WO 2018033042 A1 WO2018033042 A1 WO 2018033042A1
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fiber
foam composite
rigid foam
composite sheet
content
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French (fr)
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牛斌
曾志斌
苏永华
赵体波
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中国铁道科学研究院铁道建筑研究所
中国铁道科学研究院
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Publication of WO2018033042A1 publication Critical patent/WO2018033042A1/zh

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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K7/06—Elements
    • 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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids

Definitions

  • the invention belongs to the technical field of polymer composite materials, and relates to a high fiber content fiber reinforced polyurethane rigid foam composite board, in particular to a high fiber content fiber reinforced polyurethane rigid foam composite applied in the fields of railway, light rail and subway.
  • the sheet and its manufacturing method are made into composite sleepers, which can be extended to bridges, municipal, chemical, marine, armored vehicles, trucks, offshore drilling platforms and other fields as a walkway board, and can also be used as a template for concrete pouring construction.
  • the plates used in railways, light rails and subways, such as pedestrian walkway boards, cable trough covers, sleepers, etc. are mostly made of reinforced concrete or reactive powder concrete.
  • the quality is large, the construction quality is difficult to guarantee, and the durability is not good. Deterioration requires regular inspection and maintenance.
  • some wood materials are used instead of not only consuming a large amount of high-quality wood, but also exposed to harsh natural environment for a long time. The deterioration is serious, and cracks, defects and insect holes are prone to occur. About 5 to 10 are used. It must be replaced in the year, which greatly increases the maintenance and replacement costs of the product.
  • Some are replaced by FRP materials, but FRP materials are added in the production, a large amount of powder is added.
  • the quality of the products is also large; if the glass fiber reinforced plastic material is made into a hollow structure, its mechanical properties are greatly reduced, especially the bolt pull-out strength is too low, and there is a safety hazard, which usually has to be replaced in 5 to 10 years.
  • the fiber-reinforced polyurethane foam materials studied at home and abroad are made of polyether polyol and isocyanate.
  • the polyether polyol has high functionality and the polyurethane reaction and curing rate is fast, basically 3 minutes. It can be cured in the right and left time, and the selected polyether polyol has high viscosity and poor fluidity. It is difficult to solve the problem of uniform polyurethane and fiber impregnation before the polyurethane is cured. Therefore, the fiber content of the fiber-reinforced polyurethane foam products currently produced at home and abroad Low, polyurethane and fiber impregnation uneven, local polyurethane content, foam, local fiber content, dry yarn phenomenon, resulting in low strength, uneven strength, unstable quality.
  • the object of the present invention is to provide a high fiber content fiber reinforced polyurethane rigid foam composite sheet and a preparation method thereof, and the comprehensive performance thereof. It is better than the above materials and can be effectively replaced.
  • a high fiber content fiber reinforced polyurethane rigid foam composite board which is made of a polyurethane resin as a matrix material and a fiber as a reinforcing material.
  • the mass ratio of the polyurethane resin and the ratio of the polyurethane resin to the reinforcing fiber are as follows:
  • the present invention can also be improved as follows.
  • the reinforcing fiber is a mixture of any one or more of glass fiber, basalt fiber, carbon fiber, aramid fiber, and steel fiber.
  • the reinforcing fibers are mainly composed of long fibers, and further include chopped fibers and fiber mats.
  • the coupling agent is a silane coupling agent.
  • the anti-UV agent is a UV-based anti-UV agent.
  • the activity of the polyurethane resin reaction is lowered, the curing time of the polyurethane resin is prolonged, the immersion time with the reinforcing fiber is increased, and the viscosity of the polyether polyol is employed. It has low fluidity and increases its impregnation ability with reinforcing fibers, making it more uniform with reinforcing fiber impregnation.
  • the coupling agent By increasing the coupling agent, the wettability and dispersibility of the filler in polyurethane resin are greatly improved, and the addition is increased.
  • the impregnation ability and adhesive ability of the polyurethane resin and the reinforcing fiber make the polyurethane resin and the reinforcing fiber impregnate more thoroughly, and improve the penetration speed of the impregnated reinforcing fiber of the polyurethane resin, thereby solving the problem that the reinforcing fiber is excessive and difficult to be impregnated, thereby making the material
  • the strength performance is greatly improved and the strength uniformity is more stable; in addition, by adding a coupling agent, the electrical properties of the material can be greatly improved;
  • the fiber reinforced polyurethane rigid foam material products with a reinforcing fiber content of more than 840 kg/m 3 and a reinforcing fiber content of more than 60% make up the technical blank of the fiber reinforced polyurethane foam composite sheet, and diversify its product specifications and performances to meet different technical specifications.
