WO2018033042A1

WO2018033042A1 - High-fiber-content fiber-reinforced rigid polyurethane foam composite panel and method for manufacturing same

Info

Publication number: WO2018033042A1
Application number: PCT/CN2017/097347
Authority: WO
Inventors: 牛斌; 曾志斌; 苏永华; 赵体波
Original assignee: 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
Priority date: 2016-08-17
Filing date: 2017-08-14
Publication date: 2018-02-22
Also published as: CN106349446A; CN106349446B

Abstract

Provided are a high-fiber-content fiber-reinforced rigid polyurethane foam composite panel and method for manufacturing same; polyurethane resin is employed as a matrix material; comprised are a hybrid polyether polyol, a fire retardant, a hard-foam stabilizing agent, a coupling agent, a catalyst, a blowing agent, an antioxidant, an anti-UV agent, and isocyanate; fiber is employed as a reinforcing material and its content is greater than 60%. Using such technical means as a low-hydroxyl and low-functionality hybrid polyether polyol and a coupling agent solves the problem of insufficient impregnation of polyurethane resin with reinforcing fiber, thereby increasing the reinforcing-fiber content; it is thus possible to manufacture a fiber-reinforced rigid polyurethane foam material product having a density higher than 840 kg/m³ and a reinforcing-fiber content of more than 60%, compensating for the technical deficiency of fiber-reinforced polyurethane hard-foam composite panels, making their product specifications and performance more diverse, and satisfying different technical requirements.

Description

High fiber content fiber reinforced polyurethane rigid foam composite board and preparation method thereof

Technical field

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.

Background technique

At present, 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. In order to solve these problems, 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. After sun and rain, it is easy to appear chalking, the quality is unstable, the product has poor weather resistance, and there are safety hazards in long-term use. At the same time, 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. Some use fiber-reinforced polyurethane foam, but its fiber content is low, the strength is low, and it has been seriously collapsed during the strength test of ordinary railway and heavy-duty railway sleepers. It is not suitable for application in ordinary railways and heavy-duty railways, only suitable for application. Light rail and subway at home and abroad.

At present, 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. Due to its low fiber content and high resin content, in the production, the foam expansion of the resin generates a large amount of flash, which not only causes waste of the product, increases the production cost, but also causes great damage to the equipment and the mold. Not only that, but also because it can not solve the problem of impregnation of polyurethane and fiber, it has not produced fiber-reinforced polyurethane foam products with higher fiber content, and has not produced fiber-reinforced polyurethane foam with higher fiber content and higher density. product. At present, no reports have been reported and fiber reinforced polyurethane foams and articles having a density higher than 840 kg/m ³ and a fiber content higher than 60% have not been seen on the market.

Summary of the invention

In view of the technical deficiencies of current concrete, wood, FRP sheet and low fiber content fiber reinforced polyurethane foam sheet, 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.

The technical solution to solve the above problems of the present invention is as follows: 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:

Based on the above technical solutions, the present invention can also be improved as follows.

Further, the reinforcing fiber is a mixture of any one or more of glass fiber, basalt fiber, carbon fiber, aramid fiber, and steel fiber.

Further, the reinforcing fibers are mainly composed of long fibers, and further include chopped fibers and fiber mats.

Further, the coupling agent is a silane coupling agent.

Further, the anti-UV agent is a UV-based anti-UV agent.

The high fiber content fiber reinforced polyurethane rigid foam composite board of the invention has the following advantages:

By using a low-hydroxyl and low-functionality mixed polyether polyol, 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. 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;

By using a mixed type polyether polyol having a low hydroxyl value and a low functionality, and a coupling agent and the like, the problem of insufficient impregnation of the polyurethane resin and the reinforcing fiber is solved, thereby increasing the reinforcing fiber content and producing a density. 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.

By increasing the mass ratio of the reinforcing fibers, 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;

By adding a hard foam stabilizer, the problem of excessive pores of the polyurethane foam is avoided, and the rigid polyurethane foam is more uniform and more stable.

By adding a flame retardant, not only the viscosity of the polyether polyol is lowered, the fluidity is improved, and the flame retardancy of the material is enhanced;

By adding an antioxidant, the resistance to heat and humidity aging of the material is enhanced;

The anti-ultraviolet aging performance of the material is further enhanced by the addition of an anti-UV agent;

By increasing the chopped fibers to make the material more dense, the strength of the product is further improved;

By increasing the fiber mat, the bending strength of the product is further improved.

