CN110746738B - Phenolic resin foaming prepreg, preparation method and application thereof - Google Patents

Phenolic resin foaming prepreg, preparation method and application thereof Download PDF

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Publication number
CN110746738B
CN110746738B CN201911030141.7A CN201911030141A CN110746738B CN 110746738 B CN110746738 B CN 110746738B CN 201911030141 A CN201911030141 A CN 201911030141A CN 110746738 B CN110746738 B CN 110746738B
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phenolic resin
foaming
prepreg
fiber reinforced
reinforced material
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CN110746738A (en
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周洲
吴宏伟
袁利康
熊俊清
林立钿
王明星
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Zhuzhou Times New Material Technology Co Ltd
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Zhuzhou Times New Material Technology Co Ltd
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    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
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Abstract

The invention discloses a phenolic resin foaming prepreg, a preparation method and application thereof, wherein phenolic resin and a foaming agent are fully stirred to prepare phenolic resin glue solution, and the foaming agent takes thermoplastic polymer as a shell to wrap volatile hydrocarbon; immersing the fiber reinforced material into phenolic resin glue solution for glue dipping; baking the fiber reinforced material after gum dipping, and foaming and curing to obtain the phenolic resin foaming prepreg. The foaming prepreg is a raw material for manufacturing floors and air ducts in the field of rail transit, has the characteristics of flame retardance, heat preservation and low density, can meet the requirements of light weight, high flame retardance and environmental protection of rail transit vehicles, can effectively improve the toughness and mechanical properties of products, has excellent fatigue performance, and can meet the service requirement of rail transit for 30 years.

