CN118480201A - High-heat-resistance high-nail-holding-force glass fiber reinforced plastic pultruded profile and preparation method thereof - Google Patents

High-heat-resistance high-nail-holding-force glass fiber reinforced plastic pultruded profile and preparation method thereof Download PDF

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CN118480201A
CN118480201A CN202410644500.2A CN202410644500A CN118480201A CN 118480201 A CN118480201 A CN 118480201A CN 202410644500 A CN202410644500 A CN 202410644500A CN 118480201 A CN118480201 A CN 118480201A
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glass fiber
reinforced plastic
fiber reinforced
parts
epoxy resin
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曹也文
邢鹏铅
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Suzhou Xuanwei New Materials Co ltd
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Suzhou Xuanwei New Materials Co ltd
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Abstract

The invention belongs to the field of high polymer materials, in particular to the field of C08L63/00, and more particularly relates to a high-heat-resistance high-nail-holding-force glass fiber reinforced plastic pultruded profile and a preparation method thereof. The preparation raw materials of the glass fiber reinforced plastic pultrusion profile comprise glass fiber and liquid epoxy system materials, wherein the liquid epoxy system materials comprise, by mass, 100 parts of epoxy resin, 80-120 parts of anhydride curing agent, 1-3 parts of accelerator, 10-20 parts of internal mold release agent, 5-15 parts of toughening agent and 5-15 parts of filler. The prepared glass fiber reinforced plastic pultrusion profile product has excellent high temperature resistance and higher nail holding power, and is particularly suitable for being applied to the field of door and window profiles.

Description

High-heat-resistance high-nail-holding-force glass fiber reinforced plastic pultruded profile and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, in particular to the field of C08L63/00, and more particularly relates to a high-heat-resistance high-nail-holding-force glass fiber reinforced plastic pultruded profile and a preparation method thereof.
Background
The glass fiber reinforced plastic pultrusion profile is a composite material which is prepared by using glass fiber as a main reinforcing material and resin as an adhesive through pultrusion, and various profiles such as glass fiber reinforced plastic grids, bars, laths, pipes, angle steel, channel steel and the like are continuously pultruded. In the field of door and window profiles, the pultruded glass reinforced plastic profile has the firmness of an aluminum alloy profile and the heat preservation and corrosion resistance of a plastic steel profile, so that the pultruded glass reinforced plastic profile is considered as a fifth generation door and window profile after wood, steel, aluminum and plastic.
The most used resin in the traditional production of pultruded glass fibre reinforced plastic profiles is an unsaturated polyester material. However, with the increase of the requirements, the defects of large curing shrinkage, low strength and poor toughness of the unsaturated polyester material are gradually revealed, and the comprehensive performance requirements of high-end products (such as door and window profiles) are difficult to meet.
The prior art CN106700015A discloses a polyurethane resin system and a method for preparing a pultruded glass reinforced plastic section. Compared with the traditional unsaturated polyester, the strength and toughness of the polyurethane resin can be improved by 2-5 times, so that the pultruded glass reinforced plastic section based on the polyurethane resin has higher nail holding force and is beneficial to subsequent processing operations such as drilling, machining, assembling and the like. Currently, glass fiber reinforced plastic pultruded profiles for doors and windows mainly use polyurethane resin. However, polyurethane resins are inferior in heat resistance: the modulus retention rate of the glass fiber reinforced plastic pultrusion section based on polyurethane resin at 65 ℃ is only about 80%, and the development of the polyurethane glass fiber reinforced plastic pultrusion section is restricted.
Glass fiber reinforced plastic pultrusion profiles based on epoxy resin are currently applied to the field of wind power blades in a large quantity, and the modulus retention rate can reach 100% at 65 ℃. Therefore, epoxy resin is attractive for glass fiber reinforced plastic door and window profiles instead of polyurethane resin. However, the toughness of epoxy resin is worse than that of polyurethane resin, and the obtained glass fiber reinforced plastic door and window profiles have a larger gap in nail-holding force.
