CN112409695A - Low-warpage polypropylene modified plastic and preparation method thereof - Google Patents
Low-warpage polypropylene modified plastic and preparation method thereof Download PDFInfo
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- CN112409695A CN112409695A CN202011453976.6A CN202011453976A CN112409695A CN 112409695 A CN112409695 A CN 112409695A CN 202011453976 A CN202011453976 A CN 202011453976A CN 112409695 A CN112409695 A CN 112409695A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a low-warpage polypropylene modified plastic and a preparation method thereof. The invention mainly comprises modified glass fiber, modified microspheres, polyethyleneimine, modified liquid, polypropylene, an initiator, n-hexane, dithiothreitol, a carbonic acid solution and calcium lactate. The modified microspheres are beneficial to heat conduction in three-dimensional directions in the polypropylene plastic base material, so that the heat conduction of the polypropylene modified plastic in all directions is more uniform; the modified glass fiber can effectively improve the interface compatibility between polystyrene and polypropylene; the preparation method disclosed by the invention is simple in preparation process and easy in material acquisition, and the prepared polypropylene modified plastic is good in weather resistance, excellent in mechanical property, uniform in heat conduction, low in warpage rate, wide in application range and very practical, and can be used in high-temperature and low-temperature environments without easily causing a fracture problem.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to low-warpage polypropylene modified plastic and a preparation method thereof.
Background
With the progress of society and the development of economy, the application of plastics has penetrated the aspects of daily life of people, and the application of plastics brings great convenience to the life of people, such as automobile parts, rail transit, water cups and lunch boxes. The polypropylene plastic has small density, good mechanical property and stable property, is not easy to be corroded by chemicals, and is very popular with people, but the polypropylene belongs to a semi-crystalline polymer, and has the defects of large molding shrinkage, high warpage, brittleness and cracking at low temperature, easy deformation at high temperature and the like in the preparation process, so that the development of the polypropylene plastic is limited.
In order to optimize the performance of polypropylene plastics and expand the application range, one usually chooses to add glass fiber into polypropylene plastics to increase the heat distortion temperature of polypropylene plastics and improve the mechanical properties of polypropylene plastics. However, the cross section of the glass fiber added at ordinary times is mostly circular, the length and diameter are large, the prepared polypropylene plastic has anisotropy, and although the mechanical property and the heat resistance are improved to a certain extent, the problems of large shrinkage rate and high warping rate still exist.
Therefore, there is a need for a polypropylene modified plastic with low warpage, good mechanical properties and good weather resistance to solve the above problems.
Disclosure of Invention
The invention aims to provide a low-warpage polypropylene modified plastic and a preparation method thereof, so as to solve the problems in the background technology.
The low-warpage polypropylene modified plastic comprises the following raw material components: 30-50 parts of modified glass fiber, 20-40 parts of modified microspheres, 20-30 parts of polyethyleneimine, 30-50 parts of modified liquid, 80-100 parts of polypropylene, 10-20 parts of initiator, 15-25 parts of n-hexane, 10-20 parts of dithiothreitol, 20-30 parts of carbonic acid solution and 20-30 parts of calcium lactate; the initiator is azobisisobutyronitrile.
Further, the modified glass fiber comprises the following raw material components: 30-60 parts of mixed solution of a silane coupling agent, 80-100 parts of flat glass fiber, 10-20 parts of a catalyst, 25-45 parts of dimethylbenzene, 10-16 parts of dibenzoyl peroxide and 20-30 parts of a styrene monomer; the catalyst is ammonia water.
The raw material for preparing the modified glass fiber is the flat glass fiber, the flat glass fiber can improve the warping problem of the polypropylene plastic caused by various characteristics of the common glass fiber to a certain extent, but the capability of the flat glass fiber for improving the warping problem of the polypropylene plastic is still limited, so the flat glass fiber is further modified on the basis of the flat glass fiber. According to the invention, the flat glass is modified by introducing the styrene monomer and the polyethyleneimine on the flat glass fiber, the polyethyleneimine is modified by introducing the tertiary amine into the flat glass fiber, the tertiary amine reacts with the 4-vinylbenzyl chloride to generate the quaternary ammonium salt, the 4-vinylbenzyl chloride is further introduced onto the modified glass fiber, and the 4-vinylbenzyl chloride and the styrene generate the network structure under the action of the initiator, so that the network structure can organize the flow of polypropylene molecular chains, improve the impact resistance and mechanical property of the polypropylene modified plastic, improve the weather resistance and reduce the warping rate.
