CN114773817B - Glass fiber reinforced plastic pultrusion profile and preparation method thereof - Google Patents
Glass fiber reinforced plastic pultrusion profile and preparation method thereof Download PDFInfo
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- CN114773817B CN114773817B CN202210701287.5A CN202210701287A CN114773817B CN 114773817 B CN114773817 B CN 114773817B CN 202210701287 A CN202210701287 A CN 202210701287A CN 114773817 B CN114773817 B CN 114773817B
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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
- 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
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
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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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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Abstract
The invention provides a glass fiber reinforced plastic pultrusion section and a preparation method thereof, wherein the glass fiber reinforced plastic pultrusion section comprises a base material and a reinforcing material: the preparation raw materials of the matrix material comprise the following components in parts by mass: 30-100 parts of unsaturated polyester resin, 0.5-2 parts of unsaturated polyester resin curing agent, 15-55 parts of epoxy resin, 13-50 parts of epoxy curing agent, 0.5-3 parts of release agent, 1-8 parts of low shrinkage agent and 20-60 parts of flame retardant; the reinforcing material comprises (2-4) by volume: 1 and a composite glass fiber biaxial cloth. The transverse mechanical property and the flame retardant property of the glass fiber reinforced plastic pultrusion section are remarkably improved, the mechanical property meets the requirement of the CTI STD-137 standard of the glass fiber reinforced plastic for the cooling tower, the flame retardant property meets the requirement that the FSI in the ASTM E84 standard is less than or equal to 25, the forming process is good in manufacturability and strong in operability, the section of the pultrusion section is free of cracks, the long-term quality of the glass fiber reinforced plastic pultrusion section in the using process of the glass fiber reinforced plastic cooling tower is guaranteed, and the economy is good.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a glass fiber reinforced plastic pultrusion section and a preparation method thereof.
Background
The cooling tower is a device for cooling a liquid such as water, and water and air flow through the cooling tower to perform heat exchange and mass exchange to lower the temperature of the water and obtain cooling. The early cooling tower is mostly of a reinforced concrete structure, the reinforced concrete structure of the reinforced concrete structure cooling tower needs to be maintained once every 2 years and is subjected to anti-seepage treatment, and in addition, the reinforced concrete structure cooling tower has better corrosion resistance after being subjected to anti-corrosion treatment. After the advent of glass fiber reinforced plastic, it was quickly used in cooling towers because of its light weight, high strength, corrosion resistance, designability, beautiful appearance and moderate cost.
At present, a main frame of the glass fiber reinforced plastic cooling tower adopts a pultruded glass fiber reinforced plastic profile which is light in weight, high in strength, corrosion resistant, maintenance-free and aging resistant, is particularly suitable for the top end of a building structure and the cooling tower of a chemical industry enterprise with serious corrosion, and obtains remarkable economic and social benefits.
Compared with other glass fiber reinforced plastic molding processes, the pultruded glass fiber reinforced plastic profile has extremely excellent longitudinal mechanical properties due to high longitudinal fiber content, but has lower transverse mechanical properties, and cannot meet various mechanical property requirements of the glass fiber reinforced plastic structure for the cooling tower in the CTI STD-137 standard; on the other hand, when the glass fiber reinforced plastic section bar is applied in the field of buildings, certain flame retardant requirements need to be met, and the existing pultruded glass fiber reinforced plastic section bar has poor flame retardant performance. Therefore, there is a need to solve the above problems to facilitate the use of glass fiber reinforced plastic pultrudates in cooling towers.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the glass fiber reinforced plastic pultrusion section and the preparation method thereof, which effectively improve the transverse mechanical property and the flame retardant property of the glass fiber reinforced plastic pultrusion section, ensure that the mechanical property of the glass fiber reinforced plastic pultrusion section meets the requirement of the CTI STD-137 standard of the glass fiber reinforced plastic for the cooling tower, the flame retardant property meets the requirement that the FSI in the ASTM E84 standard is less than or equal to 25, the forming process has good manufacturability and strong operability, the section of the pultrusion section has no crack, the long-term quality of the glass fiber reinforced plastic cooling tower in the using process is ensured, and the economy is good.
In order to solve the above problems, an aspect of the present invention provides a glass fiber reinforced plastic pultruded profile comprising a base material and a reinforcing material:
the preparation raw materials of the matrix material comprise the following components in parts by mass:
30-100 parts of unsaturated polyester resin, 0.5-2 parts of unsaturated polyester resin curing agent, 15-55 parts of epoxy resin, 13-50 parts of epoxy curing agent, 0.5-3 parts of release agent, 1-8 parts of low shrinkage agent and 20-60 parts of flame retardant;
the reinforcing material comprises (2-4) by volume: 1 and a composite glass fiber biaxial cloth.
