CN112175373B - Unsaturated polyester glass fiber reinforced plastic and process steps - Google Patents
Unsaturated polyester glass fiber reinforced plastic and process steps Download PDFInfo
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Abstract
The application relates to the field of glass fiber reinforced plastics, and particularly discloses unsaturated polyester glass fiber reinforced plastics and process steps. An unsaturated polyester glass fiber reinforced plastic comprises phosphorus-containing epoxy resin, unsaturated polyester, styrene-butadiene rubber resin, continuous glass fiber, zinc stearate, a toughening blending agent, a curing agent, calcium carbonate powder, an auxiliary agent and pigment paste; the preparation method comprises the following steps: mixing phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin, then adding an auxiliary agent, zinc stearate, a toughening blending agent, a curing agent, calcium carbonate stone powder, pigment paste and continuous glass fiber to obtain resin paste, coating the resin paste on a film, thickening and curing. The glass fiber reinforced plastic has the advantages of glossy, smooth and mellow surface and strong plastic feeling on the surface.
Description
Technical Field
The application relates to the technical field of glass fiber reinforced plastics, in particular to unsaturated polyester glass fiber reinforced plastics and process steps.
Background
Compared with the traditional metal material and non-metal material, the glass fiber plastic has the characteristics of light weight, high hardness, corrosion resistance, high product design freedom, wide product use adaptability and the like, and is widely applied to the industry fields of aerospace, railway, electronic equipment, decorative buildings, home furniture, automobile parts and the like.
The glass fiber plastic in the related art is mainly prepared by taking unsaturated resin, glass fiber and filler as main base materials, and because the surface of the cured unsaturated resin has certain viscosity, the obtained product has more surface fibers, is not smooth and flat enough, has no glossiness and poor surface performance, and is limited to the application in some fields requiring higher material surface performance.
Disclosure of Invention
In order to increase the surface roundness of a glass fiber reinforced plastic product and improve the surface performance, the application provides unsaturated polyester glass fiber reinforced plastic and process steps.
In a first aspect, the present application provides an unsaturated polyester glass fiber reinforced plastic, which adopts the following technical scheme:
an unsaturated polyester glass fiber reinforced plastic comprises the following raw materials in parts by weight:
56-75 parts of phosphorus-containing epoxy resin;
unsaturated polyester: 105-130 parts of a stabilizer;
styrene-butadiene rubber resin: 45-55 parts of a modifier;
continuous glass fiber: 20-30 parts of a solvent;
zinc stearate: 5-8 parts of a stabilizer;
toughening blending agent: 3-6 parts;
curing agent: 3.5-7.5 parts;
calcium carbonate stone powder: 112-141 parts;
auxiliary agents: 0-25 parts;
pigment paste: 10-15 parts.
By adopting the technical scheme, the phosphorus-containing epoxy resin and the styrene-butadiene rubber resin are added into the plastic, the phosphorus-containing epoxy resin has excellent bonding performance and can increase the surface smoothness of the plastic, the styrene-butadiene rubber resin can enhance the toughness of the plastic and improve the roundness of the surface of the plastic, the surface plastic feeling is strong, the fluidity and the toughness of the plastic are increased by using calcium carbonate powder, the surface performance and the mechanical performance of the plastic are integrally improved by using the synergistic cooperation of the phosphorus-containing epoxy resin, the styrene-butadiene rubber resin and unsaturated polyester, the phosphorus-containing epoxy resin, the styrene-butadiene rubber resin and the unsaturated polyester can be applied to interior trim parts of the automobile industry, high-speed rails and airplanes, electronic product protective housings and the like, the application field range is enlarged, and the environment friendliness is enhanced.
Preferably, the mass ratio of the phosphorus-containing epoxy resin to the unsaturated polyester to the styrene-butadiene rubber resin is (11-12): 21: 9.
by adopting the technical scheme, the proportion of the phosphorus-containing epoxy resin, the unsaturated polyester and the styrene-butadiene rubber resin is limited, and the average friction coefficient of the plastic can be reduced through the synergistic effect of the phosphorus-containing epoxy resin, the unsaturated polyester and the styrene-butadiene rubber resin, so that the smoothness and the roundness of the surface of the plastic are further improved.
Preferably, the auxiliary agent is 18-25 parts by weight, and the auxiliary agent comprises the following components in a mass ratio of (1-2): 7: (4-6): (1-3) the halogen-free low-smoke flame-retardant filler, polystyrene, MgO and UV resistant agent.