The carbon nano tube has excellent heat conductivity, but the heat conduction effect of the carbon nano tube has anisotropy, the heat conduction effect in a fixed direction is good, the heat conduction effect in other directions is poor, the surface energy of the carbon nano tube is large, the intermolecular force among the carbon nano tubes is strong, if the carbon nano tube is directly added into a polypropylene material for compounding, the problems of high warpage and high shrinkage rate of the polypropylene plastic can be caused due to agglomeration and uneven heat conduction among the carbon nano tubes, the specific surface area of the three-dimensional boron carbonitride powder is large, the porosity is high, the property of the three-dimensional boron carbonitride powder is combined with the advantages of two materials of carbon and boron nitride, the property is stable, the chemical resistance is good, the mechanical property is excellent, the heat conduction is strong, the thermal expansion coefficient is low, the carbon nano tube is penetrated and activated by taking the carbon nano tube as a carrier, the finally prepared modified microsphere can conduct heat conduction in the three-dimensional direction, the warping problem of the polypropylene plastic can be effectively improved.
Furthermore, the modified microspheres are three-dimensional silicon carbonitride microspheres with activated carbon nanotubes inserted into the surface or internal pores.
The preparation method comprises the steps of modifying three-dimensional boron carbonitride powder when preparing modified microspheres, modifying a large number of hydroxyl groups on the surface of the modified boron carbonitride powder, activating the carbon nano tubes to ensure that the surfaces of the carbon nano tubes also have a large number of oxygen-containing functional groups, reacting the large number of hydroxyl groups contained in the modified three-dimensional boron carbonitride powder with the large number of hydroxyl groups, carboxyl groups and other groups on the activated carbon nano tubes, and successfully modifying the activated carbon nano tubes between pores of the modified three-dimensional boron carbonitride powder and organizational structure layers of the pores; under the action of rolling, the activated carbon nano tubes are inserted into the modified three-dimensional boron carbonitride powder more compactly, so that the obtained modified microspheres have better mechanical properties and heat conduction effects; the activated carbon nano tube is inserted into the three-dimensional boron carbonitride powder, so that the dispersibility of the carbon nano tube can be improved, the interface bonding force between the modified microsphere and the plastic base material is improved, and the cracking risk of polypropylene plastic is reduced. The compounding of the unidirectional heat conduction carbon fiber and the high heat conduction three-dimensional boron carbonitride powder can enable the modified microspheres to form a composite heat conduction channel in the polypropylene plastic substrate, so that the heat conduction performance of the polypropylene plastic is improved, the heat transfer in the polypropylene plastic is more uniform, and the warping problem of the polypropylene plastic is further improved.
Further, the modification solution comprises 4-vinylbenzyl chloride and sodium thioacetate, wherein the mass ratio of the 4-vinylbenzyl chloride to the sodium thioacetate is (3-5): 2.
furthermore, the silane coupling agent mixed liquid comprises, by weight, 30-50 parts of a vinyl silane coupling agent, 25-35 parts of an epoxy hydrocarbon silane coupling agent and 15-25 parts of a carboxyl silane coupling agent.
A preparation method of low-warpage polypropylene modified plastic comprises the following steps:
s1, preparing modified microspheres:
A. preparing modified three-dimensional boron carbonitride powder;
B. preparing activated carbon nanotubes;
C. synthesizing modified microspheres;
s2, preparing modified glass fiber:
A. placing the silane coupling agent mixed solution into ethanol, stirring and dispersing, adding flat glass fiber and a catalyst, stirring, taking out and drying to obtain a material B;
B. placing the material B in a dimethylbenzene solution, stirring and dispersing, adding dibenzoyl peroxide and a styrene monomer, and stirring to obtain a modified glass fiber;
according to the invention, the flat glass fiber is modified by the mixed solution of the silane coupling agent, groups such as epoxy group, carboxyl group, vinyl group and the like are modified on the flat glass fiber, and then the flat glass fiber is soaked in the solution of dimethylbenzene, dibenzoyl peroxide and styrene for further agricultural reaction, so that the surface of the flat glass fiber is successfully modified with a styrene monomer, and the modified glass fiber is obtained.