Preferably, the preparation raw materials of the base material comprise the following components in parts by mass:
60-70 parts of unsaturated polyester resin, 1-1.4 parts of unsaturated polyester resin curing agent, 30-40 parts of epoxy resin, 27-36 parts of epoxy curing agent, 1-2 parts of release agent, 3-5 parts of low shrinkage agent and 32-45 parts of flame retardant.
Preferably, the volume of the reinforcing material accounts for 55-60% of the volume of the glass fiber reinforced plastic pultruded profile.
Preferably, the mass ratio of the unsaturated polyester resin to the epoxy resin is (1.5-2.4): 1.
preferably, the composite glass fiber biaxial cloth comprises: biaxial cloth, chopped glass fiber yarn and glass fiber surface felt which are composed of glass fiber yarn in the 0-degree direction and glass fiber yarn in the 90-degree direction;
the surface density of the composite glass fiber biaxial cloth is 920-950g/m 2 (ii) a The surface density of the 0-degree direction glass fiber yarn is 120-200g/m 2 (ii) a The surface density of the glass fiber yarn in the 90-degree direction is 470-550g/m 2 (ii) a The surface density of the chopped glass fiber yarn is 200-250g/m 2 (ii) a The surface density of the glass fiber surface felt is 30-50g/m 2 。
Preferably, the 90 ° direction glass fiber yarns comprise 12% to 15% by volume of the reinforcing material.
Preferably, the flame retardant comprises phosphate, antimony trioxide and aluminum hydroxide, and the mass ratio of the phosphate to the antimony trioxide to the aluminum hydroxide is 2: (0.5-1.5): (4-8).
Preferably, the raw materials for preparing the matrix material further comprise the following components in parts by mass:
0.5-1.5 parts of anti-ultraviolet aging agent and 1-2 parts of color paste.
Preferably, the unsaturated polyester resin is o-benzene type unsaturated polyester resin, the solid content of the o-benzene type unsaturated polyester resin is 60-65%, the acid value is 16-27mgKOH/g, and the viscosity at 25 ℃ is 500-700m Pa.s;
the unsaturated polyester resin curing agent is peroxide, and comprises TBPB, BPO and BPPD;
the epoxy resin is E51 type epoxy resin, the viscosity of the epoxy resin at 25 ℃ is 11000-14000 mPa & s, and the epoxy equivalent is 184-194 g/mol;
the epoxy curing agent is an anhydride curing agent, the viscosity of the epoxy curing agent at 25 ℃ is 100-300m Pa & s, and the acid value is 500-700 mgKOH/g;
the release agent is an internal release agent, and is one or a combination of a plurality of stearate release agents, lipid release agents and organic phosphorus compound release agents;
the low shrinkage agent is one or a combination of a plurality of polar low shrinkage agents and nonpolar low shrinkage agents, and the low shrinkage agent is one or a combination of a plurality of PE powder, polystyrene, saturated polyester and polyvinyl acetate;
the ultraviolet aging resistant agent is UV-531.
The invention also provides a preparation method of the glass fiber reinforced plastic pultrusion section, which comprises the following steps:
s1, mixing the preparation raw materials of the base material to obtain a mixed glue solution;
s2, impregnating the reinforcing material with the mixed glue solution;
and S3, pultrusion is carried out on the reinforcing material impregnated with the mixed glue solution, and the glass fiber reinforced plastic pultrusion section is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the glass fiber reinforced plastic pultrusion section, the unsaturated polyester resin and the epoxy resin are compounded in the base material, the unsaturated polyester resin is low in price, good in technological performance, general in mechanical performance, relatively sharp in curing exothermic peak, large in curing shrinkage rate, and prone to generating cracks for thick-wall pultrusion sections. The epoxy resin has excellent comprehensive mechanical property, a gentle curing exothermic peak and small curing shrinkage rate, is not easy to generate cracks for thick-wall pultruded profiles, but has higher price and poor process performance, and the pultrusion speed is lower when the pultruded profiles are prepared, so the mechanical property of the pultruded profiles can be obviously improved, the curing characteristic of unsaturated polyester resin can be improved, and the section cracks of the pultruded profiles can be eliminated after the epoxy resin and the pultruded profiles are compounded in a proper proportion.