By adopting the technical scheme, the halogen-free low-smoke flame-retardant filler is added into the plastic, so that the plastic has a flame-retardant effect; the polystyrene can reduce the shrinkage rate of the unsaturated polyester during curing and improve the surface smoothness of the plastic; MgO has a thickening effect on a plastic system, so that the curing time can be reduced, and the production efficiency is improved; the anti-UV agent can resist the irradiation of ultraviolet rays, has an anti-aging effect, can increase the functions of plastics according to the design requirements, and has strong adaptability.
Preferably, the halogen-free low-smoke flame-retardant filler is a phosphorus-nitrogen intumescent flame retardant.
By adopting the technical scheme, the phosphorus-nitrogen intumescent flame retardant has the advantages of flame resistance, smoke suppression and low toxicity, is less in addition amount, is environment-friendly, and has the effects of environmental protection and economy.
Preferably, the toughening blending agent is maleic anhydride modified polyethylene.
By adopting the technical scheme, the maleic acid rod modified polyethylene is added into the plastic raw material, and the strongly polar maleic anhydride side group is introduced into the molecular main chain of the non-polar polyethylene, so that the polyethylene can be used as a bridge for bonding and compatibility between calcium carbonate stone powder and phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin, the cross-linking and bonding properties between the calcium carbonate stone powder and the phosphorus-containing epoxy resin are improved, and the polyethylene has the advantages of filling and enhancing mechanical properties, thereby improving the mechanical properties of the plastic.
Preferably, the curing agent is prepared from triethanolamine, menthane diamine and 2-ethyl-4-methylimidazole according to the mass ratio of (1-2): (2-3): (1-3) in proportion.
By adopting the technical scheme, the curing agent is prepared by compounding triethanolamine, menthane diamine and 2-ethyl-4 methylimidazole according to a certain proportion, the triethanolamine, the menthane diamine and the 2-ethyl-4 methylimidazole have strong binding capacity with the phosphorus-containing epoxy resin, the curing is uniform, the curing effect is quick, the using amount of a single curing agent can be reduced, and the plastic prepared by using the curing agent has strong mechanical property.
Preferably, the particle size of the calcium carbonate stone powder is 0.02-0.1 μm.
By adopting the technical scheme, the rheological property of the plastic can be changed by the calcium carbonate powder, the rigidity of the plastic is ensured while the toughness of the plastic is improved by controlling the particle size of the calcium carbonate powder to be between 0.02 and 0.1 micrometer, and the surface gloss, flatness and roundness of the plastic are improved.
Preferably, the calcium carbonate stone powder is modified calcium carbonate stone powder, and the modified calcium carbonate stone powder is obtained by adopting the following preparation steps: weighing 10-15 parts by weight of calcium carbonate powder, adding 20-40 parts by weight of ethanol, uniformly stirring, controlling the temperature system to be 60-80 ℃, then adding 8-12 parts by weight of ethyl orthosilicate, stirring for 20-30 min, filtering and drying to obtain the modified calcium carbonate powder.
By adopting the technical scheme, the tetraethoxysilane is utilized to carry out surface modification on the calcium carbonate powder, so that the polarity of the calcium carbonate powder is converted into the non-polarity, the dispersion stability of the calcium carbonate powder in the unsaturated polyester, the phosphorus-containing epoxy resin and the styrene-butadiene rubber resin organic phase is improved, the agglomeration of the calcium carbonate powder is effectively prevented, and the surface smoothness and the smoothness of the plastic are improved.
In a second aspect, the present application provides a process step of an unsaturated polyester glass fiber reinforced plastic, which adopts the following technical scheme:
the process steps of the unsaturated polyester glass fiber reinforced plastic comprise the following steps:
step one, mixing and stirring phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin uniformly for 5-10 min to obtain a first mixture;
step two, adding an auxiliary agent, zinc stearate, a toughening blending agent and a curing agent into the first mixture obtained in the step one, controlling the temperature system to be 70-85 ℃, and mixing and stirring for 20-30 min to obtain a second mixture;
step three, sequentially adding calcium carbonate stone powder, pigment paste and continuous glass fiber into the second mixture obtained in the step two, mixing and stirring uniformly, and carrying out ultrasonic treatment for 5-15 min to obtain resin paste;
and step four, uniformly coating the resin paste obtained in the step three on a film, thickening and curing, and demolding after hands are not stuck to obtain the glass fiber reinforced plastic.