S3, preparing a modification liquid: under the protection of nitrogen, 4-vinyl benzyl chloride is placed in N-methyl pyrrolidone to be stirred and dissolved, sodium thioglycolate is added, and stirring is continued to obtain a modified solution;
s4, synthesizing polypropylene modified plastic:
A. placing the modified glass fiber and the modified microspheres in a polyethyleneimine solution for ultrasonic dispersion, centrifuging, filtering, washing and drying to obtain a material C;
after the modified glass fiber and the modified microsphere are prepared, the modified glass fiber and the modified microsphere are further mixed and dipped into a polyethyleneimine solution for reaction. The polyethyleneimine belongs to a cationic electrolyte, the molecule of the polyethyleneimine contains a large amount of tertiary amine and active amino, modified glass fiber and modified microspheres are soaked in a polyethyleneimine solution, and active groups such as epoxy groups and carboxyl groups on the modified glass fiber and the modified microspheres can react with amino groups on polyethyleneimine molecular chains, so that the polyethyleneimine is modified on the modified glass fiber and the modified microspheres.
B. And mixing and stirring the material C, the modified solution, the polypropylene and the initiator, adding n-hexane and dithiothreitol, adding carbonic acid solution and calcium lactate, stirring, extruding and granulating to obtain the polypropylene modified plastic.
Firstly, reacting sodium thioacetate with 4-vinyl benzyl chloride, reacting the sodium thioacetate with part of the benzyl chloride to generate thioester, and protecting sulfydryl to obtain modified liquid; and mixing the modified solution with the material B and the polypropylene, wherein the benzyl chloride which does not react with the sodium thioacetate in the other part of the modified solution reacts with the tertiary amine on the modified glass fiber and the modified glass fiber to generate the positively charged quaternary ammonium salt on the surfaces of the modified glass fiber and the modified microsphere, and because the surfaces of the modified glass fiber and the modified microsphere have the same charges and the mutual repulsive force between the same charges, the agglomeration phenomenon between the modified glass fiber and the modified microsphere is obviously weakened, the problem of uneven distribution of the modified glass fiber and the modified microsphere in a plastic matrix is effectively solved, the dispersity of the single microsphere and the high-performance glass fiber is greatly improved, and the impact resistance of the polypropylene plastic is improved. Styrene and 4-vinylbenzyl chloride on the modified microspheres are polymerized under the action of an initiator and high temperature, polypropylene, polyvinyl benzyl chloride and polypropylene molecular chains are entangled with each other, and the modified glass fibers are used as network nodes to form a compact and stable network structure; the formed molecular chain network can effectively prevent the polypropylene molecular chain from flowing along the radial direction of the modified glass fiber, thereby fundamentally avoiding the warping problem of the traditional polypropylene plastic.
After materials C, modification liquid, polypropylene and the like are polymerized, n-hexane is added to remove thioacetate generated before, the original sulfydryl on a 4-vinylbenzyl chloride molecular chain is exposed, carbonic acid solution and calcium lactate are added, calcium ions in the calcium lactate are dissociated and adsorbed on the sulfydryl, nano calcium carbonate is generated in situ under the action of the carbonic acid solution, the nano calcium carbonate directly grows on the polymer network molecular chain, the problem that nano calcium carbonate particles are easy to agglomerate is effectively avoided, the dispersibility of the nano calcium carbonate particles is effectively improved, and the mechanical property of the polypropylene composite plastic is further enhanced. The dithiothreitol can maintain the stability of sulfydryl, and avoid the oxidation of sulfydryl to influence the reaction.