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.

Further, 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.

Further, 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. .

Further, 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 .} .

DRAWINGS

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;

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 parts represented by the labels in the drawings are as follows:

1, creel, 2, high pressure foaming equipment, 3, mobile casting equipment, 4, crawler laminating host, 5, cutting machine, 6, long fiber, 7, chopped fiber, 8, polyurethane resin, 9, high Fiber content fiber reinforced polyurethane rigid foam composite sheet.

detailed description

The principles and features of the present invention are described in the following with reference to the accompanying drawings.

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 .

As shown in FIG. 1, 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.

As shown in FIG. 2, in 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. Specifically, 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 .

Example 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, 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. The properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 1.

Table 1

Example 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, 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. The properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 2.

Table 2

Example 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 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.

table 3

Example 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, 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. The properties of the composite sheet produced according to the formulation and operating conditions of this example are shown in Table 4.

Table 4

Example 5:

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.

table 5

Example 6

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.

Table 6

Comparative analysis

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.

By increasing the mass ratio of the reinforcing fibers to more than 60%, not only the production cost is reduced, but also the strength of the fiber-reinforced polyurethane rigid foam composite sheet at the same density is greatly improved, and the product is more compact, the water absorption amount and the like are greatly reduced, and the product is improved. Water resistance;

There have been no reports or physical observations of fiber reinforced polyurethane foams and products having a product density higher than 840 kg/m ³ and a fiber content higher than 60%. Through the preparation method of the present invention, a material having a density of 800±50 kg/m ³ is produced, and the physical properties of the fiber-reinforced polyurethane foam composite materials and products produced by well-known domestic and foreign manufacturers are tested. The results are shown in Table 7.

Table 7

Comparative analysis

It can be seen that 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.

The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection of the present invention. Within the scope.

Claims

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, characterized in that the mass ratio of the polyurethane resin and the mass ratio of the polyurethane resin to the reinforcing fiber are as follows :
The high fiber content fiber reinforced polyurethane rigid foam composite board according to claim 1, wherein the reinforcing fiber is a mixture of any one or more of glass fiber, basalt fiber, carbon fiber, aramid fiber and steel fiber.
The high fiber content fiber reinforced polyurethane rigid foam composite sheet according to claim 1 or 2, wherein the reinforcing fibers are mainly composed of continuous long fibers, and further comprise chopped fibers and fiber mats.
A method for producing a high fiber content fiber reinforced polyurethane rigid foam composite sheet according to claim 3, which is produced by a continuous molding process, and the continuous molding process comprises unwinding long fibers and fiber mats, and injecting polyurethane resin , adding chopped fibers, uniform impregnation, curing, cooling, and fixed length cutting in the crawler laminating machine.
The method for fabricating a high fiber content fiber reinforced polyurethane rigid foam composite sheet according to claim 4, wherein the uniform impregnation is specifically impregnating the polyurethane resin through a high pressure foaming machine, a moving casting device and a corresponding tooling. The surface and interior of the fiber.
The method for manufacturing a high fiber content fiber reinforced polyurethane rigid foam composite sheet according to claim 4, wherein the crawler type laminating machine is composed of a crawler laminating machine and a side stopper, and the side stopper It is fixed on the crawler laminator, and the height and width of the cavity are adjusted according to the size of the stopper.
High fiber content fiber reinforced polyurethane rigid foam composite sheet according to any one of claims 4 to 6 The manufacturing method is characterized in that the high-fiber content fiber-reinforced polyurethane rigid foam composite sheet after the fixed length cutting has a thickness of 10 mm to 120 mm.
The method for preparing a high fiber content fiber reinforced polyurethane rigid foam composite sheet according to any one of claims 4 to 6, characterized in that the high fiber content fiber reinforced polyurethane rigid foam composite sheet after the fixed length cutting has a width of 100 mm. 600mm.
The method for preparing a high fiber content fiber reinforced polyurethane rigid foam composite sheet according to any one of claims 4 to 6, characterized in that the high fiber content fiber reinforced polyurethane rigid foam composite sheet after the fixed length cutting has a density of 200 kg/ m 3 to 2000 kg/m 3 .