By adopting the technical scheme, the phosphorus-containing epoxy resin, the unsaturated polyester and the styrene-butadiene rubber resin are preliminarily mixed in advance, and then other components in the plastic are sequentially added, so that the dispersion uniformity of the components in the plastic can be improved, the fusion degree of the components in the plastic is improved, and the mechanical property and the surface property of the plastic are improved.
Preferably, in the thickening and curing process of the fourth step, the film coated with the resin paste is sent to a curing room with an air blowing device to accelerate thickening and curing, the temperature of the system is controlled to be 35-40 ℃, and the time is controlled to be 8-10 h.
By adopting the technical scheme, the thickening and curing of the plastic are accelerated by adopting the air blowing equipment, so that the production efficiency can be improved, the surface shrinkage rate of the plastic is reduced, and the smoothness and the roundness of the surface of the plastic are improved.
In summary, the present application has the following beneficial effects:
1. the phosphorus-containing epoxy resin and the styrene-butadiene rubber resin are added into the plastic, the phosphorus-containing epoxy resin has excellent bonding performance and can increase the surface smoothness of the plastic, the styrene-butadiene rubber resin can enhance the toughness of the plastic and improve the surface roundness of the plastic, the calcium carbonate powder is used for increasing the fluidity and toughness of the plastic, and the phosphorus-containing epoxy resin, the styrene-butadiene rubber resin and the unsaturated polyester are cooperatively used for integrally improving the surface performance and mechanical property of the plastic;
2. the proportion of the phosphorus-containing epoxy resin, the unsaturated polyester and the styrene-butadiene rubber resin is limited, and the average friction coefficient of the plastic can be reduced through the synergistic effect of the phosphorus-containing epoxy resin, the unsaturated polyester and the styrene-butadiene rubber resin, so that the smoothness and the roundness of the surface of the plastic are further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
TABLE 1 sources of raw materials
Examples
Example 1
The unsaturated polyester glass fiber reinforced plastic is prepared by the following preparation steps, wherein the components and parts by weight are shown in Table 2:
step one, mixing and stirring phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin uniformly under low shearing force for 5min to obtain a first mixture;
step two, adding zinc stearate, a toughening blending agent and a curing agent into the first mixture obtained in the step one, controlling the temperature system to be 80 ℃, and mixing and stirring for 30min under low shearing force to obtain a second mixture, wherein the toughening blending agent is polyvinyl butyral;
step three, sequentially adding calcium carbonate stone powder, pigment paste and continuous glass fiber into the second mixture obtained in the step two, mixing and stirring uniformly under low shearing force, and performing ultrasonic treatment for 10min to obtain resin paste;
and step four, uniformly coating the resin paste obtained in the step three on a film, standing for thickening and curing, and demolding after hands are not stuck to obtain the glass fiber reinforced plastic.
Example 2
The unsaturated polyester glass fiber reinforced plastic is prepared by the following preparation steps, wherein the components and the parts by weight are shown in Table 2:
step one, mixing and stirring phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin uniformly under low shearing force for 10min to obtain a first mixture;
step two, adding zinc stearate, a toughening blending agent and a curing agent into the first mixture obtained in the step one, controlling the temperature system to be 85 ℃, and mixing and stirring for 25min under low shearing force to obtain a second mixture, wherein the toughening blending agent is polyvinyl butyral;
step three, sequentially adding calcium carbonate stone powder, pigment paste and continuous glass fiber into the second mixture obtained in the step two, mixing and stirring uniformly under low shearing force, and performing ultrasonic treatment for 15min to obtain resin paste;
and step four, uniformly coating the resin paste obtained in the step three on a film, standing for thickening and curing, and demolding after hands are not stuck to obtain the glass fiber reinforced plastic.
Example 3
The unsaturated polyester glass fiber reinforced plastic is prepared by the following preparation steps, wherein the components and parts by weight are shown in Table 2:
step one, mixing and stirring phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin uniformly under low shear force for 5min to obtain a first mixture;
step two, adding zinc stearate, a toughening blending agent and a curing agent into the first mixture obtained in the step one, controlling the temperature system to be 70 ℃, and mixing and stirring for 20min under low shearing force to obtain a second mixture, wherein the toughening blending agent is polyvinyl butyral;
step three, sequentially adding calcium carbonate stone powder, pigment paste and continuous glass fiber into the second mixture obtained in the step two, mixing and stirring uniformly under low shearing force, and carrying out ultrasonic treatment for 5min to obtain resin paste;
and step four, uniformly coating the resin paste obtained in the step three on a film, standing for thickening and curing, and demolding after hands are not stuck to obtain the glass fiber reinforced plastic.