Description

Phenolic resin foaming prepreg, preparation method and application thereof
Technical Field
The invention relates to a material for the field of rail transit, in particular to a phenolic resin foaming prepreg, a preparation method and application thereof.
Background
The existing floor and duct materials in the rail transit field are mainly aluminum alloy materials, have the characteristics of large mass and poor heat insulation, and are difficult to meet the flame retardant requirement of EN45445-3 in flame retardance, and the existing materials cannot meet the existing requirements.
The phenolic resin foaming material is obtained by foaming and curing a foaming phenolic resin mixture, and has good heat insulation, flame retardance and fire resistance. The main component in the foaming phenolic resin mixture is phenolic resin, the phenolic resin is generally synthesized from phenol and formaldehyde under the action of a catalyst, but phenol and formaldehyde residues exist in the phenolic resin due to incomplete reaction, the release of free phenol and free formaldehyde into the air can influence the atmospheric environment and the human health, and the produced prepreg is insufficient in foaming uniformity and stability and has a great influence on the mechanical properties of products.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides a phenolic resin foaming prepreg with flame retardance, heat preservation, low density and excellent mechanical property, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the preparation method of the phenolic resin foaming prepreg comprises the following steps:
s1, fully stirring phenolic resin and a foaming agent to prepare phenolic resin glue solution, wherein the foaming agent takes a thermoplastic polymer as a shell to wrap volatile hydrocarbon;
s2, immersing the fiber reinforced material into the phenolic resin glue solution obtained in the S1 for glue dipping;
s3, baking the fiber reinforced material subjected to gum dipping, and foaming and curing to obtain the phenolic resin foaming prepreg.
Further, the free phenol of the phenolic resin in S1 is 4.0-7.5wt%, the free formaldehyde is less than 1.2wt%, the viscosity is 800-1000cp/25 ℃, the moisture content is 21.5-25.5wt%, the solid content is 66.5-72.5wt%, and the pH value is 8.0-9.0.
Further, the foaming agent in the step S1 is an expandable microsphere foaming agent.
Further, the mass ratio of the phenolic resin to the foaming agent in the S1 is 10:1-13:1.
Further, the fiber reinforced material in S2 is carbon fiber, glass fiber, aramid fiber or polyester fiber.
Further, the surface density of the fiber reinforced material in S2 is 50-400g/m 2 。
Further, the temperature of the baking channel for baking in the step S3 is divided into three sections which are sequentially arranged and respectively are 80-90 ℃,125-140 ℃ and 130-145 ℃.
A phenolic resin foaming prepreg is prepared by the preparation method.
The application of the phenolic resin foaming prepreg comprises the steps of stacking a plurality of layers of phenolic resin foaming prepregs, performing hot pressing and curing to form a fiber reinforced foam board, cutting the fiber reinforced foam board into long strips, overturning for 90 degrees, splicing the long strips into a required width by glue, and then sandwiching the long strips between two layers of glass fiber reinforced plastic panels to prepare the floor product.
The application of the phenolic resin foaming prepreg is that the phenolic resin foaming prepreg is pressed into the air duct board after being stacked in a plurality of layers.
Compared with the prior art, the invention has the beneficial effects that:
the foaming prepreg is a raw material for manufacturing floors and air ducts in the field of rail transit, has the characteristics of flame retardance, heat preservation and low density, and can meet the requirements of light weight, high flame retardance and environmental protection of rail transit vehicles. The hydrocarbon-thermoplastic polymer foaming agent is adopted to be combined with the phenolic resin prepared by the invention in a friendly way, and the toughness and mechanical property of the product can be effectively improved through the low-density fiber reinforced material, the fatigue performance is superior, and the service requirement of rail transit for 30 years can be met.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of the present invention is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The phenolic resin of the invention is an environment-friendly water-soluble resol phenolic resin which is prepared by carrying out addition polycondensation reaction on phenol and formaldehyde under the action of base catalysis, controlling the reaction temperature and the reaction time to reach a target condensation degree (between 4 and 10), adding an aldehyde scavenger to reduce the content of free formaldehyde (formaldehyde which does not participate in the reaction), and then carrying out vacuum dehydration to reach target moisture and viscosity. The aldehyde trapping agent is a urea derivative compound.
The performance parameters of the environment-friendly water-soluble resole are shown in the following table:
wherein, the content of free formaldehyde in the phenolic resin is less than 1.2%, which can effectively reduce the formaldehyde content of the product and improve the environmental protection performance.
In a specific embodiment of the invention, the method for preparing the phenolic resin foamed prepreg comprises the following steps:
(1) Adding phenolic resin and foaming agent into a container, and fully stirring to prepare phenolic resin glue solution.
The foaming agent is hydrocarbon-thermoplastic polymer foaming agent, which takes thermoplastic polymer as a shell to wrap volatile hydrocarbon to form microspheres, and can be commercially available expandable microsphere foaming agent.
After the hydrocarbon-thermoplastic polymer foaming agent is foamed, the foaming particles are 30-200 microns, the foaming uniformity and stability are good, the foaming particles can well exist between fiber reinforced materials and are wrapped by phenolic resin, and the foaming particles are tightly combined with the phenolic resin and the fiber reinforced materials, so that the toughness and fatigue performance of the product are improved. At the same time, the initial foaming temperature is also matched with the curing temperature of the prepreg.
Preferably, the mass ratio of the phenolic resin to the foaming agent is 10:1-13:1. The stirring speed is 30-80r/min, and the stirring time is 15-30min.
(2) And (3) introducing the phenolic resin glue solution obtained in the step (1) into a glue dipping tank, dipping the fiber reinforced material into the phenolic resin glue solution, and continuously dipping.
The fiber reinforcement material can be one of carbon fiber, glass fiber, aramid fiber and polyester fiber, preferably has an areal density of 50-400g/m 2 . Preferably, the mass ratio of the phenolic resin glue solution to the fiber reinforced material is 3.5:1-5:1. Either a chopped strand mat or a continuous fiber mat may be used.