The method specifically comprises the following steps:
s1, preparing modified microspheres:
A. preparing modified three-dimensional boron carbonitride powder;
B. preparing activated carbon nanotubes;
C. synthesizing modified microspheres: placing the activated carbon nano tube and the modified three-dimensional boron carbonitride powder in deionized water for ultrasonic dispersion for 2-3h, rolling, carrying out suction filtration and drying to obtain modified microspheres;
s2, preparing modified glass fiber:
A. placing the mixed solution of the silane coupling agent in ethanol, stirring and dispersing, adding flat glass fiber and a catalyst, stirring and reacting at the rotating speed of 200-400r/min for 40-80min, taking out and drying to obtain a material B;
B. placing the material B in a xylene solution, stirring and dispersing, adding dibenzoyl peroxide and styrene monomers at the temperature of 70-90 ℃, and stirring and reacting for 50-60min at the speed of 400r/min under 200-;
s3, preparing a modification liquid: dissolving 4-vinylbenzyl chloride in N-methylpyrrolidone under stirring, adding sodium thioacetate under the heating condition of 45-65 ℃, and continuously stirring for reacting for 4-6 hours to obtain a modified solution;
s4, synthesizing polypropylene modified plastic:
A. placing the modified glass fiber and the modified microspheres in a polyethyleneimine solution for ultrasonic dispersion for 1-2h, centrifuging, filtering, washing and drying to obtain a material C;
B. mixing the material C, the modification solution, polypropylene and an initiator, stirring and reacting for 1-2h at the temperature of 80-110 ℃, adding n-hexane and dithiothreitol, continuing to stir and react for 2-4h, adding carbonic acid solution and calcium lactate, stirring and reacting for 2-3h at the rotating speed of 600r/min with 400-.
Further, the S3-S4 is required to be performed under a nitrogen atmosphere.
Further, the preparation method of the modified three-dimensional boron carbonitride powder in the step s1 comprises the following steps: (1) heating the three-dimensional boron carbonitride powder at the temperature of 900-1000 ℃ for 1-2h, cooling to room temperature, placing in deionized water, performing ultrasonic dispersion, performing suction filtration, washing and drying to obtain a material A; (2) placing polyvinyl alcohol in deionized water, stirring and dissolving, adding the material A, continuously stirring and reacting for 2-3h, and performing suction filtration and drying to obtain modified three-dimensional boron carbonitride powder; the ultrasonic dispersion power is 100-160W; temperature: 40-60 ℃; time: 1-2 h.
According to the invention, firstly, Van der Waals force among three-dimensional boron carbonitride organizational structures is reduced through high temperature and ultrasonic dispersion, and the lamellar distance among the organizational structures is increased, so that more space can be provided for modification of later-stage active groups and insertion of carbon nano tubes. The high-temperature reaction condition and the ultrasonic dispersion condition need to be strictly controlled within the specified range of the invention, so that the problem that the three-dimensional boron carbonitride powder is completely crushed or the organizational structure is not opened is avoided, and the later modification effect is influenced.
The invention further mixes the three-dimensional boron carbonitride powder after high-temperature treatment with the polyvinyl alcohol, and with the addition of the three-dimensional boron carbonitride powder, partial hydrogen bonds in the polyvinyl alcohol are destroyed and are in hydrogen bond with hydroxyl groups on the three-dimensional boron carbonitride powder, so that the polyvinyl alcohol is modified on the three-dimensional boron carbonitride powder, and the modification of the polyvinyl alcohol provides more hydroxyl active sites for the three-dimensional boron carbonitride powder.
Further, the preparation method of the activated carbon nanotube in the step s1 includes: and (3) placing the carbon nano tube in concentrated nitric acid, stirring and reacting for 1-2h, and filtering, washing and drying to obtain the activated carbon nano tube.
The invention uses concentrated nitric acid to activate the carbon nano tube, and the concentrated nitric acid can not only modify a large amount of active groups on the carbon nano tube, but also can not influence the structure and the property of the carbon nano tube.
Compared with the prior art, the invention has the following beneficial effects:
the modified microspheres in the invention are beneficial to conducting heat conduction in three-dimensional directions in the polypropylene plastic substrate, so that the heat conduction of the polypropylene modified plastic in all directions is more uniform, and the warping problem of the polypropylene plastic is effectively improved; the activated carbon nano tubes on the modified microspheres can provide a large number of active sites for the modified microspheres, and are beneficial to modification of polyethyleneimine in the later period.