Example 4
The unsaturated polyester glass fiber reinforced plastic is prepared by the following preparation steps, wherein the components and the parts by weight are shown in Table 2:
step one, mixing and stirring phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin uniformly under low shearing force for 5min to obtain a first mixture;
step two, adding an auxiliary agent, zinc stearate, a toughening blending agent and a curing agent into the first mixture obtained in the step one, controlling a temperature system to be 70 ℃, mixing and stirring for 20min under low shearing force, and obtaining a second mixture, wherein the toughening blending agent is polyvinyl butyral, and the auxiliary agent is prepared from a halogen-free low-smoke flame-retardant filler, polystyrene, MgO and an anti-UV agent in a mass ratio of 1: 7: 4:2, and the halogen-free low-smoke flame-retardant filler is a phosphorus-nitrogen intumescent flame retardant;
step three, sequentially adding calcium carbonate stone powder, pigment paste and continuous glass fiber into the second mixture obtained in the step two, mixing and stirring uniformly under low shearing force, and carrying out ultrasonic treatment for 5min to obtain resin paste;
and step four, uniformly coating the resin paste obtained in the step three on a film, standing for thickening and curing, and demolding after hands are not stuck to obtain the glass fiber reinforced plastic.
TABLE 2 summary of the components and weight contents of examples 1-4
In examples 1 to 4, the calcium carbonate stone powder had a particle size of 0.5. mu.m.
Example 5
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that the auxiliary agent is 25kg, and the auxiliary agent is prepared from a halogen-free low-smoke flame-retardant filler, polystyrene, MgO and an anti-UV agent in a mass ratio of (1: 7): mixing at a ratio of 6: 1.
Example 6
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that 22kg of auxiliary agent is prepared from a halogen-free low-smoke flame-retardant filler, polystyrene, MgO and an anti-UV agent in a mass ratio of (2: 7): 5: 3.
Example 7
An unsaturated polyester glass fiber reinforced plastic, which is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that the toughening blending agent is polyvinyl acetate.
Example 8
An unsaturated polyester glass fiber reinforced plastic, which is different from the embodiment 3 in that the toughening blending agent is maleic anhydride modified polyethylene.
Example 9
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that the phosphorus-containing epoxy resin is 55kg, the unsaturated polyester is 105kg and the styrene-butadiene rubber resin is 45kg, wherein the mass ratio of the phosphorus-containing epoxy resin to the unsaturated polyester to the styrene-butadiene rubber resin is 11:21: 9.
Example 10
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that 72kg of phosphorus-containing epoxy resin, 126kg of unsaturated polyester and 54kg of styrene-butadiene rubber resin are adopted, and the mass ratio of the phosphorus-containing epoxy resin to the unsaturated polyester to the styrene-butadiene rubber resin is 12:21: 9.
Example 11
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that a curing agent is prepared from triethanolamine, menthane diamine and 2-ethyl-4-methylimidazole according to the mass ratio of 1: 2:3, and mixing the components in proportion.
Example 12
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that a curing agent is prepared from triethanolamine, menthane diamine and 2-ethyl-4-methylimidazole according to the mass ratio of 2: 3: 1 proportion of the components.
Example 13
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that a curing agent is prepared from triethanolamine, menthane diamine and 2-ethyl-4-methylimidazole according to the mass ratio of 1: 3: 2, and mixing the components in a ratio of 2.
Example 14
An unsaturated polyester glass fiber-reinforced plastic differing from example 3 in that the particle size of the calcium carbonate stone powder was 0.02 μm.
Example 15
An unsaturated polyester glass fiber-reinforced plastic differing from example 3 in that the particle size of the calcium carbonate stone powder was 0.05 μm.
Example 16
An unsaturated polyester glass fiber-reinforced plastic differing from example 3 in that the particle size of calcium carbonate stone powder was 0.1 μm.