Preferably, a dipping machine is used for controlling the running speed of the fiber reinforced material and the release film (PET film, mainly leading the prepreg to be well molded and transported) to be 2m/min-5m/min, and the interval between the glue squeezing rollers is 0.15-0.3mm.
(3) Baking the impregnated fiber reinforced material, performing preliminary foaming and curing, and then rolling the cut pieces to prepare the phenolic resin foaming prepreg.
Preferably, the temperature of the drying tunnel for baking is divided into three sections which are sequentially arranged, wherein the temperatures are respectively 80-90 ℃,125-140 ℃ and 130-145 ℃. The first section is mainly used for drying the prepreg, and the second section is mainly used for initially curing phenolic resin to reach a certain curing degree.
Preferably, the mass ratio of the phenolic resin to the fiber reinforced material after preliminary foaming and curing is 3:1-4.8:1.
example 1
(1) Adding phenolic resin and commercially available expandable microsphere foaming agent into a container, and fully stirring to prepare phenolic resin glue solution. The mass ratio of the phenolic resin to the foaming agent is 10:1.2. The stirring speed is 30-80r/min, and the stirring time is 15-30min.
(2) And (3) introducing the phenolic resin glue solution obtained in the step (1) into a glue dipping tank, dipping the fiber reinforced material into the phenolic resin glue solution, and continuously dipping. The fiber reinforcement material used is glass fiber. The mass ratio of the phenolic resin glue solution to the fiber reinforced material is 6.6:1. And controlling the running speed of the fiber reinforced material and the release film to be 3m/min by using a gum dipping machine, wherein the distance between the gum squeezing rollers is 0.2mm.
(3) Baking the impregnated fiber reinforced material, performing preliminary foaming and curing, and then rolling the cut pieces to prepare the phenolic resin foaming prepreg. The temperature of the baking channel for baking is divided into three sections which are sequentially arranged and respectively 80-90 ℃,125-140 ℃ and 130-145 ℃. The mass ratio of the phenolic resin to the fiber reinforced material after preliminary foaming and curing is 4.3:1.
The prepared prepreg has the following surface density280g/m 2 The multi-layer stack is further cured by hot pressing to form a fiber reinforced foam board with a required thickness D, the fiber reinforced foam board is cut into strips with a certain width L by adopting cutting equipment, the strips are turned over for 90 degrees, namely the width L is changed into thickness, the thickness D is changed into width, the strips are spliced by glue, a plurality of widths D are spliced into a required width D (which is formed by a plurality of strip widths), the upper surface and the lower surface are brushed with double-component polyurethane glue, glass fiber reinforced plastic panels with the thickness of 1mm are simultaneously attached to the upper surface and the lower surface, the fiber reinforced foam splicing board is clamped in the middle, and a floor product with the thickness of 15mm or 18mm is manufactured by adopting the method. After 1000 ten-thousand tests at a frequency of 60kg per square meter and 3g acceleration per person, namely, 5Hz of 14kN, the product is free from cracking and layering, and the permanent deformation is less than +/-1 mm. At the same time, the floor with 15mm meets the flat pull strength>4.5MPa, flattening strength>4.5Mpa, flexural strength>Mechanical properties such as 60MPa and the like, and the heat conductivity coefficient is less than 0.04W/(m.K).
Example 2
(1) Adding phenolic resin and commercially available expandable microsphere foaming agent into a container, and fully stirring to prepare phenolic resin glue solution. The mass ratio of the phenolic resin to the foaming agent is 10:1.2. The stirring speed is 30-80r/min, and the stirring time is 15-30min.
(2) And (3) introducing the phenolic resin glue solution obtained in the step (1) into a glue dipping tank, dipping the fiber reinforced material into the phenolic resin glue solution, and continuously dipping. The fiber reinforcement material used is glass fiber. The mass ratio of the phenolic resin glue solution to the fiber reinforced material is 4.2:1. And controlling the running speed of the fiber reinforced material and the release film to be 2.5m/min by using a gum dipping machine, wherein the distance between the gum squeezing rollers is 0.18mm.
(3) Baking the impregnated fiber reinforced material, performing preliminary foaming and curing, and then rolling the cut pieces to prepare the phenolic resin foaming prepreg. The temperature of the baking channel for baking is divided into three sections which are sequentially arranged and respectively 80-90 ℃,125-140 ℃ and 130-145 ℃. The mass ratio of the phenolic resin to the fiber reinforced material after preliminary foaming and curing is 2.4:1.
The surface density of the prepared prepreg is 170g/m 2 The multi-layer stacked air duct board with the density of 160 (1+/-10%) kg/m is pressed into an air duct board with the thickness of 10mm 3 The method comprisesThe air duct plate is assembled into an air duct product through splicing. The product meets the highest flame retardant requirements of EN45545-2, R1 and HL3, and has a heat conductivity coefficient of less than 0.04W/(m.K) and a flattening intensity>Flexural Strength 1.5MPa>5MPa, tensile Strength>6MPa。
Example 3
(1) Adding phenolic resin and commercially available expandable microsphere foaming agent into a container, and fully stirring to prepare phenolic resin glue solution. The mass ratio of the phenolic resin to the foaming agent is 10:1.2. The stirring speed is 30-80r/min, and the stirring time is 15-30min.
(2) And (3) introducing the phenolic resin glue solution obtained in the step (1) into a glue dipping tank, dipping the fiber reinforced material into the phenolic resin glue solution, and continuously dipping. The fiber reinforcement material used is polyester fiber. The mass ratio of the phenolic resin glue solution to the fiber reinforced material is 4.7:1. And controlling the running speed of the fiber reinforced material and the release film to be 2.5m/min by using a gum dipping machine, wherein the distance between the gum squeezing rollers is 0.18mm.
(3) Baking the impregnated fiber reinforced material, performing preliminary foaming and curing, and then rolling the cut pieces to prepare the phenolic resin foaming prepreg. The temperature of the baking channel for baking is divided into three sections which are sequentially arranged and respectively 80-90 ℃,125-140 ℃ and 130-145 ℃. The mass ratio of the phenolic resin to the fiber reinforced material after preliminary foaming and curing is 2.7:1.
The surface density of the prepared prepreg is 160g/m 2 The multi-layer stacked air duct board with the density of 160 (1+/-10%) kg/m is pressed into an air duct board with the thickness of 10mm 3 The air duct plate is assembled into an air duct product through splicing. The product meets the flame retardant requirements of EN45545-2, R1 and HL1, and has a heat conductivity coefficient of less than 0.04W/(m.K) and a flattening intensity>Flexural Strength 1.5MPa>5MPa, tensile Strength>6MPa。
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.