  • the mass ratio of the reinforcing fibers is more than 60%, which not only reduces the manufacturing cost, but also greatly improves the strength of the fiber-reinforced polyurethane rigid foam composite sheet at the same density, and at the same time, the product is denser, the water absorption amount, and the like. Significantly lower indicators, etc., improve the water resistance of the product;
  • the anti-ultraviolet aging performance of the material is further enhanced by the addition of an anti-UV agent;
  • the invention provides a high fiber content fiber reinforced polyurethane rigid foam composite sheet, which can effectively replace the current high quality concrete, wood, glass fiber reinforced plastic sheet and the low fiber content fiber reinforced polyurethane foam composite sheet studied at home and abroad, and can be widely applied to railways, In the fields of light rail and subway, it is used to make composite sleepers and can be applied to various walkway step boards and concrete construction templates.
  • the invention also relates to a method for manufacturing a high fiber content fiber reinforced polyurethane rigid foam composite board It is made by continuous molding process.
  • the continuous molding process includes seven processes of unwinding long fibers and fiber mats, injecting polyurethane resin, adding chopped fibers, uniformly impregnating, crawling laminating, curing, and fixed length cutting.
  • the uniform impregnation is specifically: uniformly impregnating the polyurethane resin on the surface and inside of the reinforcing fiber through a high-pressure foaming device, a moving casting device, and a corresponding tooling.
  • the crawler laminating machine is composed of a crawler laminating machine and a side stopper, and the side stopper is fixed on the crawler laminator, and the height and the width of the cavity are adjusted according to the size of the stopper. .
  • the fixed length cutting is performed by a cutting machine, and the cut high fiber content fiber reinforced polyurethane rigid foam composite sheet has a thickness of 10 mm to 120 mm, a width of 100 mm to 600 mm, and a density of 200 kg/m 3 to 2000 kg/m 3 . .
  • FIG. 1 is a schematic view showing a production process of a high fiber content fiber reinforced polyurethane rigid foam composite sheet according to the present invention
  • FIG. 2 is a schematic view showing the structure of a high fiber content fiber reinforced polyurethane rigid foam composite sheet according to the present invention.
  • the invention relates to a high fiber content fiber reinforced polyurethane rigid foam composite sheet 9 which is made of a polyurethane resin 8 as a matrix material and a fiber as a reinforcing material.
  • the mass ratio of the polyurethane resin 8 and the mass ratio of the urethane resin 8 to the reinforcing fibers are as follows:
  • the reinforcing fiber is a mixture of any one or more of glass fiber, basalt fiber, carbon fiber, aramid fiber, and steel fiber.
  • the reinforcing fibers are mainly composed of long fibers 6, and further include chopped fibers 7 and fiber mats.
  • the coupling agent is a silane coupling agent.
  • the anti-UV agent is a UV-based anti-UV agent.
  • the invention also relates to a method for manufacturing a high fiber content fiber reinforced polyurethane rigid foam composite sheet 9, which is produced by a continuous molding process, and the continuous molding process comprises unwinding long fibers 6 and fiber mats, injection polyurethane resin 8, and adding short Cut fiber 7, uniform impregnation, crawler lamination mainframe 4 solidification, cooling, fixed length cutting seven processes.
  • the uniform impregnation is specifically to uniformly impregnate the urethane resin 8 on the surface and inside of the reinforcing fiber through the high pressure foaming device 2, the mobile casting device 3, and the corresponding tooling.
  • the crawler laminating machine 4 is composed of a crawler laminating machine and a side stopper, and the side stopper is fixed on the crawler laminating machine, and the height and width of the cavity are adjusted according to the size of the stopper.
  • the fixed length cutting is performed by the cutting machine 5, and the cut high fiber content fiber reinforced polyurethane rigid foam composite sheet has a thickness of 10 mm to 120 mm, a width of 100 mm to 600 mm, and a density of 200 kg/m 3 to 2000 kg/m 3 .
  • the continuous molding process of the high fiber content fiber reinforced polyurethane rigid foam composite sheet of the present invention is carried out by the apparatus shown in the drawing, firstly unwinding the long fiber and the fiber mat in the creel 1, injecting the polyurethane resin, and adding short.
  • the fiber is cut, and then uniformly impregnated by the high pressure foaming device 2, the mobile casting device 3 and the corresponding tooling, and then solidified in the crawler laminating machine 4, and after cooling, the cured plate is cut by the cutter 5.
  • the high fiber content fiber reinforced polyurethane rigid foam composite sheet 9 obtained after cutting a long fiber 6 and a chopped fiber 7 extending in the longitudinal direction are provided inside, and the outer portion is wrapped with a polyurethane resin 8, and the curing is performed.
  • the high fiber content fiber reinforced polyurethane rigid foam composite sheet 9 is obtained.