2. The reinforced material of the glass fiber reinforced plastic pultrusion section bar adopts the composite glass fiber biaxial cloth, the composite glass fiber biaxial cloth is an integrated structure formed by connecting the glass fiber biaxial cloth with other types of glass fiber products such as felt, yarn and the like in a bonding or sewing mode, compared with the glass fiber products such as single and separated cloth, felt and the like, the composite glass fiber biaxial cloth has more regular structure, is easy to be fully paved and difficult to curl, and has better uniformity when being combined with resin materials, thereby improving the mechanical property of the glass fiber reinforced plastic pultrusion section bar, and compared with the uniaxial cloth, the adoption of the biaxial cloth has better manufacturability, faster production speed in operation and easier control. Furthermore, the composite glass fiber biaxial cloth comprises glass fiber biaxial cloth, chopped glass fiber yarns and a glass fiber surface felt, wherein the chopped glass fiber yarns can enhance the uniformity of resin impregnation and improve the permeability of the resin impregnation, so that the mechanical performance of the product is improved; the surface felt can form a resin-rich layer on the surface of the product, prevent moisture from being absorbed into the product, corrode glass fiber, improve the ultraviolet resistance of the product and prolong the service life of the product; the application further uses a surfacing mat made of glass fibers, which does not contain other organic matter compared to other types of fibers, such as polyester fibers, and does not affect the flame retardant properties of the composite material. The invention further reasonably designs the surface density of each glass fiber product in the composite glass fiber biaxial cloth and limits the content of the glass fiber yarns in the 90-degree direction, thereby better improving the transverse mechanical property of the pultruded profile.
3. The glass fiber reinforced plastic pultrusion section bar adopts the synergistic flame retardant consisting of the phosphate, the antimony trioxide and the aluminum hydroxide, optimizes the proportional relation of the phosphate, the antimony trioxide and the aluminum hydroxide, can obviously improve the flame retardant property of the glass fiber reinforced plastic pultrusion section bar under the synergistic action of the three flame retardants, reduces the dosage of the flame retardant, ensures that the flame retardant meets the requirement that the FSI in the ASTM E84 standard is less than or equal to 25, and simultaneously has the minimum influence on the mechanical property of the glass fiber reinforced plastic pultrusion section bar.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the present invention provides a glass fiber reinforced plastic pultruded profile comprising a base material and a reinforcing material:
the preparation raw materials of the matrix material comprise the following components in parts by mass:
30-100 parts of unsaturated polyester resin, 0.5-2 parts of unsaturated polyester resin curing agent, 15-55 parts of epoxy resin, 13-50 parts of epoxy curing agent, 0.5-3 parts of release agent, 1-8 parts of low shrinkage agent and 20-60 parts of flame retardant;
the reinforcing material comprises (2-4) by volume: 1 and a composite glass fiber biaxial cloth.
The composite glass fiber biaxial cloth refers to the composite of the glass fiber biaxial cloth and other types of glass fiber products, and can be the composite of chopped glass fiber yarns for example; compounding refers to the bonding together of different types of fiberglass materials by gluing or sewing to form an integral structure. The glass fiber biaxial cloth is formed by sewing two layers of glass fiber yarns in different directions through chemical fiber yarns. Specifically, the glass fiber biaxial cloth may be, for example, a cloth stitch-bonded by two layers of glass fiber yarns of 0 ° and 90 °, or a cloth stitch-bonded by other two different angle fiber yarns.
According to the glass fiber reinforced plastic pultrusion section, the unsaturated polyester resin and the epoxy resin are compounded in the base material, the unsaturated polyester resin is low in price, good in technological performance, general in mechanical performance, relatively sharp in curing exothermic peak, large in curing shrinkage rate, and prone to generating cracks for thick-wall pultrusion sections. The epoxy resin has excellent comprehensive mechanical property, a gentle curing exothermic peak and small curing shrinkage rate, is not easy to generate cracks for thick-wall pultruded profiles, but has higher price and poor process performance, and the pultrusion speed is lower when the pultruded profiles are prepared, so that the mechanical property of the pultruded profiles can be obviously improved, the curing property of unsaturated polyester resin can be improved, and the section cracks of the pultruded profiles can be eliminated after the epoxy resin and the pultruded profiles are compounded in a proper proportion. The reinforced material adopts composite glass fiber biaxial cloth, the composite glass fiber biaxial cloth is formed by connecting the glass fiber biaxial cloth with other types of glass fiber products such as felt, yarn and the like in a bonding or sewing mode and the like, compared with the glass fiber products such as single and separated cloth and felt, the composite glass fiber biaxial cloth has more regular structure, is easy to be fully paved and not easy to curl, has better uniformity when being combined with resin materials, thereby improving the mechanical property of the glass fiber reinforced plastic pultrusion section bar, and compared with the biaxial cloth, the composite glass fiber biaxial cloth has better manufacturability, has higher production speed in operation and is easier to control.
Preferably, the preparation raw materials of the base material comprise the following components in parts by mass:
60-70 parts of unsaturated polyester resin, 1-1.4 parts of unsaturated polyester resin curing agent, 30-40 parts of epoxy resin, 27-36 parts of epoxy curing agent, 1-2 parts of release agent, 3-5 parts of low shrinkage agent and 32-45 parts of flame retardant.
Preferably, the volume of the reinforcing material accounts for 55-60% of the volume of the glass fiber reinforced plastic pultruded profile.
Preferably, the mass ratio of the unsaturated polyester resin to the epoxy resin is (1.5-2.4): 1.
through a great amount of experiments and trials of the inventor, when the proportion of the unsaturated polyester resin and the epoxy resin is controlled within the range, the mechanical property of the glass fiber reinforced plastic pultruded profile can be better improved, and the fracture cracks of the pultruded profile can be eliminated.