The modified glass fiber is mainly prepared by modifying flat glass fiber, styrene and polyethyleneimine are modified on the flat glass fiber to obtain the modified glass fiber, the styrene on the modified glass fiber is polymerized under the action of an initiator to generate polystyrene, a styrene molecular chain can be entangled with a polypropylene molecular chain in the polymerization process, a stable polymer network is formed by taking the modified glass fiber as the center, the polypropylene molecular chain can be effectively fixed, the flow of the polypropylene molecular chain in a high-temperature state is reduced, and the warping problem of polypropylene plastic is further reduced. The modified glass fiber can effectively improve the interface compatibility between polystyrene and polypropylene. The polystyrene has excellent chemical resistance and impact resistance, and the addition of the polystyrene can effectively improve the impact resistance of the polypropylene modified plastic and prevent breakage.
According to the invention, after the modified microspheres and the modified glass fibers are treated by polyethyleneimine, a large amount of tertiary amine is carried on the surfaces of the modified microspheres and the modified glass fibers, the tertiary amine reacts with part of benzyl chloride on 4-vinylbenzyl chloride to generate quaternary ammonium salt, so that the 4-vinylbenzyl chloride is fixed on the modified microspheres and the modified glass fibers, the 4-vinylbenzyl chloride is polymerized and generates poly-4-vinylbenzyl chloride under the action of an initiator, and the poly-4-vinylbenzyl chloride is further interwoven and entangled with polystyrene and polypropylene molecular chains, so that the polymer network in the polypropylene modified plastic is further strengthened, the weather resistance of the polypropylene modified plastic is further strengthened, and the problem of high warping is further improved; the modified glass fiber and the modified glass fiber of the invention are both provided with quaternary ammonium salt with positive charge characteristic, under the action of electrostatic repulsion, the dispersibility between the modified glass fiber and the modified glass fiber is enhanced, and the polypropylene modified plastic prepared by the invention also has certain sterilization and bacteriostasis effects due to the existence of the quaternary ammonium salt.
In the invention, n-hexane is particularly added to remove thioacetate on the poly-4-vinylbenzyl chloride, so that the original sulfydryl on the poly-4-vinylbenzyl chloride is exposed, the sulfydryl has a certain adsorption effect on calcium ions with positive charges, the calcium ions adsorbed by the sulfydryl generate nano calcium carbonate in situ on a polymer network molecular chain under the action of a carbonic acid solution, and the addition of the nano calcium carbonate can further enhance the impact resistance of the polypropylene modified plastic.
The preparation method disclosed by the invention is simple in preparation process and easy in material acquisition, and the prepared polypropylene modified plastic is good in weather resistance, excellent in mechanical property, uniform in heat conduction, low in warpage rate, wide in application range and very practical, and can be used in high-temperature and low-temperature environments without easily causing a fracture problem.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
The low-warpage polypropylene modified plastic comprises the following raw material components: the modified glass fiber modified polypropylene composite material comprises, by weight, 30 parts of modified glass fiber, 20 parts of modified microspheres, 20 parts of polyethyleneimine, 30 parts of modified liquid, 80 parts of polypropylene, 10 parts of an initiator, 15 parts of n-hexane, 10 parts of dithiothreitol, 20 parts of a carbonic acid solution and 20 parts of calcium lactate.
The modified glass fiber comprises the following raw material components: the glass fiber reinforced composite material comprises, by weight, 30 parts of a silane coupling agent mixed solution, 80 parts of flat glass fibers, 10 parts of a catalyst, 25 parts of xylene, 10 parts of dibenzoyl peroxide and 20 parts of a styrene monomer.
The modifying solution comprises 4-vinylbenzyl chloride and sodium thioacetate, wherein the mass ratio of the 4-vinylbenzyl chloride to the sodium thioacetate is 3: 2.
the silane coupling agent mixed liquid comprises the following raw material components, by weight, 30 parts of vinyl silane coupling agent, 25 parts of epoxy hydrocarbon silane coupling agent and 15 parts of carboxyl silane coupling agent.
S1, preparing modified microspheres:
A. preparing modified three-dimensional boron carbonitride powder:
a. heating the three-dimensional boron carbonitride powder at 900 ℃ for 1h, cooling to room temperature, placing in deionized water, performing ultrasonic dispersion, setting the ultrasonic power at 100W, the temperature at 40 ℃ and the ultrasonic dispersion time at 1h, and performing suction filtration, washing and drying to obtain a material A;
b. and (3) placing the polyvinyl alcohol into deionized water, stirring and dissolving, adding the material A, continuously stirring and reacting for 2 hours, and carrying out suction filtration and drying to obtain the modified three-dimensional boron carbonitride powder.