Claims (4)

1. The preparation method of the phenolic resin foaming prepreg is characterized by comprising the following steps of:
s1, fully stirring phenolic resin and a foaming agent to prepare phenolic resin glue solution; the free phenol in the phenolic resin is 4.0-7.5wt%, the free formaldehyde is less than 1.2wt%, the viscosity is 800-1000cp/25 ℃, the moisture content is 21.5-25.5wt%, the solid content is 66.5-72.5wt%, and the pH value is 8.0-9.0; the foaming agent takes a thermoplastic polymer as a shell to wrap volatile hydrocarbon; the mass ratio of the phenolic resin to the foaming agent is 10:1-13:1;
s2, immersing the fiber reinforced material into the phenolic resin glue solution obtained in the step S1 for glue dipping; the mass ratio of the phenolic resin glue solution to the fiber reinforced material is 3.5:1-5:1, and the surface density of the fiber reinforced material is 50-400g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The fiber reinforced material is carbon fiber, glass fiber, aramid fiber or polyester fiber;
s3, baking the impregnated fiber reinforced material, and foaming and curing to obtain phenolic resin foaming prepreg; the temperature of the baking channel for baking is divided into three sections which are sequentially arranged and respectively 80-90 ℃,125-140 ℃ and 130-145 ℃.
2. A phenolic resin foamed prepreg prepared by the method of claim 1.
3. The application of the phenolic resin foaming prepreg is characterized in that the phenolic resin foaming prepreg in claim 2 is stacked in multiple layers, hot pressed and cured to form a fiber reinforced foam board, the fiber reinforced foam board is cut into strips, the strips are spliced into a required width by glue after being turned over by 90 degrees, and then the strips are sandwiched by two layers of glass fiber reinforced plastic panels to form a floor product.
4. The use of a phenolic resin foamed prepreg according to claim 2, wherein the phenolic resin foamed prepreg is laminated in a plurality of layers and pressed into an air duct board.
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