Preferably, the reinforcing material comprises a volume ratio of 3:1 and a composite glass fiber biaxial cloth.
Preferably, the composite glass fiber biaxial cloth comprises: biaxial cloth, chopped glass fiber yarn and glass fiber surface felt which are composed of 0-degree direction glass fiber yarn and 90-degree direction glass fiber yarn.
The composite glass fiber biaxial cloth comprises glass fiber biaxial cloth, chopped glass fiber yarns and a glass fiber surface felt, wherein the chopped glass fiber yarns can enhance the uniformity of resin in infiltration and improve the permeability of the resin, so that the mechanical performance of a product is improved; the surface felt can form a resin-rich layer on the surface of the product, prevent moisture from being absorbed into the product, corrode glass fiber, improve the ultraviolet resistance of the product and prolong the service life of the product. The application further uses a surfacing mat made of glass fibers, which does not contain other organic matter compared to other types of fibers, such as polyester fibers, and does not affect the flame retardant properties of the composite material. The biaxial cloth, the chopped glass fiber yarn and the glass fiber surface felt which are composed of the glass fiber yarns in the directions of 0 degrees and 90 degrees are compounded into 3 types of fiber products, the biaxial cloth, the chopped yarn and the glass fiber surface felt are compounded into a whole by gluing or sewing, and compared with the cloth, the felt and the yarn which are separated independently, the biaxial cloth, the chopped yarn and the glass fiber surface felt have the advantages of more regular structure, easy full spreading, difficult curling and better uniformity when being combined with a resin material.
Preferably, the areal density of the composite glass fiber biaxial cloth is 920- 2 The surface density of the 0-degree direction glass fiber yarn is 120-200g/m 2 (ii) a The surface density of the glass fiber yarn in the 90-degree direction is 470-550g/m 2 (ii) a The surface density of the chopped glass fiber yarn is 200-250g/m 2 (ii) a The surface density of the glass fiber surface felt is 30-50g/m 2 。
The invention can better improve the transverse mechanical property of the pultruded profile by further reasonably designing the surface density of each glass fiber product in the composite glass fiber biaxial cloth.
Preferably, in the composite glass fiber biaxial cloth, the 90-degree-direction glass fiber yarns account for 12-15% of the volume content of the reinforcing material. By further limiting the content of the glass fiber yarn in the 90 ° direction to the above ratio, the transverse mechanical properties of the glass fiber reinforced plastic profile can be further improved.
Preferably, the flame retardant comprises phosphate, antimony trioxide and aluminum hydroxide, and the mass ratio of the phosphate to the antimony trioxide to the aluminum hydroxide is 2: (0.5-1.5): (4-8); more preferably, the mass ratio of the phosphate to the antimony trioxide to the aluminum hydroxide is 2: 1: 6.
the invention adopts the synergistic flame retardant consisting of the phosphate, the antimony trioxide and the aluminum hydroxide, optimizes the proportional relation of the three flame retardants, can obviously improve the flame retardant property of the glass fiber reinforced plastic pultrusion section under the synergistic action of the three flame retardants, reduces the dosage of the flame retardant, ensures that the flame retardant meets the requirement that the FSI in the ASTM E84 standard is less than or equal to 25, and simultaneously has the minimum influence on the mechanical property of the glass fiber reinforced plastic pultrusion section.
Preferably, the raw materials for preparing the base material also comprise the following components in parts by mass:
0.5-1.5 parts of anti-ultraviolet aging agent and 1-2 parts of color paste.
Preferably, the unsaturated polyester resin is o-benzene type unsaturated polyester resin, the solid content of the o-benzene type unsaturated polyester resin is 60-65%, the acid value is 16-27mgKOH/g, and the viscosity at 25 ℃ is 500-700 mPa.s.
Preferably, the unsaturated polyester resin curing agent is a peroxide, the unsaturated polyester resin curing agent comprises TBPB, BPO and BPPD; TBPB tert-butyl peroxybenzoate; BPO, i.e. dibenzoyl peroxide; BPPD is bis (2-phenoxyethyl) peroxydicarbonate.
Preferably, the epoxy resin is E51 type epoxy resin, the viscosity of the epoxy resin at 25 ℃ is 11000-14000m Pa.s, and the epoxy equivalent is 184-194 g/mol.
Preferably, the epoxy curing agent is an anhydride curing agent, the viscosity of the epoxy curing agent at 25 ℃ is 100-300 mPa.s, and the acid value is 500-700 mgKOH/g.
Preferably, the release agent is an internal release agent, and the release agent is one or a combination of more of a stearate release agent, a lipid release agent and an organic phosphorus compound release agent.