B. Preparing activated carbon nanotubes: placing the carbon nano tube in concentrated nitric acid, stirring and reacting for 1h, and carrying out suction filtration, washing and drying to obtain an activated carbon nano tube;
C. synthesizing modified microspheres: placing the activated carbon nano tube and the modified three-dimensional boron carbonitride powder in deionized water, ultrasonically dispersing for 2 hours, rolling, filtering, and drying to obtain modified microspheres;
s2, preparing modified glass fiber:
A. placing the silane coupling agent mixed solution into ethanol, stirring and dispersing, adding flat glass fibers and a catalyst, stirring and reacting at the rotating speed of 200r/min for 40min, taking out and drying to obtain a material B;
B. placing the material B in a dimethylbenzene solution, stirring and dispersing, adding dibenzoyl peroxide and a styrene monomer at 70 ℃, and stirring and reacting at 200r/min for 50min to obtain modified glass fiber;
s3, preparing a modification liquid: placing 4-vinylbenzyl chloride in N-methylpyrrolidone, stirring and dissolving, adding sodium thioacetate under the heating condition of 45 ℃, and continuously stirring and reacting for 4 hours to obtain a modified solution;
s4, synthesizing polypropylene modified plastic:
A. placing the modified glass fiber and the modified microspheres in a polyethyleneimine solution for ultrasonic dispersion for 1h, centrifuging, filtering, washing and drying to obtain a material C;
B. mixing the material C, the modified solution, polypropylene and an initiator, stirring and reacting for 1h at 80 ℃, adding n-hexane and dithiothreitol, continuously stirring and reacting for 2h, adding carbonic acid solution and calcium lactate, stirring and reacting for 2h at the rotating speed of 400r/min, raising the temperature to 160 ℃, and extruding and granulating to obtain the polypropylene modified plastic.
Example 2
The low-warpage polypropylene modified plastic comprises the following raw material components: the modified glass fiber modified polypropylene composite material comprises, by weight, 40 parts of modified glass fiber, 30 parts of modified microspheres, 25 parts of polyethyleneimine, 40 parts of modified liquid, 90 parts of polypropylene, 15 parts of an initiator, 20 parts of n-hexane, 15 parts of dithiothreitol, 25 parts of a carbonic acid solution and 25 parts of calcium lactate.
The modified glass fiber comprises the following raw material components: 45 parts of mixed solution of a silane coupling agent, 90 parts of flat glass fiber, 15 parts of catalyst, 35 parts of dimethylbenzene, 13 parts of dibenzoyl peroxide and 25 parts of styrene monomer.
The modifying solution comprises 4-vinylbenzyl chloride and sodium thioacetate, wherein the mass ratio of the 4-vinylbenzyl chloride to the sodium thioacetate is 2: 1.
The silane coupling agent mixed liquid comprises, by weight, 40 parts of a vinyl silane coupling agent, 30 parts of an epoxy hydrocarbon silane coupling agent and 20 parts of a carboxyl silane coupling agent.
S1, preparing modified microspheres:
A. preparing modified three-dimensional boron carbonitride powder:
a. heating the three-dimensional boron carbonitride powder at 950 ℃ for 1.5h, cooling to room temperature, placing in deionized water, performing ultrasonic dispersion, setting the ultrasonic power at 130W, the temperature at 50 ℃ and the ultrasonic dispersion time at 1.5h, performing suction filtration, washing and drying to obtain a material A;
b. and (3) placing the polyvinyl alcohol into deionized water, stirring and dissolving, adding the material A, continuously stirring and reacting for 2.5 hours, and performing suction filtration and drying to obtain the modified three-dimensional boron carbonitride powder.