  • the fiber mat may be disposed on the outer side surface of the urethane resin 8 enclosing the long fibers 6 and the short fibers 7.
  • the long fibers 6 and the short fibers 7 may be arranged in a plurality of rows and alternately arranged to form a matrix array structure, and the polyurethane resin 8 is wrapped around the long fibers 6 and the short fibers 7 to form a rectangular parallelepiped plate having a thickness. It is 10 mm to 120 mm, the width is 100 mm to 600 mm, and the density is 200 kg/m 3 to 2000 kg/m 3 . Preferably, the apparent total density is 800 kg/m 3 to 1800 kg/m 3 .
  • the proportion of the polyurethane resin and the ratio of the polyurethane resin to the reinforcing fiber are as follows: the polyether polyol A having a hydroxyl value of 400 to 480 and a functionality of 1 to 3, 90 parts, a hydroxyl value of 60 to 160, and a functionality of 1 to 2 10 parts of polyether polyol B, 10 parts of flame retardant, 5 parts of hard foam stabilizer, 15 parts of coupling agent, 0.3 parts of catalyst, 0.1 part of foaming agent, 0.3 part of antioxidant, 0.3 part of anti-UV agent, 120 parts of isocyanate; long fiber: 430 parts, chopped fiber 10 parts, fiber mat 5 parts.
  • the reinforcing fiber content is 64%
  • the production density is 1400 ⁇ 50kg/m 3 fiber reinforced polyurethane rigid foam composite sheet specification: 260mm ⁇ 50mm ⁇ 3000mm.
  • Track type laminating host parameter setting running speed: 0.4m/min, temperature: 90°C/60°C.
  • Table 1 The properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 1.
  • the proportion of the polyurethane resin and the ratio of the polyurethane resin to the reinforcing fiber are as follows: the polyether polyol A having a hydroxyl value of 400 to 480 and a functionality of 1 to 3, 95 parts, a hydroxyl value of 60 to 160, and a functionality of 1 to 2 5 parts of polyether polyol B, 10 parts of flame retardant, 3 parts of hard foam stabilizer, 5 parts of coupling agent, 0.3 parts of catalyst, 0.1 part of foaming agent, 0.3 part of antioxidant, 0.3 part of anti-UV agent, 110 parts of isocyanate; long fiber: 410 parts, chopped fiber 10 parts, fiber mat 0 parts.
  • the reinforcing fiber content is 65%, the production density is 1200 ⁇ 50kg/m 3 fiber reinforced polyurethane rigid foam composite sheet specification: 240mm ⁇ 50mm ⁇ 3000mm.
  • Track type laminating host parameter setting running speed: 0.6m/min, temperature: 90°C/60°C.
  • Table 2 The properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 2.
  • the proportion of the polyurethane resin and the ratio of the polyurethane resin to the reinforcing fiber are as follows: the polyether polyol A having a hydroxyl value of 400 to 480 and a functionality of 1 to 3, 90 parts, a hydroxyl value of 60 to 160, and a functionality of 1 to 2 5 parts of polyether polyol B, 15 parts of flame retardant, 5 parts of hard foam stabilizer, 10 parts of coupling agent, 0.2 parts of catalyst, 0.3 part of foaming agent, 0.5 part of antioxidant, 0.5 part of anti-UV agent, 115 parts of isocyanate; long fiber: 520 parts, chopped fiber 5 parts, 1 part of fiber mat.
  • the reinforcing fiber content is 68.5%
  • the production density is 1000 ⁇ 50kg/m 3 fiber reinforced polyurethane rigid foam composite sheet specification: 500mm ⁇ 30mm ⁇ 3000mm.
  • Track type laminating host parameter setting running speed: 0.5m/min, temperature: 90°C/70°C.
  • the properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 3.
  • the proportion of the polyurethane resin and the ratio of the polyurethane resin to the reinforcing fiber are as follows: the polyether polyol A having a hydroxyl value of 400 to 480 and a functionality of 1 to 3, 95 parts, a hydroxyl value of 60 to 160, and a functionality of 1 to 2 10 parts of polyether polyol B, 5 parts of flame retardant, 5 parts of hard foam stabilizer, 10 parts of coupling agent, 0.1 part of catalyst, 0.1 part of foaming agent, 0.25 part of antioxidant, 0.25 part of anti-UV agent, 125 parts of isocyanate; long fiber: 460 parts, chopped fiber 10 parts, fiber mat 0.
  • the reinforcing fiber content is 65%, the production density is 800 ⁇ 50kg/m 3 fiber reinforced polyurethane rigid foam composite sheet specification: 200mm ⁇ 60mm ⁇ 3000mm.
  • Track type laminating host parameter setting running speed: 0.4m/min, temperature: 80°C/70°C.
  • Table 4 The properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 4.