Preferably, the low shrinkage agent is one or a combination of several of polar low shrinkage agent and nonpolar low shrinkage agent, and the low shrinkage agent is one or a combination of several of PE powder, polystyrene, saturated polyester and polyvinyl acetate.
Preferably, the anti-ultraviolet aging agent is UV-531, and the main component is 2-hydroxy-4-n-octoxy benzophenone.
Preferably, the purity of the antimony trioxide is more than or equal to 99.8 percent.
Preferably, the viscosity of the phosphoric acid ester is 15 mPa.s at 25 ℃.
Preferably, the glass fibers are alkali-free glass fibers.
Preferably, the glass fiber is one or a mixture of glass fibers with specifications of 9600tex, 4800tex and 2400 tex.
The invention also provides a preparation method of the glass fiber reinforced plastic pultrusion section, which comprises the following steps:
s1, mixing the preparation raw materials of the base material to obtain a mixed glue solution;
s2, impregnating the reinforcing material with the mixed glue solution;
and S3, pultrusion is carried out on the reinforcing material impregnated with the mixed glue solution, and the glass fiber reinforced plastic pultrusion section is obtained.
The starting materials used in the following examples are all commercially available.
Example 1
This example is a channel glass fiber reinforced plastic pultrudate of size 152.4 x 43 x 6.4 comprising a matrix material and a reinforcement material, the volume of the reinforcement material being 55% of the glass fiber reinforced plastic pultrudate.
The preparation raw materials of the matrix material comprise the following components in parts by mass:
60 parts of unsaturated polyester resin 1008A, 0.24 part of BPPD, 0.6 part of BPO, 0.18 part of TBPB, 0.40 part of E51 type epoxy resin CYD-12840 parts, 91036 part of epoxy curing agent JHY, 1 part of release agent, 2 parts of PE powder, 2 parts of saturated polyester, 10 parts of phosphate ester, 5 parts of antimony trioxide, 30 parts of aluminum hydroxide, UV-5311 parts and 1 part of color paste.
Wherein the solid content of the unsaturated polyester resin is 62 percent, the acid value is 19mgKOH/g, and the viscosity at 25 ℃ is 550 mPa.s; the viscosity of the epoxy resin at 25 ℃ is 12000m Pa.s, and the epoxy equivalent is 190 g/mol; the viscosity of the epoxy curing agent at 25 ℃ is 150m Pa.s, and the acid value is 600 mgKOH/g;
the reinforcing material is composed of 9600tex alkali-free glassThe surface density of the glass fiber yarn is 940g/m 2 The ratio of the two to the composite glass fiber biaxial cloth of (3) is 3: 1. The composite glass fiber biaxial cloth consists of 0-degree-direction glass fiber yarns, 90-degree-direction glass fiber yarns, chopped glass fiber yarns and a glass fiber surface felt; wherein the surface density of the glass fiber yarn in the 0-degree direction is 170g/m 2 (ii) a The surface density of the glass fiber yarn in the 90-degree direction is 500g/m 2 (ii) a The chopped glass fiber yarn has an areal density of 230g/m 2 (ii) a The surface density of the glass fiber surface felt is 40g/m 2 The 90 ° direction glass fiber yarn accounted for 13.5% of the reinforcing material volume content.
The preparation method of the glass fiber reinforced plastic pultruded profile of the embodiment comprises the following steps:
s1, putting the weighed preparation raw materials of the base material into a resin barrel, and stirring for 10-15 minutes by using a high-speed stirrer to obtain a mixed glue solution;
s2, introducing the mixed glue solution into a resin glue tank, and fully impregnating the glass fiber yarns and the composite glass fiber biaxial cloth;
and S3, starting a pultrusion machine, forming the reinforced material garbage impregnated with the mixed glue solution, and finally cutting at a fixed length to obtain the glass fiber reinforced plastic pultrusion section.
Example 2
This example is a channel glass reinforced plastic pultrudate of size 152.4 x 43 x 6.4 comprising a matrix material and a reinforcement material, the volume of the reinforcement material being 57% of the glass reinforced plastic pultrudate.
The preparation raw materials of the matrix material comprise the following components in parts by mass:
70 parts of unsaturated polyester resin 1008A, 0.28 part of BPPD, 0.7 part of BPO, 0.21 part of TBPB, 0.30 part of E51 type epoxy resin CYD-12830 parts, JHY 91027 parts of epoxy curing agent, 1 part of release agent, 3 parts of PE powder, 2 parts of polyvinyl acetate, 8 parts of phosphate ester, 4 parts of antimony trioxide, 25 parts of aluminum hydroxide, 5311 parts of UV-light and 1 part of color paste.