B. Preparing activated carbon nanotubes: placing the carbon nano tube in concentrated nitric acid, stirring and reacting for 1.5h, and filtering, washing and drying to obtain an activated carbon nano tube;
C. synthesizing modified microspheres: placing the activated carbon nano tube and the modified three-dimensional boron carbonitride powder in deionized water, ultrasonically dispersing for 2.5h, rolling, carrying out suction filtration and drying to obtain modified microspheres;
s2, preparing modified glass fiber:
A. placing the silane coupling agent mixed solution into ethanol, stirring and dispersing, adding flat glass fibers and a catalyst, stirring and reacting at the rotating speed of 300r/min for 60min, taking out and drying to obtain a material B;
B. placing the material B in a dimethylbenzene solution, stirring and dispersing, adding dibenzoyl peroxide and a styrene monomer at the temperature of 80 ℃, and stirring and reacting at 300r/min for 55min to obtain modified glass fiber;
s3, preparing a modification liquid: placing 4-vinylbenzyl chloride in N-methylpyrrolidone, stirring and dissolving, adding sodium thioacetate under the heating condition of 55 ℃, and continuously stirring and reacting for 5 hours to obtain a modified solution;
s4, synthesizing polypropylene modified plastic:
A. placing the modified glass fiber and the modified microspheres in a polyethyleneimine solution for ultrasonic dispersion for 1.5h, centrifuging, filtering, washing and drying to obtain a material C;
B. mixing the material C, the modified solution, polypropylene and an initiator, stirring and reacting for 1.5h at 90 ℃, adding n-hexane and dithiothreitol, continuously stirring and reacting for 3h, adding a carbonic acid solution and calcium lactate, stirring and reacting for 2.5h at the rotating speed of 500r/min, raising the temperature to 170 ℃, and extruding and granulating to obtain the polypropylene modified plastic.
Example 3
The low-warpage polypropylene modified plastic comprises the following raw material components: the modified glass fiber composite material comprises, by weight, 50 parts of modified glass fiber, 40 parts of modified microspheres, 30 parts of polyethyleneimine, 50 parts of modified liquid, 100 parts of polypropylene, 20 parts of an initiator, 25 parts of n-hexane, 20 parts of dithiothreitol, 30 parts of a carbonic acid solution and 30 parts of calcium lactate.
The modified glass fiber comprises the following raw material components: the glass fiber reinforced composite material comprises, by weight, 60 parts of a silane coupling agent mixed solution, 100 parts of flat glass fibers, 20 parts of a catalyst, 45 parts of xylene, 16 parts of dibenzoyl peroxide and 30 parts of a styrene monomer.
The modifying solution comprises 4-vinylbenzyl chloride and sodium thioacetate, wherein the mass ratio of the 4-vinylbenzyl chloride to the sodium thioacetate is 5: 2.
the silane coupling agent mixed liquid comprises, by weight, 50 parts of a vinyl silane coupling agent, 35 parts of an epoxy hydrocarbon silane coupling agent and 25 parts of a carboxyl silane coupling agent.
S1, preparing modified microspheres:
A. preparing modified three-dimensional boron carbonitride powder:
a. heating the three-dimensional boron carbonitride powder at 1000 ℃ for 2h, cooling to room temperature, placing in deionized water, performing ultrasonic dispersion, setting the ultrasonic power at 160W, the temperature at 60 ℃ and the ultrasonic dispersion time at 2h, and performing suction filtration, washing and drying to obtain a material A;
b. and (3) placing the polyvinyl alcohol into deionized water, stirring and dissolving, adding the material A, continuously stirring and reacting for 3 hours, and carrying out suction filtration and drying to obtain the modified three-dimensional boron carbonitride powder.
B. Preparing activated carbon nanotubes: placing the carbon nano tube in concentrated nitric acid, stirring and reacting for 2 hours, and filtering, washing and drying to obtain an activated carbon nano tube;
C. synthesizing modified microspheres: placing the activated carbon nano tube and the modified three-dimensional boron carbonitride powder in deionized water, ultrasonically dispersing for 3 hours, rolling, filtering, and drying to obtain modified microspheres;
s2, preparing modified glass fiber:
A. placing the silane coupling agent mixed solution into ethanol, stirring and dispersing, adding flat glass fibers and a catalyst, stirring and reacting at the rotating speed of 400r/min for 80min, taking out and drying to obtain a material B;
B. placing the material B in a dimethylbenzene solution, stirring and dispersing, adding dibenzoyl peroxide and a styrene monomer at the temperature of 90 ℃, and stirring and reacting at the speed of 400r/min for 60min to obtain modified glass fiber;
s3, preparing a modification liquid: placing 4-vinylbenzyl chloride in N-methylpyrrolidone, stirring and dissolving, adding sodium thioacetate under the heating condition of 65 ℃, and continuously stirring and reacting for 6 hours to obtain a modified solution;
s4, synthesizing polypropylene modified plastic:
A. placing the modified glass fiber and the modified microspheres in a polyethyleneimine solution for ultrasonic dispersion for 2 hours, centrifuging, filtering, washing and drying to obtain a material C;
B. mixing the material C, the modified solution, polypropylene and an initiator, stirring and reacting for 2h at 110 ℃, adding n-hexane and dithiothreitol, continuously stirring and reacting for 4h, adding carbonic acid solution and calcium lactate, stirring and reacting for 3h at the rotating speed of 600r/min, raising the temperature to 190 ℃, and extruding and granulating to obtain the polypropylene modified plastic.