Example 17
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in that calcium carbonate stone powder is modified calcium carbonate stone powder and is prepared by the following steps: weighing 10 parts by weight of calcium carbonate powder, adding the calcium carbonate powder into 40 parts by weight of ethanol, uniformly stirring, controlling the temperature system to be 80 ℃, then adding 8 parts by weight of ethyl orthosilicate, stirring for 20min, filtering and drying to obtain the modified calcium carbonate powder.
Example 18
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in that calcium carbonate stone powder is modified calcium carbonate stone powder and is prepared by the following steps: weighing 15 parts by weight of calcium carbonate stone powder, adding the calcium carbonate stone powder into 20 parts by weight of ethanol, uniformly stirring, controlling the temperature system to be 60 ℃, then adding 12 parts by weight of ethyl orthosilicate, stirring for 30min, filtering and drying to obtain the modified calcium carbonate stone powder.
Example 19
An unsaturated polyester glass fiber reinforced plastic, which is different from the embodiment 3 in that in the thickening and curing process in the fourth step, the film coated with the resin paste is sent to a curing room with a blowing device to be subjected to thickening and curing acceleration, and the temperature of the system is controlled to be 35 ℃ and the time is 8 hours.
Example 20
An unsaturated polyester glass fiber reinforced plastic, which is different from the embodiment 3 in that in the thickening and curing process in the fourth step, the film coated with the resin paste is sent to a curing room with a blowing device to be subjected to thickening and curing, and the temperature of the system is controlled to be 40 ℃ and the time is 10 hours.
Example 21
An unsaturated polyester glass fiber reinforced plastic is prepared by the following preparation steps:
step one, mixing and stirring 72kg of phosphorus-containing epoxy resin, 126kg of unsaturated polyester and 54kg of styrene-butadiene rubber resin uniformly under low shearing force for 5min to obtain a first mixture;
step two, adding 22kg of auxiliary agent, 5kg of zinc stearate, 3kg of maleic anhydride modified polyethylene and 6.5kg of curing agent into the first mixture obtained in the step one, controlling the temperature system to be 70 ℃, mixing and stirring for 20min under low shearing force to obtain a second mixture, wherein the auxiliary agent is prepared from phosphorus-nitrogen intumescent flame retardant, polystyrene, MgO and anti-UV agent according to the mass ratio of 2: 7: 5:3, and the curing agent is prepared by mixing triethanolamine, menthane diamine and 2-ethyl-4-methylimidazole according to a mass ratio of 1: 2:3, mixing the components in proportion;
step three, sequentially adding 135kg of modified calcium carbonate stone powder, 13kg of pigment paste and 25kg of continuous glass fiber into the second mixture obtained in the step two, mixing and stirring uniformly under low shearing force, and carrying out ultrasonic treatment for 5min to obtain resin paste;
the modified calcium carbonate stone powder is prepared by the following steps: weighing 10 parts by weight of calcium carbonate stone powder, adding 40 parts by weight of 60% ethanol water, uniformly stirring, controlling the temperature system to be 80 ℃, then adding 8 parts by weight of ethyl orthosilicate, stirring for 20min, filtering and drying to obtain the modified calcium carbonate stone powder;
and step four, uniformly coating the resin paste obtained in the step three on a film, conveying the film coated with the resin paste to a curing room with a blowing device, carrying out thickening and curing at a controlled system temperature of 40 ℃ for 10 hours, and demolding after the film is not sticky, thereby obtaining the glass fiber reinforced plastic.
Comparative example
Comparative example 1
An unsaturated polyester glass fiber reinforced plastic is different from the plastic in example 3 in that the phosphorus-containing epoxy resin in the raw material components is replaced by unsaturated polyester.
Comparative example 2
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in example 3 in that the styrene-butadiene rubber resin in the raw material components is replaced by the unsaturated polyester.
Comparative example 3
An unsaturated polyester glass fiber reinforced plastic is different from the unsaturated polyester glass fiber reinforced plastic in the embodiment 3 in that the phosphorus-containing epoxy resin and the styrene-butadiene rubber resin in the raw materials are replaced by the unsaturated polyester.