Wherein the solid content of the unsaturated polyester resin is 62%, the acid value is 19mgKOH/g, and the viscosity at 25 ℃ is 550 mPa.s; the viscosity of the epoxy resin at 25 ℃ is 12000m Pa s, and the epoxy equivalent is 190 g/mol; the viscosity of the epoxy curing agent at 25 ℃ is 150m Pa.s, and the acid value is 600 mgKOH/g;
the reinforcing material is formed by alkali-free glass fiber yarns with the specification of 9600tex, and the surface density of the reinforcing material is 940g/m 2 The ratio of the two to the composite glass fiber biaxial cloth of (1) was 3.11: 1. The composite glass fiber biaxial cloth consists of 0-degree-direction glass fiber yarns, 90-degree-direction glass fiber yarns, chopped glass fiber yarns and a glass fiber surface felt; wherein the surface density of the glass fiber yarn in the 0-degree direction is 160g/m 2 (ii) a The areal density of the glass fiber yarn in the 90 DEG direction was 520g/m 2 (ii) a The chopped glass fiber yarn had an areal density of 210g/m 2 (ii) a The surface density of the glass fiber surface felt is 50g/m 2 The 90 ° direction glass fiber yarn accounted for 13.6% of the reinforcing material volume content.
The preparation method of the glass fiber reinforced plastic pultruded profile of the embodiment comprises the following steps:
s1, putting the weighed preparation raw materials of the base material into a resin barrel, and stirring for 10-15 minutes by using a high-speed stirrer to obtain a mixed glue solution;
s2, introducing the mixed glue solution into a resin glue tank, and fully impregnating the glass fiber yarns and the composite glass fiber biaxial cloth;
and S3, starting a pultrusion machine, forming the reinforced material garbage impregnated with the mixed glue solution, and finally cutting at a fixed length to obtain the glass fiber reinforced plastic pultrusion section.
Example 3
This example is a channel glass reinforced plastic pultruded profile of size 152.4 x 43 x 6.4 comprising a matrix material and a reinforcement material, the volume of reinforcement material comprising 60% of the glass reinforced plastic pultruded profile.
The preparation raw materials of the matrix material comprise the following components in parts by mass:
65 parts of unsaturated polyester resin 1008A, 0.26 part of BPPD, 0.65 part of BPO, 0.2 part of TBPB, E51 type epoxy resin CYD-12835 parts, epoxy curing agent JHY 91032 parts, 2 parts of release agent, 2 parts of PE powder, 1 part of polyvinyl acetate, 12 parts of phosphate ester, 6 parts of antimony trioxide, 36 parts of aluminum hydroxide, UV-5310.5 parts and 2 parts of color paste.
Wherein the solid content of the unsaturated polyester resin is 62%, the acid value is 19mgKOH/g, and the viscosity at 25 ℃ is 550 mPa.s; the viscosity of the epoxy resin at 25 ℃ is 12000m Pa.s, and the epoxy equivalent is 190 g/mol; the viscosity of the epoxy curing agent at 25 ℃ is 150m Pa.s, and the acid value is 600 mgKOH/g;
the reinforcing material is composed of alkali-free glass fiber yarns with the specification of 9600tex and the surface density of 930g/m 2 The ratio of the two to the composite glass fiber biaxial cloth of (1) was 3.33: 1. The composite glass fiber biaxial cloth consists of glass fiber yarns in 0-degree directions, glass fiber yarns in 90-degree directions, chopped glass fiber yarns and a glass fiber surface felt; wherein the surface density of the glass fiber yarn in the 0-degree direction is 180g/m 2 (ii) a The surface density of the glass fiber yarn in the 90-degree direction is 480g/m 2 (ii) a The chopped glass fiber yarn has an areal density of 230g/m 2 (ii) a The surface density of the glass fiber surface felt is 40g/m 2 The 90-degree direction glass fiber yarn accounts for 12% of the volume content of the glass fiber reinforced plastic pultrusion section.
The preparation method of the glass fiber reinforced plastic pultruded profile of the embodiment comprises the following steps:
s1, putting the weighed preparation raw materials of the base material into a resin barrel, and stirring for 10-15 minutes by using a high-speed stirrer to obtain a mixed glue solution;
s2, introducing the mixed glue solution into a resin glue tank, and fully impregnating the glass fiber yarns and the composite glass fiber biaxial cloth;
and S3, starting a pultrusion machine, forming the reinforced material garbage impregnated with the mixed glue solution, and finally cutting at a fixed length to obtain the glass fiber reinforced plastic pultrusion section.
Example 4
The difference between the glass fiber reinforced plastic pultruded profile of this example and example 1 is that the raw materials for preparing the matrix material comprise 80 parts of unsaturated polyester resin 1008A and 20 parts of E51 type epoxy resin, and the preparation method and the rest raw materials are the same as those of example 1.
Example 5
The difference between the glass fiber reinforced plastic pultruded profile of this example and example 1 is that in the raw materials for preparing the base material, 60 parts of aluminum hydroxide is used as the flame retardant, and the preparation method and other raw materials are the same as those in example 1.