The prior art CN116144142B discloses an epoxy resin-anhydride curing agent for pultrusion of composite materials and a preparation method thereof, wherein the preparation raw materials comprise epoxy resin, a diluent, a wetting dispersant or a defoaming agent or an internal mold release agent, an organic anhydride curing agent, a toughening agent and an accelerator, the composite materials can not generate chromatic aberration after the curing agent is used, but the use of functional auxiliary agents such as the diluent, the wetting dispersant or the defoaming agent can influence the nail holding power and the heat resistance of the materials, thereby influencing the application of the composite materials in the field of door and window profiles.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a preparation method of a glass fiber reinforced plastic pultruded profile with high heat resistance and high nail holding force, which at least comprises the following steps:
The glass fiber is led out from the creel, passes through the yarn guide plate, enters the trough filled with the liquid epoxy system material, continuously pulls the glass fiber fully soaked by the liquid epoxy system material through the die by the traction device, gradually solidifies the liquid epoxy system material to form a composite material when the glass fiber passes through the heated die, and then pulls the composite material out of the die to form a continuous glass fiber reinforced plastic pultrusion profile, and the material can be cut to obtain a single glass fiber reinforced plastic pultrusion profile, wherein the mass content of the glass fiber in the glass fiber reinforced plastic pultrusion profile is 60-85 wt%.
Preferably, the glass fibers comprise continuous glass fibers and/or continuous glass fiber mats.
Preferably, the continuous glass fiber mat comprises one or more of a glass fiber chopped strand mat, a glass fiber edge mat, a glass fiber composite mat, a glass fiber uni-axial hemming fabric and a glass fiber multi-axial hemming fabric.
Preferably, the gram weight of the continuous glass fiber mat is 240-650 g/m 2.
Preferably, the mold is heated in three stages: front, middle and rear regions; wherein the heating temperature of the front area is 120-160 ℃; the heating temperature in the middle area is 140-180 ℃; the heating temperature of the rear area is 160-200 ℃.
Preferably, the pultrusion speed of the composite material is 200-1000 mm/min, and in actual production, the pultrusion speed can be adjusted within the range according to the size of the profile.
The liquid epoxy system material comprises the following raw materials in parts by mass: 100 parts of epoxy resin, 80-120 parts of anhydride curing agent, 1-3 parts of accelerator, 10-20 parts of internal mold release agent, 5-15 parts of toughening agent and 5-15 parts of filler.
Preferably, the epoxy resin includes one or more of liquid glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, aliphatic epoxy resin and alicyclic epoxy resin.
Further preferably, the epoxy resin is glycidyl ether type epoxy resin; as a practical example, the glycidyl ether epoxy resin is purchased from Jiangsu Yang agriculture and forestry lake chemical industry Co., ltd, model YN1827.
Preferably, the anhydride curing agent comprises one or more of tung oil anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene hexahydrophthalic anhydride, glutaric anhydride, terpene anhydride, nadic anhydride or methyl nadic anhydride.
Further preferably, the acid anhydride curing agent is methyl tetrahydrophthalic anhydride; as a practical case, the methyl tetrahydrophthalic anhydride is purchased from Zhejiang alpha chemical engineering Co., ltd, and the model is AMT-122.
Preferably, the accelerator comprises one or more of tertiary amine accelerators, boron accelerators, benzyl triethyl ammonium chloride and imidazole accelerators.
Further preferably, the promoter is benzyl triethyl ammonium chloride; as a practical case, the benzyl triethyl ammonium chloride was purchased from Kent catalytic materials Co., ltd.
Preferably, the internal mold release agent comprises one or more of phosphate mold release agents, polyether polyols and stearic acid derivatives.
Further preferably, the internal mold release agent is a mixture of polyether polyol and stearic acid derivative; as a practical case, the mixture of polyether polyol and stearic acid derivative was purchased from Jiangsu clock mountain New Material Co., ltd., model ZS-280A.
The toughening agent selected in the invention is ZYHtoughen0436 of Shanghai ocher macro new material science and technology Co., ltd, is capsule-shaped liquid core-shell rubber with the size of 100-200nm, and is provided with a nanoscale styrene-butadiene rubber core wrapped by a nanoscale acrylic shell.
Preferably, the filler comprises one or more of titanium dioxide, lanthanum trioxide, wollastonite, talcum powder, quartz powder, calcium carbonate and kaolin.
Further preferably, the filler is wollastonite, and the aspect ratio of wollastonite is (3-6): 1, the grain diameter is 200-500 meshes; as a practical example, the wollastonite is XYNFW-A325 of southern wollastonite Inc. of New England, having a particle size of 325 mesh and an aspect ratio of 4:1.
The invention also provides a glass fiber reinforced plastic pultruded profile prepared by the preparation method.