  • the proportion of the polyurethane resin and the ratio of the polyurethane resin to the reinforcing fiber are as follows: the polyether polyol A having a hydroxyl value of 400 to 480 and a functionality of 1 to 3, 92 parts, a hydroxyl value of 60 to 160, and a functionality of 1 to 2 8 parts of polyether polyol B, 10 parts of flame retardant, 2.5 parts of hard foam stabilizer, 15 parts of coupling agent, 1 part of catalyst, 1 part of foaming agent, 1 part of antioxidant, 1 part of anti-UV agent, 100 parts of isocyanate; long fiber: 1330 parts, 30 pieces of chopped fibers, 10 parts of fiber mat.
  • the reinforcing fiber content is 85%, the production density is 1500 ⁇ 50kg/m 3 fiber reinforced polyurethane rigid foam composite sheet specification: 600mm ⁇ 10mm ⁇ 3000mm.
  • Track type laminating host parameter setting running speed: 0.4m/min, temperature: 90°C/60°C.
  • the properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 5.
  • the proportion of the polyurethane resin and the ratio of the polyurethane resin to the reinforcing fiber are as follows: a polyether polyol A having a hydroxyl value of 400 to 480 and a functionality of 1 to 3, a hydroxyl value of 60 to 160, and a functionality of 1 to 2. 7 parts of polyether polyol B, 10 parts of flame retardant, 2.5 parts of hard foam stabilizer, 15 parts of coupling agent, 0.8 parts of catalyst, 0.6 part of foaming agent, 0.7 part of antioxidant, 0.5 part of anti-UV agent, 135 parts of isocyanate; long fiber: 1940 parts, 40 pieces of chopped fibers, 20 parts of fiber mat.
  • the reinforcing fiber content is 88%, the production density is 1800 ⁇ 50kg/m 3 fiber reinforced polyurethane rigid foam composite sheet specification: 100mm ⁇ 100mm ⁇ 3000mm.
  • Track type laminating host parameter setting running speed: 0.4m/min, temperature: 90°C/60°C.
  • the properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 6.