Performance test
The average friction coefficient of the plastic samples of examples 1-21 and comparative examples 1-3 was measured using a plastic friction coefficient tester, the size of the plastic sample was 10cm × 10cm × 10cm, and the larger the friction coefficient, the worse the roundness of the plastic was;
the tensile elastic modulus (MPa) of examples 1-21 and comparative examples 1-3 is measured by GB/T1447 tensile property test method of fiber reinforced plastics;
the impact strength (kJ. m) of the simply supported beams of examples 1 to 21 and comparative examples 1 to 3 was measured by GB/T1043.1-2008 "measurement of impact Properties of Plastic simply supported beams 2 )；
The compressive strength (MPa) of examples 1-21 and comparative examples 1-3 was measured by GB/T1451-2005 & methods for testing the compressive Properties of fiber-reinforced plastics.
TABLE 3 summary of test data for examples 1-6
TABLE 4 summary of test data for example 3 and comparative examples 1-3
As can be seen from comparison of the test data of example 3 and comparative example 1 in Table 4, the phosphorous epoxy resin has excellent adhesive property by adding the phosphorous epoxy resin to the plastic, and at the same time, the surface smoothness of the plastic can be increased, and the static friction coefficient and the dynamic friction coefficient of the plastic are reduced.
According to the comparison of the detection data of the example 3 and the comparative example 2 in the table 4, the styrene-butadiene rubber resin is added into the plastic, so that the static friction coefficient and the dynamic friction coefficient of the plastic are reduced, the tensile elastic modulus, the impact strength and the compression strength of the simple beam are improved, the toughness of the plastic can be enhanced by the styrene-butadiene rubber resin, and meanwhile, the surface smoothness and the surface performance of the plastic are improved.
According to the comparison of the detection data of the example 3 and the comparative examples 1 to 3 in the table 4, the synergistic effect of the phosphorus-containing epoxy resin, the unsaturated polyester and the styrene butadiene rubber polyester can obviously reduce the static friction coefficient and the dynamic friction coefficient of the plastic, improve the tensile elasticity and the compressive strength, and improve the mechanical property and the surface property of the plastic.
TABLE 5 summary of assay data for examples 3, 7-8
According to the comparison of the detection data of the examples 3 and 7-8 in the table 5, it can be known that the maleic acid rod modified polyethylene is added into the plastic raw material, and the strongly polar maleic anhydride side group is introduced into the molecular main chain of the nonpolar polyethylene, so that the polyethylene can be used as a bridge for the cohesiveness and compatibility between calcium carbonate stone powder and phosphorus-containing epoxy resin, unsaturated polyester and styrene-butadiene rubber resin, the mutual crosslinking and bonding properties are improved, and compared with polyvinyl acetate and polyvinyl butyral, the maleic acid rod modified polyethylene has the advantages of filling and enhancing the mechanical properties, so that the tensile elastic modulus, the simple beam impact strength and the compressive strength of the plastic are improved.
TABLE 6 summary of assay data for examples 3, 9-10
According to the comparison of the detection data of the examples 3 and 9-10 in the table 6, the static friction coefficient and the dynamic friction coefficient of the plastic can be reduced by limiting the proportion of the phosphorus-containing epoxy resin, the unsaturated polyester and the styrene-butadiene rubber resin, so that the smoothness and the smoothness of the surface of the plastic are further improved.
TABLE 7 summary of assay data for examples 3, 11-13
According to the comparison of the detection data of the examples 3 and 11-13 in the table 7, the curing agent is prepared by compounding triethanolamine, menthane diamine and 2-ethyl-4 methylimidazole according to a certain proportion, the triethanolamine, the menthane diamine and the 2-ethyl-4 methylimidazole have strong binding capacity with phosphorus-containing epoxy resin, are uniformly cured and have quick curing effect, the use amount of a single curing agent can be reduced, and the plastic prepared by using the curing agent has strong mechanical property and can improve the tensile elastic modulus, the impact strength and the compression strength of the plastic.
TABLE 8 summary of assay data for examples 3, 14-16
According to the comparison of the detection data of the examples 3 and 14 to 16 in the table 8, the calcium carbonate powder can change the rheological property of the plastic, and by controlling the particle size of the calcium carbonate powder to be between 0.02 and 0.1 μm, the static friction coefficient and the dynamic friction coefficient of the plastic are reduced, the tensile elastic modulus and the compressive strength are improved, the toughness of the plastic is improved, the rigidity of the plastic is ensured, and the surface gloss, the flatness and the roundness of the plastic are improved.