Advantageous effects
According to the invention, epoxy resin is used as a main body preparation raw material of the glass fiber reinforced plastic pultrusion steel, so that the traditional polyurethane resin material is replaced, the high heat resistance of the glass fiber reinforced plastic pultrusion profile can be realized, and the modulus retention rate of the product at 65 ℃ can reach 100%.
And (II) the YN1827 glycidyl ether type epoxy resin of Jiangsu Yang nong lake chemical industry Co., ltd. Is used as a preparation raw material, and compared with other types of epoxy resins on the market which are used as raw materials of glass fiber reinforced plastic pultrusion profiles, the glass fiber reinforced plastic pultrusion profile product has better heat resistance and toughness.
(III) the present invention uses specific toughening agents: ZYHtoughen 0436 of Shanghai Haematitum-brightening new material technology Co., ltd can greatly improve the toughness of epoxy system materials on the premise of not sacrificing heat resistance, thereby improving the nail-holding force of glass fiber reinforced plastic pultrusion sectional materials.
(IV) the invention is characterized by specific granular filler wollastonite, especially particle size 325 mesh, aspect ratio 4:1, the wollastonite has a higher length-diameter ratio, so that the cracking resistance of the epoxy system material can be effectively improved, and the nail holding force of the glass fiber reinforced plastic pultrusion profile is improved.
The invention can ensure that the glass fiber reinforced plastic pultrusion section bar has higher nail holding power which is more than 630N/mm through the combination of specific raw materials and the preparation process, is particularly suitable for being applied to the field of door and window section bar production, has easily obtained raw materials and simple preparation process, and can realize industrial production of products.
Detailed Description
Example 1
The first aspect of the present invention provides a method for preparing a glass fiber reinforced plastic pultruded profile with high heat resistance and high nail holding power, which specifically comprises the following steps:
Leading out glass fiber from a creel, passing through a yarn guide plate, entering a trough filled with liquid epoxy system material, continuously pulling the glass fiber fully soaked by the liquid epoxy system material through a die by a traction device, gradually solidifying the liquid epoxy system material to form a composite material when the glass fiber passes through the heated die, and then pulling the composite material out of the die at a pulling and extruding speed of 500mm/min to form a continuous glass fiber reinforced plastic pulling and extruding section, wherein the single glass fiber reinforced plastic pulling and extruding section can be obtained after the material is cut; wherein the mass content of glass fiber in the glass fiber reinforced plastic pultrusion profile is 65wt%; the die adopts three-section heating of a front area, a middle area and a rear area, and the heating temperature of the front area is 150 ℃; the heating temperature in the middle area is 160 ℃; the post zone heating temperature was 180 ℃.
The glass fiber is continuous glass fiber felt, and is purchased from Chongqing International composite material Co., ltd, and the model is ECT468G-4800Tex.
The raw materials of the raw material liquid epoxy system material of the glass fiber reinforced plastic pultrusion profile are as follows in parts by mass: 100 parts of epoxy resin, 100 parts of anhydride curing agent, 2 parts of accelerator, 15 parts of internal mold release agent, 10 parts of toughening agent and 10 parts of filler.
The epoxy resin is glycidyl ether type epoxy resin, and is purchased from Jiangsu Yang nong jin lake chemical industry Co., ltd, and the model is YN1827.
The anhydride curing agent is methyl tetrahydrophthalic anhydride, and is purchased from Zhejiang alpha chemical engineering Co., ltd, and the model is AMT-122.
The promoter is benzyl triethyl ammonium chloride, available from Kent catalytic materials Co.
The internal release agent is purchased from Jiangsu clock mountain new material Co.Ltd, and the model is ZS-280A.
The toughening agent is purchased from Shanghai ocher major materials science and technology Co., ltd, and the model is ZYHtoughen0436.
The filler is wollastonite which is purchased from southern wollastonite Inc. of New city, the model is XYNFW-A325, the particle size is 325 meshes, and the length-diameter ratio is 4:1.
The second aspect of the present example provides a glass fiber reinforced plastic pultruded profile prepared according to the preparation method.