  • the invention discloses a high fiber content fiber reinforced polyurethane rigid foam composite board, which solves the problem of insufficient polyurethane and fiber impregnation by adopting various technical means such as low hydroxyl value low functionality mixed polyether polyol and coupling agent. , thereby increasing the fiber content, capable of producing a fiber reinforced polyurethane rigid foam material having a density higher than 840 kg/m 3 and a fiber content of more than 60%, and making up for the technical blank of the high fiber content fiber reinforced polyurethane foam composite sheet, and making the product Diversified specifications and performance to meet different technical requirements.
  • the high fiber content fiber reinforced polyurethane rigid foam composite sheet has a fiber content of more than 60%, and the mechanical properties, ultraviolet aging resistance, electrical properties and water resistance of the produced material are obtained under the condition that the density is almost the same. And many other indicators are far superior to the products of well-known manufacturers at home and abroad.

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Abstract

一种高纤维含量纤维增强聚氨酯硬泡复合板材及其制作方法，以聚氨酯树脂为基体材料，包括混合型聚醚多元醇、阻燃剂、硬泡稳定剂、偶联剂、催化剂、发泡剂、抗氧剂、抗紫外剂、异氰酸酯，以纤维为增强材料，其含量大于60％。通过采用低羟值低官能度的混合型聚醚多元醇、偶联剂等多种技术手段，解决了聚氨酯树脂与增强纤维浸渍不充分的问题，从而提高了增强纤维含量，能够制作出密度高于840kg/m3且增强纤维含量大于60％的纤维增强聚氨酯硬泡材料制品，弥补了纤维增强聚氨酯硬泡复合板材的技术空白，使其产品规格及性能多元化，满足不同的技术指标要求。

Description

高纤维含量纤维增强聚氨酯硬泡复合板材及其制作方法 技术领域
本发明属于高分子复合材料技术领域，本发明涉及一种高纤维含量纤维增强聚氨酯硬泡复合板材，尤其是涉及一种应用在铁路、轻轨及地铁等领域的高纤维含量纤维增强聚氨酯硬泡复合板材及其制作方法，制成复合材料轨枕，可推广到桥梁、市政、化工、船舶、装甲车、货车、海洋钻井平台等领域作为步道板使用，还可用作混凝土浇注施工的模板。
背景技术
目前铁路、轻轨及地铁等领域采用的板材，如人行步道板、电缆槽盖板、轨枕等大都采用钢筋混凝土或活性粉末混凝土制作而成，质量大、施工质量难以保证、耐久性不好，容易劣化，需要定期检查维修。为了解决这些问题，有的采用木质材料进行替代，不仅需要消耗大量的优质木材，而且长期暴露在恶劣的自然环境里，劣化比较严重，容易出现裂纹、缺陷及虫蛀孔洞，大约使用5～10年就必须更换，大大增加了产品的维护及更换成本。有的采用玻璃钢材料进行替代，但是玻璃钢材料在生产中，加入了大量的粉料，经日晒雨淋后，很容易出现粉化现象，质量不稳定，产品耐候性差，长期使用存在安全隐患，同时其制品质量也较大；若将玻璃钢材料制成空心结构，其力学性能大大降低，尤其是螺栓抗拔强度太低，存在安全隐患，一般5～10年就必须更换。有的使用纤维增强聚氨酯泡沫材料，但其纤维含量低，强度低，在普通铁路和重载铁路轨枕强度测试过程中出现了严重塌陷，不适合应用在普通铁路和重载铁路中，仅适合应用在国内外的轻轨和地铁。
目前国内外研究的纤维增强聚氨酯泡沫材料，所用的聚氨酯均由聚醚多元醇与异氰酸酯反应而成，其采用的聚醚多元醇官能度较高，聚氨酯反应和固化速率很快，基本上3分钟左右的时间即可固化，并且其选用的聚醚多元醇粘度大，流动性差，很难在聚氨酯固化前解决聚氨酯与纤维浸渍均匀的问题，故国内外目前制作的纤维增强聚氨酯泡沫材料制品中纤维含量低，且聚氨酯与纤维浸渍不均匀，局部聚氨酯含量多，泡沫大，局部纤维含量多，出现干纱现象，致使制作的产品强度低，且强度不均匀，质量不稳定。由于其纤维含量低，树脂含量高，在生产 中，树脂发泡膨胀产生大量的飞边，不仅造成了产品浪费，制作成本增高，而且对设备及模具造成了极大的损伤。不仅如此，还由于其无法解决聚氨酯与纤维的浸渍问题，故其未制作出较高纤维含量的纤维增强聚氨酯泡沫材料制品，更未制作出较高纤维含量、较高密度的纤维增强聚氨酯泡沫材料制品。目前，尚未见报道并且市场上未见到密度高于840kg/m3且纤维含量高于60％的纤维增强聚氨酯泡沫材料及制品。
发明内容