Example 6
The difference between the glass fiber reinforced plastic pultruded profile of this example and example 1 is that the flame retardant in the base material preparation raw materials was 5 parts of phosphate, 10 parts of antimony trioxide, and 40 parts of aluminum hydroxide, and the preparation method and other preparation raw materials were the same as example 1.
Example 7
The difference between the glass fiber reinforced plastic pultrusion section of the embodiment and the embodiment 1 is that in the reinforced material, the composite biaxial cloth cover density is 940g/m 2 The areal density of the glass fiber yarn in the 0 ℃ direction was 340g/m 2 (ii) a The surface density of the glass fiber yarn in the 90-degree direction is 340g/m 2 (ii) a The area density of the chopped glass fiber yarn is 220g/m 2 (ii) a The surface density of the glass fiber surface felt is 40g/m 2 The preparation method and other preparation raw materials are the same as those in example 1.
Comparative example
The difference between the glass fiber reinforced plastic pultruded profile of the comparative example and the example 1 is that the reinforcing material adopts alkali-free glass fiber yarn, biaxial cloth and glass fiber surface felt which are separated and not compounded into a whole, the areal density of the three fiber materials is the same as that in the example 1, and the preparation method and other preparation raw materials are the same as that in the example 1.
Determination of performance of glass fiber reinforced plastic pultruded profile
The mechanical properties, flame retardant properties and aging resistance of the glass fiber reinforced plastic pultruded profiles obtained in the above examples and comparative examples were measured. Tensile strength test method reference standard ASTM D638; compressive strength test method reference is made to standard ASTM D6641; flexural strength test method reference standard ASTM D790; short beam shear strength test method reference standard ASTM D2344; load bearing strength test method reference standard ASTM D953; notched impact strength test method reference standard ASTM D256; the flame spread index test method is referred to standard ASTM E84. The test results are shown in table 1 below. As can be seen from the following experimental results, compared with the comparative examples, the glass fiber reinforced plastic pultrusion sections of the examples of the application have better mechanical property and flame retardant property. Compared with the embodiment 1, the embodiment 4 has different proportions of unsaturated polyester resin and epoxy resin, but the mechanical properties of the glass fiber reinforced plastic pultruded profile of the embodiment 4 are inferior to the embodiment 1, especially the transverse compression strength and the bearing strength, and the longitudinal short beam shear strength is lower; the flame retardant of the embodiment 5 does not adopt a synergistic flame retardant, the flame retardant performance of the glass fiber reinforced plastic extruded section can meet the requirement, but in order to obtain similar flame retardant effect, the amount of the flame retardant which needs to be added is larger, so that the mechanical performance of the glass fiber reinforced plastic extruded section is negatively influenced, and the mechanical performance of the glass fiber reinforced plastic extruded section is greatly reduced compared with that of the embodiment 1; the flame retardant of the embodiment 6 adopts the synergistic flame retardant, but the proportions of the three flame retardants are different from those of the embodiment 1, the flame retardant performance of the glass fiber reinforced plastic pultrusion section can meet the requirement, but in order to obtain similar flame retardant effect, the amount of the flame retardant which needs to be added is larger, so that the mechanical performance of the glass fiber reinforced plastic pultrusion section is negatively affected, and the mechanical performance of the glass fiber reinforced plastic pultrusion section is greatly reduced compared with that of the embodiment 1; the areal densities of the various articles in the composite biaxial cloth in example 7 were different from those in example 1, and the compressive strength and load bearing strength were inferior to those in example 1. Wherein, the examples 1-3 are preferred embodiments, the mechanical property of the glass fiber reinforced plastic pultrusion section prepared in the examples 1-3 meets the requirement of the CTI STD-137 standard of the glass fiber reinforced plastic for the cooling tower, and the flame retardant property meets the requirement that the FSI is less than or equal to 25 in the ASTM E84 standard.
TABLE 1
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The glass fiber reinforced plastic pultrusion section comprises a base material and a reinforcing material, and is characterized in that:
the preparation raw materials of the matrix material comprise the following components in parts by mass:
30-100 parts of unsaturated polyester resin, 0.5-2 parts of unsaturated polyester resin curing agent, 15-55 parts of epoxy resin, 13-50 parts of epoxy curing agent, 0.5-3 parts of release agent, 1-8 parts of low shrinkage agent and 20-60 parts of flame retardant;
the reinforcing material comprises (2-4) by volume: 1, the glass fiber and the composite glass fiber biaxial cloth;
the composite glass fiber biaxial cloth comprises: biaxial cloth, chopped glass fiber yarn and glass fiber surface felt which are composed of glass fiber yarn in the 0-degree direction and glass fiber yarn in the 90-degree direction;
the surface density of the composite glass fiber biaxial cloth is 920-950g/m 2 (ii) a The surface density of the 0-degree direction glass fiber yarn is 120-200g/m 2 (ii) a The surface density of the glass fiber yarn in the 90-degree direction is 470-550g/m 2 (ii) a The surface density of the chopped glass fiber yarn is 200-250g/m 2 (ii) a The surface density of the glass fiber surface felt is 30-50g/m 2 ；
The flame retardant comprises phosphate, antimony trioxide and aluminum hydroxide, wherein the mass ratio of the phosphate to the antimony trioxide to the aluminum hydroxide is 2: (0.5-1.5): (4-8).