Example 2
The first aspect of the present invention provides a method for preparing a glass fiber reinforced plastic pultruded profile with high heat resistance and high nail holding power, which specifically comprises the following steps:
Leading out glass fiber from a creel, passing through a yarn guide plate, entering a trough filled with liquid epoxy system material, continuously pulling the glass fiber fully soaked by the liquid epoxy system material through a die by a traction device, gradually solidifying the liquid epoxy system material to form a composite material when the glass fiber passes through the heated die, and then pulling the composite material out of the die at a pulling and extruding speed of 600mm/min to form a continuous glass fiber reinforced plastic pulling and extruding section, wherein the material can obtain a single glass fiber reinforced plastic pulling and extruding section after being cut, and the mass content of the glass fiber in the glass fiber reinforced plastic pulling and extruding section is 70wt%; the die adopts three-section heating of a front area, a middle area and a rear area, and the heating temperature of the front area is 140 ℃; the heating temperature in the middle area is 160 ℃; the post zone heating temperature was 190 ℃.
The glass fiber is continuous glass fiber felt, and is purchased from Chongqing International composite material Co., ltd, and the model is ECT468G-4800Tex.
The raw materials of the raw material liquid epoxy system material of the glass fiber reinforced plastic pultrusion profile are as follows in parts by mass: 100 parts of epoxy resin, 80 parts of anhydride curing agent, 1 part of accelerator, 12 parts of internal mold release agent, 8 parts of toughening agent and 8 parts of filler.
The epoxy resin is glycidyl ether type epoxy resin, and is purchased from Jiangsu Yang nong jin lake chemical industry Co., ltd, and the model is YN1827.
The anhydride curing agent is methyl tetrahydrophthalic anhydride, and is purchased from Zhejiang alpha chemical engineering Co., ltd, and the model is AMT-122.
The promoter is benzyl triethyl ammonium chloride, available from Kent catalytic materials Co.
The internal release agent is purchased from Jiangsu clock mountain new material Co.Ltd, and the model is ZS-280A.
The toughening agent is purchased from Shanghai ocher major materials science and technology Co., ltd, and the model is ZYHtoughen0436.
The filler is wollastonite which is purchased from southern wollastonite Inc. of New city, the model is XYNFW-A325, the particle size is 325 meshes, and the length-diameter ratio is 4:1.
The second aspect of the present example provides a glass fiber reinforced plastic pultruded profile prepared according to the preparation method.
Example 3
The first aspect of the present invention provides a method for preparing a glass fiber reinforced plastic pultruded profile with high heat resistance and high nail holding power, which specifically comprises the following steps:
Leading out glass fiber from a creel, passing through a yarn guide plate, entering a trough filled with liquid epoxy system material, continuously pulling the glass fiber fully soaked by the liquid epoxy system material through a die by a traction device, gradually solidifying the liquid epoxy system material to form a composite material when the glass fiber passes through the heated die, and then pulling the composite material out of the die at a pulling and extruding speed of 800mm/min to form a continuous glass fiber reinforced plastic pulling and extruding section, wherein the glass fiber reinforced plastic pulling and extruding section can be obtained by cutting the material, and the mass content of the glass fiber in the glass fiber reinforced plastic pulling and extruding section is 70wt%; the mold adopts three-section heating of a front area, a middle area and a rear area, and the heating temperature of the front area is 160 ℃; the heating temperature in the middle area is 180 ℃; the post zone heating temperature was 200 ℃.
The glass fiber is continuous glass fiber felt, and is purchased from Chongqing International composite material Co., ltd, and the model is ECT468G-4800Tex.
The raw materials of the raw material liquid epoxy system material of the glass fiber reinforced plastic pultrusion profile are as follows in parts by mass: 100 parts of epoxy resin, 120 parts of anhydride curing agent, 3 parts of accelerator, 20 parts of internal mold release agent, 15 parts of toughening agent and 15 parts of filler.
The epoxy resin is glycidyl ether type epoxy resin, and is purchased from Jiangsu Yang nong jin lake chemical industry Co., ltd, and the model is YN1827.
The anhydride curing agent is methyl tetrahydrophthalic anhydride, and is purchased from Zhejiang alpha chemical engineering Co., ltd, and the model is AMT-122.
The promoter is benzyl triethyl ammonium chloride, available from Kent catalytic materials Co.
The internal release agent is purchased from Jiangsu clock mountain new material Co.Ltd, and the model is ZS-280A.
The toughening agent is purchased from Shanghai ocher major materials science and technology Co., ltd, and the model is ZYHtoughen0436.