针对目前混凝土、木质、玻璃钢板材及低纤维含量的纤维增强聚氨酯泡沫板材等技术上的不足，本发明的目的是提供一种高纤维含量纤维增强聚氨酯硬泡复合板材及其制作方法，其综合性能优于以上材质的板材，能够有效替代。
本发明解决上述问题的技术方案如下：一种高纤维含量纤维增强聚氨酯硬泡复合板材，其以聚氨酯树脂为基体材料，以纤维为增强材料。以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的质量比例如下：
Figure PCTCN2017097347-appb-000001
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述增强纤维为玻璃纤维、玄武岩纤维、碳纤维、芳纶纤维、钢纤维中的任意一种或多种混合。
进一步，所述增强纤维以长纤维为主体，还包括短切纤维和纤维毡。
进一步，所述偶联剂为硅烷偶联剂。
进一步，所述抗紫外剂为UV类抗紫外剂。
本发明的一种高纤维含量纤维增强聚氨酯硬泡复合板材，具有如下优点：
通过采用低羟值低官能度的混合型聚醚多元醇，降低了聚氨酯树脂反应的活性，延长了聚氨酯树脂的固化时间，增加了其与增强纤维的浸渍时间，同时采用的聚醚多元醇粘度较低、流动性好，增加了其与增强纤维的浸渍能力，使其与增强纤维浸渍更加均匀；通过增加偶联剂，大大提高了填料在聚氨酯树脂中的润湿性和分散性，增加了聚氨酯树脂与增强纤维的浸渍能力及粘合能力，使聚氨酯树脂与增强纤维浸渍更加彻底，并提高聚氨酯树脂的浸渍增强纤维的浸透速度，解决了增强纤维过多，不易浸渍的问题，从而使材料强度性能大幅度提高及强度均匀性更加稳定；另外，通过添加偶联剂，还可以大大提高材料的电气性能；
通过采用低羟值低官能度的混合型聚醚多元醇、使用偶联剂等多种技术手段，解决了聚氨酯树脂与增强纤维浸渍不充分的问题，从而提高了增强纤维含量，能够制作出密度高于840kg/m3且增强纤维含量大于60％的纤维增强聚氨酯硬泡材料制品，弥补了纤维增强聚氨酯泡沫复合板材的技术空白，使其产品规格及性能多元化，满足不同的技术指标要求。
通过提高增强纤维的质量比例，使增强纤维的质量比例大于60％，不仅减少了制作成本，而且大大的提高了同等密度下纤维增强聚氨酯硬泡复合板材的强度，同时产品更加致密，吸水量等指标等大幅降低，提高了产品的耐水性能；
通过添加硬泡稳定剂，避免了聚氨酯泡沫泡孔过大问题的发生，使聚氨酯硬泡更加均匀，更加稳定。
通过添加阻燃剂，不仅降低了聚醚多元醇的粘度，使其流动性好，而且增强了材料的阻燃性能；
通过添加抗氧剂，增强了材料的耐湿热老化的性能；
通过添加抗紫外剂，进一步增强了材料的抗紫外日光老化的性能；
通过增加短切纤维，使材料更加致密，进一步提高了产品的强度；
通过增加纤维毡，进一步提高了产品的抗弯曲强度。
本发明提供的一种高纤维含量纤维增强聚氨酯硬泡复合板材，能够有效取代目前优质的混凝土、木质、玻璃钢板材及国内外研究的低纤维含量纤维增强聚氨酯泡沫复合板材，可广泛应用于铁路、轻轨及地铁等领域，用于制作复合材料轨枕，并可推广应用到各种人行道步板和混凝土施工模板。
本发明还涉及一种高纤维含量纤维增强聚氨酯硬泡复合板材的制作方法，采 用连续成型工艺制作而成，其连续成型工艺包括放卷长纤维及纤维毡、注射聚氨酯树脂、加入短切纤维、均匀浸渍、履带式层压主机内固化、冷却、定长切割七个工序。
进一步，所述均匀浸渍具体是将聚氨酯树脂通过高压发泡设备、移动浇注设备及对应的工装均匀浸渍在增强纤维的表面及内部。
进一步，所述履带式层压主机是由履带式层压机及侧边挡块共同组成，侧边挡块固定在履带式层压机上，模腔的高度及宽度依据挡块的尺寸进行调整。
进一步，定长切割是通过切割机进行的，切割后的高纤维含量纤维增强聚氨酯硬泡复合板材，其厚度为10mm～120mm，宽度为100mm～600mm，密度为200kg/m3～2000kg/m3。
附图说明
图1为本发明高纤维含量纤维增强聚氨酯硬泡复合板材的生产工艺示意图；
图2为本发明高纤维含量纤维增强聚氨酯硬泡复合板材的结构示意图。
附图中各标号所代表的部件列表如下：
1、纱架，2、高压发泡设备，3、移动浇注设备，4、履带式层压主机，5、切割机，6、长纤维，7、短切纤维，8、聚氨酯树脂，9、高纤维含量纤维增强聚氨酯硬泡复合板材。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
本发明涉及一种高纤维含量纤维增强聚氨酯硬泡复合板材9，其以聚氨酯树脂8为基体材料，以纤维为增强材料。以质量份计，聚氨酯树脂8的配方及聚氨酯树脂8与增强纤维的质量比例如下：
Figure PCTCN2017097347-appb-000002
Figure PCTCN2017097347-appb-000003
所述增强纤维为玻璃纤维、玄武岩纤维、碳纤维、芳纶纤维、钢纤维中的任意一种或多种混合。
所述增强纤维以长纤维6为主体，还包括短切纤维7和纤维毡。
所述偶联剂为硅烷偶联剂。
所述抗紫外剂为UV类抗紫外剂。
本发明还涉及一种高纤维含量纤维增强聚氨酯硬泡复合板材9的制作方法，采用连续成型工艺制作而成，其连续成型工艺包括放卷长纤维6及纤维毡、注射聚氨酯树脂8、加入短切纤维7、均匀浸渍、履带式层压主机4内固化、冷却、定长切割七个工序。