2. The glass fiber reinforced plastic pultruded profile according to claim 1, wherein the raw materials for preparing the matrix material comprise the following components in parts by mass:
60-70 parts of unsaturated polyester resin, 1-1.4 parts of unsaturated polyester resin curing agent, 30-40 parts of epoxy resin, 27-36 parts of epoxy curing agent, 1-2 parts of release agent, 3-5 parts of low shrinkage agent and 32-45 parts of flame retardant.
3. The glass fiber reinforced plastic pultruded profile according to claim 1, wherein:
the volume of the reinforcing material accounts for 55-60% of the volume of the glass fiber reinforced plastic pultrusion section.
4. A glass fibre reinforced plastic pultruded profile according to claim 2, wherein:
the mass ratio of the unsaturated polyester resin to the epoxy resin is (1.5-2.4): 1.
5. a glass fibre reinforced plastic pultruded profile according to claim 1, wherein:
the 90-degree-direction glass fiber yarns account for 12-15% of the volume content of the reinforcing material.
6. The glass fiber reinforced plastic pultruded profile according to claim 1, wherein the raw materials for preparing the matrix material further comprise the following components in parts by mass:
0.5-1.5 parts of anti-ultraviolet aging agent and 1-2 parts of color paste.
7. A glass fibre reinforced plastic pultruded profile according to claim 6, wherein:
the unsaturated polyester resin is o-benzene type unsaturated polyester resin, the solid content of the o-benzene type unsaturated polyester resin is 60-65%, the acid value is 16-27mgKOH/g, and the viscosity at 25 ℃ is 500-700m Pa.s;
the unsaturated polyester resin curing agent is peroxide, and comprises TBPB, BPO and BPPD;
the epoxy resin is E51 type epoxy resin, the viscosity of the epoxy resin at 25 ℃ is 11000-14000m Pa & s, and the epoxy equivalent is 184-194 g/mol;
the epoxy curing agent is an anhydride curing agent, the viscosity of the epoxy curing agent at 25 ℃ is 100-300m Pa & s, and the acid value is 500-700 mgKOH/g;
the release agent is an internal release agent, and is one or a combination of a plurality of stearate release agents, lipid release agents and organic phosphorus compound release agents;
the low shrinkage agent is one or a combination of a plurality of polar low shrinkage agents and nonpolar low shrinkage agents, and the low shrinkage agent is one or a combination of a plurality of PE powder, polystyrene, saturated polyester and polyvinyl acetate;
the anti-ultraviolet aging agent is UV-531.
8. A method of producing a glass fibre reinforced plastic pultruded profile according to any of claims 1 to 7, comprising the steps of:
s1, mixing the preparation raw materials of the base material to obtain a mixed glue solution;
s2, impregnating the reinforced material with the mixed glue solution;
and S3, pultrusion is carried out on the reinforcing material impregnated with the mixed glue solution, and the glass fiber reinforced plastic pultrusion section is obtained.
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| JP2004189583A (en) * | 2002-10-15 | 2004-07-08 | Nippon Electric Glass Co Ltd | Glass composition, and glass fiber |
| CN1560134A (en) * | 2004-02-24 | 2005-01-05 | 天津市金锚科技发展有限公司 | Preparing composite of modifing glass fiber reinforced plastics pultrusion section bar and preparation method thereof |
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| CN110628194A (en) * | 2019-09-17 | 2019-12-31 | 北玻院(滕州)复合材料有限公司 | Glass fiber reinforced plastic pultrusion section for cooling tower and preparation method thereof |
| KR20200042548A (en) * | 2018-10-15 | 2020-04-24 | (재)한국건설생활환경시험연구원 | Composition for lighting panel having translucenc and anti flammable properties |
| CN114015178A (en) * | 2021-12-03 | 2022-02-08 | 江苏澳兰德新材料科技有限公司 | Low-temperature-resistant glass fiber reinforced plastic pultrusion section and preparation method thereof |
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| JP2004189583A (en) * | 2002-10-15 | 2004-07-08 | Nippon Electric Glass Co Ltd | Glass composition, and glass fiber |
| CN1560134A (en) * | 2004-02-24 | 2005-01-05 | 天津市金锚科技发展有限公司 | Preparing composite of modifing glass fiber reinforced plastics pultrusion section bar and preparation method thereof |
| JP2008055772A (en) * | 2006-08-31 | 2008-03-13 | Kyocera Chemical Corp | Manufacturing process of pultrusion-molded product |
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