TABLE 9 summary of assay data for examples 3, 17-21
According to the comparison of the detection data of the examples 3 and 17 to 18 in the table 9, the calcium carbonate powder is subjected to surface modification by using ethyl orthosilicate, so that the polarity of the calcium carbonate powder is converted into non-polarity, the dispersion stability of the calcium carbonate powder in the organic phase of unsaturated polyester, phosphorus-containing epoxy resin and styrene butadiene rubber resin is improved, the agglomeration of the calcium carbonate powder is effectively prevented, the static friction coefficient and the dynamic friction coefficient are reduced, and the surface smoothness and smoothness of the plastic are improved.
According to the comparison of the detection data of the examples 3 and 19 to 20 in the table 9, the thickening and curing of the plastic are accelerated by adopting the air blowing equipment, so that the production efficiency can be improved, the surface shrinkage rate of the plastic is reduced, the static friction coefficient and the dynamic friction coefficient of the plastic are reduced, and the smoothness and the roundness of the surface of the plastic are improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The unsaturated polyester glass fiber reinforced plastic is characterized by comprising the following raw materials in parts by weight:
56-75 parts of phosphorus-containing epoxy resin;
unsaturated polyester: 105-130 parts of a stabilizer;
styrene-butadiene rubber resin: 45-55 parts of a modifier;
continuous glass fiber: 20-30 parts of a solvent;
zinc stearate: 5-8 parts;
toughening blending agent: 3-6 parts;
curing agent: 3.5-7.5 parts;
calcium carbonate stone powder: 112-141 parts;
auxiliary agents: 0 to 25 portions;
pigment paste: 10 to 15 portions of the raw materials are mixed,
the mass ratio of the phosphorus-containing epoxy resin to the unsaturated polyester to the styrene-butadiene rubber resin is (11-12): 21: 9.
2. the unsaturated polyester glass fiber reinforced plastic according to claim 1, wherein: the auxiliary agent comprises 18-25 parts by weight of (1-2): 7: (4-6): (1-3) a halogen-free low-smoke flame-retardant filler, polystyrene, MgO and an anti-UV agent.
3. The unsaturated polyester glass fiber reinforced plastic as claimed in claim 1, wherein the toughening blending agent is maleic anhydride modified polyethylene.
4. The unsaturated polyester glass fiber reinforced plastic as claimed in claim 1, wherein the curing agent is prepared from triethanolamine, menthane diamine, 2-ethyl-4 methyl imidazole according to the mass ratio of (1-2): (2-3): (1-3) in a certain proportion.
5. The unsaturated polyester glass fiber reinforced plastic according to claim 1, wherein the calcium carbonate powder has a particle size of 0.02 μm to 0.1 μm.
6. The unsaturated polyester glass fiber reinforced plastic as claimed in claim 1, wherein the calcium carbonate stone powder is modified calcium carbonate stone powder, and the modified calcium carbonate stone powder is obtained by the following preparation steps: weighing 10-15 parts by weight of calcium carbonate powder, adding 20-40 parts by weight of ethanol, uniformly stirring, controlling the temperature system to be 60-80 ℃, then adding 8-12 parts by weight of ethyl orthosilicate, stirring for 20-30 min, filtering and drying to obtain the modified calcium carbonate powder.
7. The method for preparing unsaturated polyester glass fiber reinforced plastic according to any one of claims 1 to 6, comprising the steps of:
step one, mixing and stirring phosphorus-containing epoxy resin, unsaturated polyester and styrene butadiene rubber resin uniformly for 5-10 min to obtain a first mixture;
step two, adding an auxiliary agent, zinc stearate, a toughening blending agent and a curing agent into the first mixture obtained in the step one, controlling the temperature system to be 70-85 ℃, and mixing and stirring for 20-30 min to obtain a second mixture;
step three, sequentially adding calcium carbonate stone powder, pigment paste and continuous glass fiber into the second mixture obtained in the step two, mixing and stirring uniformly, and carrying out ultrasonic treatment for 5-15 min to obtain resin paste;
and step four, uniformly coating the resin paste obtained in the step three on a film, thickening and curing, and demolding after hands are not stuck to obtain the glass fiber reinforced plastic.
8. The method for preparing unsaturated polyester glass fiber reinforced plastic according to claim 7, wherein the method comprises the following steps: in the thickening and curing process of the fourth step, the film coated with the resin paste is sent to a curing room with an air blowing device for accelerating thickening and curing, the temperature of the system is controlled to be 35-40 ℃, and the time is 8-10 hours.
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