所述均匀浸渍具体是将聚氨酯树脂8通过高压发泡设备2、移动浇注设备3及对应的工装均匀浸渍在增强纤维的表面及内部。
所述履带式层压主机4是由履带式层压机及侧边挡块共同组成，侧边挡块固定在履带式层压机上，模腔的高度及宽度依据挡块的尺寸进行调整。
定长切割是通过切割机5进行的，切割后的高纤维含量纤维增强聚氨酯硬泡复合板材，其厚度为10mm～120mm，宽度为100mm～600mm，密度为200kg/m3～2000kg/m3。
如图1所示，本发明高纤维含量纤维增强聚氨酯硬泡复合板材的连续成型工艺通过图中所示的装置进行，先在纱架1放卷长纤维及纤维毡、注射聚氨酯树脂、加入短切纤维，再通过高压发泡设备2、移动浇注设备3及对应的工装实现均匀浸渍，然后在履带式层压主机4内固化，冷却后通过切割机5对固化后的板材进行切割。
如图2所示，切割后得到的高纤维含量纤维增强聚氨酯硬泡复合板材9中，内部设有沿长度方向延伸的长纤维6和短切纤维7，其外部包裹有聚氨酯树脂8，固化即得所述高纤维含量纤维增强聚氨酯硬泡复合板材9。纤维毡可以设置在包裹 住长纤维6和短纤维7的聚氨酯树脂8的外侧表面。具体的，长纤维6和短纤维7可以自身排列成多排，并交替间隔设置，形成矩阵式阵列结构，聚氨酯树脂8包裹在长纤维6和短纤维7外，形成长方体形的板材，其厚度为10mm～120mm，宽度为100mm～600mm，密度为200kg/m3～2000kg/m3，优选的，其表观总密度在800kg/m3～1800kg/m3。
实施例1：
以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的比例如下：羟值400～480、官能度1～3的聚醚多元醇A 90份，羟值60～160、官能度1～2的聚醚多元醇B 10份，阻燃剂10份，硬泡稳定剂5份，偶联剂15份，催化剂0.3份，发泡剂0.1份，抗氧剂0.3份，抗紫外剂0.3份，异氰酸酯120份；长纤维：430份，短切纤维10份，纤维毡5份。其中增强纤维含量为64％，制作密度1400±50kg/m3纤维增强聚氨酯硬泡复合板材规格：260mm×50mm×3000mm。
履带式层压主机参数设置：运行速度：0.4m/min，温度：90℃/60℃。按照本实施例的配方及运行条件制作的复合板材性能如表1所示。
表1
Figure PCTCN2017097347-appb-000004
实施例2：
以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的比例如下：羟值 400～480、官能度1～3的聚醚多元醇A 95份，羟值60～160、官能度1～2的聚醚多元醇B 5份，阻燃剂10份，硬泡稳定剂3份，偶联剂5份，催化剂0.3份，发泡剂0.1份，抗氧剂0.3份，抗紫外剂0.3份，异氰酸酯110份；长纤维：410份，短切纤维10份，纤维毡0份。其中增强纤维含量为65％，制作密度1200±50kg/m3纤维增强聚氨酯硬泡复合板材规格：240mm×50mm×3000mm。
履带式层压主机参数设置：运行速度：0.6m/min，温度：90℃/60℃。按照本实施例的配方及运行条件制作的复合板材性能如表2所示。
表2
Figure PCTCN2017097347-appb-000005
实施例3：
以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的比例如下：羟值400～480、官能度1～3的聚醚多元醇A 90份，羟值60～160、官能度1～2的聚醚多元醇B 5份，阻燃剂15份，硬泡稳定剂5份，偶联剂10份，催化剂0.2份，发泡剂0.3份，抗氧剂0.5份，抗紫外剂0.5份，异氰酸酯115份；长纤维：520份，短切纤维5份，纤维毡1份。其中增强纤维含量为68.5％，制作密度1000±50kg/m3纤维增强聚氨酯硬泡复合板材规格：500mm×30mm×3000mm。
履带式层压主机参数设置：运行速度：0.5m/min，温度：90℃/70℃。按照本实施例的配方及运行条件制作的复合板材性能如表3所示。
表3
Figure PCTCN2017097347-appb-000006
实施例4：
以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的比例如下：羟值400～480、官能度1～3的聚醚多元醇A 95份，羟值60～160、官能度1～2的聚醚多元醇B 10份，阻燃剂5份，硬泡稳定剂5份，偶联剂10份，催化剂0.1份，发泡剂0.1份，抗氧剂0.25份，抗紫外剂0.25份，异氰酸酯125份；长纤维：460份，短切纤维10份，纤维毡0。其中增强纤维含量为65％，制作密度800±50kg/m3纤维增强聚氨酯硬泡复合板材规格：200mm×60mm×3000mm。
履带式层压主机参数设置：运行速度：0.4m/min，温度：80℃/70℃。按照本实施例的配方及运行条件制作的复合板材性能如表4所示。
表4
Figure PCTCN2017097347-appb-000007
Figure PCTCN2017097347-appb-000008
实施例5：