The filler is wollastonite which is purchased from southern wollastonite Inc. of New city, the model is XYNFW-A325, the particle size is 325 meshes, and the length-diameter ratio is 4:1.
The second aspect of the present example provides a glass fiber reinforced plastic pultruded profile prepared according to the preparation method.
Comparative example 1
This example provides a glass fiber reinforced plastic pultruded profile, which has the same preparation raw materials as in example 1, except that the epoxy resin described in example 1 is replaced with polyurethane resin of equal parts by mass, wherein the polyurethane resin is Baydur PUL 4501 created by kesi.
Comparative example 2
The present example provides a glass fiber reinforced plastic pultruded profile, which has the same preparation raw materials as those of example 1, except that the epoxy resin used in the present example is Techstorm/5241/5245 of Daosheng Tianhe materials science and technology (Shanghai) Co., ltd.
Evaluation of Performance
Test object: the glass fiber reinforced plastic pultrusion profile corresponding to the embodiment 1 and the comparative embodiment 2
The test items and results are detailed in Table 1
TABLE 1

Claims (10)

1. A preparation method of a high heat-resistant high nail-holding strength glass fiber reinforced plastic pultruded profile is characterized by comprising the following steps: at least comprises the following steps:
Leading out glass fiber from a creel, passing through a yarn guide plate, entering a trough filled with liquid epoxy system material, continuously pulling the glass fiber fully soaked by the liquid epoxy system material through a die by a traction device, gradually solidifying the liquid epoxy system material to form a composite material when the glass fiber passes through the heated die, and then pulling the composite material out of the die to form a continuous glass fiber reinforced plastic pultrusion profile, wherein the material is cut to obtain a single glass fiber reinforced plastic pultrusion profile, and the mass content of the glass fiber in the glass fiber reinforced plastic pultrusion profile is 60-85 wt%;
The liquid epoxy system material comprises the following raw materials in parts by mass: 100 parts of epoxy resin, 80-120 parts of anhydride curing agent, 1-3 parts of accelerator, 10-20 parts of internal mold release agent, 5-15 parts of toughening agent and 5-15 parts of filler.
2. The method for preparing the glass fiber reinforced plastic pultruded profile according to claim 1, wherein the method comprises the following steps: the glass fibers include continuous glass fibers and/or continuous glass fiber mats.
3. The method for preparing the glass fiber reinforced plastic pultruded profile according to claim 2, wherein the method comprises the following steps: the continuous glass fiber felt comprises one or more of a glass fiber chopped strand mat, a glass fiber edge sealing mat, a glass fiber composite mat, a glass fiber single-axial hemming fabric and a glass fiber multi-axial hemming fabric.
4. A method of producing a pultruded glass fibre reinforced plastic profile according to claim 3, characterized in that: the epoxy resin comprises one or more of liquid glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, aliphatic epoxy resin and alicyclic epoxy resin.
5. The method for preparing a glass fiber reinforced plastic pultruded profile according to claim 4, wherein: the epoxy resin is glycidyl ether type epoxy resin.
6. The method for preparing the glass fiber reinforced plastic pultruded profile according to claim 5, wherein the method comprises the following steps: the anhydride curing agent comprises one or more of tung oil anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene hexahydrophthalic anhydride, glutaric anhydride, terpene anhydride, nadic anhydride or methyl nadic anhydride.
7. The method for preparing a glass fiber reinforced plastic pultruded profile according to claim 6, wherein: the accelerator comprises one or more of tertiary amine accelerators, boron accelerators, benzyl triethyl ammonium chloride and imidazole accelerators.
8. The method for preparing a glass fiber reinforced plastic pultruded profile according to claim 7, wherein: the internal release agent comprises one or more of phosphate release agent, polyether polyol and stearic acid derivative.
9. The method for preparing the glass fiber reinforced plastic pultruded profile according to claim 8, wherein the method comprises the following steps: the filler comprises one or more of titanium white, lanthanum oxide, wollastonite, talcum powder, quartz powder, calcium carbonate and kaolin.
10. A glass fiber reinforced plastic pultruded profile prepared by the method for preparing a glass fiber reinforced plastic pultruded profile according to claim 9.
CN202410644500.2A 2024-05-23 2024-05-23 High-heat-resistance high-nail-holding-force glass fiber reinforced plastic pultruded profile and preparation method thereof Pending CN118480201A (en)

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Application Number Priority Date Filing Date Title
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