以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的比例如下：羟值400～480、官能度1～3的聚醚多元醇A 92份，羟值60～160、官能度1～2的聚醚多元醇B 8份，阻燃剂10份，硬泡稳定剂2.5份，偶联剂15份，催化剂1份，发泡剂1份，抗氧剂1份，抗紫外剂1份，异氰酸酯100份；长纤维：1330份，短切纤维30份，纤维毡10份。其中增强纤维含量为85％，制作密度1500±50kg/m3纤维增强聚氨酯硬泡复合板材规格：600mm×10mm×3000mm。
履带式层压主机参数设置：运行速度：0.4m/min，温度：90℃/60℃。按照本实施例的配方及运行条件制作的复合板材性能如表5所示。
表5
Figure PCTCN2017097347-appb-000009
实施例6：
以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的比例如下：羟值 400～480、官能度1～3的聚醚多元醇A 93份，羟值60～160、官能度1～2的聚醚多元醇B 7份，阻燃剂10份，硬泡稳定剂2.5份，偶联剂15份，催化剂0.8份，发泡剂0.6份，抗氧剂0.7份，抗紫外剂0.5份，异氰酸酯135份；长纤维：1940份，短切纤维40份，纤维毡20份。其中增强纤维含量为88％，制作密度1800±50kg/m3纤维增强聚氨酯硬泡复合板材规格：100mm×100mm×3000mm。
履带式层压主机参数设置：运行速度：0.4m/min，温度：90℃/60℃。按照本实施例的配方及运行条件制作的复合板材性能如表6所示。
表6
Figure PCTCN2017097347-appb-000010
对比例分析
本发明一种高纤维含量纤维增强聚氨酯硬泡复合板材，通过采用低羟值低官能度的混合型聚醚多元醇、偶联剂等多种技术手段，解决了聚氨酯与纤维浸渍不充分的问题，从而提高了纤维含量，能够制作出密度高于840kg/m3且纤维含量大于60％的纤维增强聚氨酯硬泡材料制品，弥补了高纤维含量纤维增强聚氨酯泡沫复合板材的技术空白，使其产品规格及性能多元化，满足不同的技术指标要求。
通过提高增强纤维的质量比例到大于60％，不仅减少了制作成本，而且大大提高了同等密度下纤维增强聚氨酯硬泡复合板材的强度，同时产品更加致密，吸水量等指标大幅降低，提高了产品的耐水性能；
目前未见到产品密度高于840kg/m3且纤维含量高于60％的纤维增强聚氨酯泡沫材料及制品的报道及实物。通过本发明制作方法，制作密度为800±50kg/m3的材料，与国内外知名厂家制作的纤维增强聚氨酯泡沫复合材料及制品的实物进行测试对比，结果如表7所示。
表7
Figure PCTCN2017097347-appb-000011
对比分析结论
可见，本发明一种高纤维含量纤维增强聚氨酯硬泡复合板材，其纤维含量大于60％，在密度相差无几的情况下，所制作的材料的力学性能、耐紫外老化性能、电气性能、耐水性能等多种指标都远远优于国内外知名厂家的制品。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种高纤维含量纤维增强聚氨酯硬泡复合板材，其以聚氨酯树脂为基体材料，以纤维为增强材料，其特征在于，以质量份计，聚氨酯树脂的配方及聚氨酯树脂与增强纤维的质量比例如下：
    Figure PCTCN2017097347-appb-100001
  2. 根据权利要求1所述高纤维含量纤维增强聚氨酯硬泡复合板材，其特征在于，所述增强纤维为玻璃纤维、玄武岩纤维、碳纤维、芳纶纤维、钢纤维中的任意一种或多种混合。
  3. 根据权利要求1或2所述高纤维含量纤维增强聚氨酯硬泡复合板材，其特征在于，所述增强纤维以连续长纤维为主体，还包括短切纤维和纤维毡。
  4. 一种如权利要求3所述高纤维含量纤维增强聚氨酯硬泡复合板材的制作方法，其特征在于，采用连续成型工艺制作而成，其连续成型工艺包括放卷长纤维及纤维毡、注射聚氨酯树脂、加入短切纤维、均匀浸渍、在履带式层压主机内固化、冷却、定长切割七个工序。
  5. 根据权利要求4所述高纤维含量纤维增强聚氨酯硬泡复合板材的制作方法，其特征在于，所述均匀浸渍具体是将聚氨酯树脂通过高压发泡机、移动浇注设备及对应的工装均匀浸渍在增强纤维的表面及内部。
  6. 根据权利要求4所述高纤维含量纤维增强聚氨酯硬泡复合板材的制作方法，其特征在于，所述履带式层压主机是由履带式层压机及侧边挡块共同组成，侧边挡块固定在履带式层压机上，模腔的高度及宽度依据挡块的尺寸进行调整。
  7. 根据权利要求4至6任一项所述高纤维含量纤维增强聚氨酯硬泡复合板材 的制作方法，其特征在于，定长切割后的高纤维含量纤维增强聚氨酯硬泡复合板材，其厚度为10mm～120mm。
  8. 根据权利要求4至6任一项所述高纤维含量纤维增强聚氨酯硬泡复合板材的制作方法，其特征在于，定长切割后的高纤维含量纤维增强聚氨酯硬泡复合板材，其宽度为100mm～600mm。
  9. 根据权利要求4至6任一项所述高纤维含量纤维增强聚氨酯硬泡复合板材的制作方法，其特征在于，定长切割后的高纤维含量纤维增强聚氨酯硬泡复合板材，其密度为200kg/m3～2000kg/m3。
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