Experiment: the polypropylene-modified plastic samples obtained in examples 1 to 7 were prepared into flat plate samples having dimensions of 10mm × 5mm × 1mm using an injection molding machine, and the following experiments were carried out:
tensile strength: according to the ISO527-2 standard requirement, the standard sample is made into a test sample strip by an injection molding machine, the test temperature is 24 ℃, and the test speed is 20 mm/min.
And (3) testing the bending strength: preparing a standard sample into a test sample strip by using an injection molding machine according to the ISO178 standard requirement, wherein the test temperature is 24 ℃, and the test speed is 20 mm/min.
Notched impact strength test: testing according to GB/T1043.1-2008 standard; notch type: type A, test temperature 24 ℃.
Heat distortion temperature: the test was performed with reference to the ASTM D648 standard.
Warping degree: performing a warpage test according to the standard of GBT 4677.5-1984; the length of 10mm was taken as the length of the bent side, and warpage (%). warping height/length of the bent side (10mm) × 100%.
As can be seen from the data in the table, the tensile strength, the bending strength and the notch impact strength of the polypropylene modified plastic samples prepared in the examples 1-3 are obviously improved compared with those of common polypropylene plastics, and the mechanical properties are excellent; the thermal deformation temperature is above 150 ℃, after-30 ℃ falling ball impact test, the surface of the polypropylene modified plastic has no cracks and damages, and the high and low temperature resistance is excellent. The polypropylene modified plastic prepared by the invention has good weather resistance, excellent mechanical property, low warpage rate, and far higher comprehensive performance than common polypropylene plastic, and has very high practicability.
Example 4
The difference from the embodiment 3 lies in that no modified microsphere is added, the prepared polypropylene modified plastic has poor impact strength, insufficient mechanical properties and unstable polymer network due to the lack of the modified microsphere and the lack of the heat conduction microsphere with the three-dimensional heat conduction direction as a polymer network node, polypropylene molecules easily flow under the action of high temperature, so that the polypropylene plastic sample has insufficient mechanical properties, uneven heat conduction exists in the three-dimensional direction, the warpage rate is high, and the weather resistance is poor.
Example 5
The difference from the example 3 is that the flat glass fiber is not modified, and because the flat glass fiber lacks 4-vinylbenzyl chloride and styrene monomer to be copolymerized to form a stable network structure, the shape compatibility of the common flat glass fiber and the polypropylene plastic base material is poor, and the mechanical property of the prepared polypropylene plastic sample is reduced compared with the example 3.
Example 6
The difference from the example 3 is that n-hexane is not added, thioacetate on poly-4-vinylbenzyl chloride is removed due to lack of n-hexane, a polymer network lacks of sulfydryl to adsorb calcium ions, generated nano calcium carbonate is agglomerated in polypropylene modified plastics, mechanical properties of polypropylene modified plastics samples are reduced to some extent, weather resistance is poor, and warping rate is insufficient compared with the example 3.
Example 7
The difference from the embodiment 3 is that the modified microspheres and the modified glass fibers are not treated by polyethyleneimine, because the unmodified microspheres of polyethyleneimine and the modified glass fibers lack tertiary amine provided by the polyethyleneimine to be used as adsorption sites to adsorb 4-vinylbenzyl chloride, quaternary ammonium salts with the same charge cannot be formed on the modified microspheres and the modified glass fibers, the dispersibility between the modified microspheres and the modified glass fibers is poor, the mechanical property of the prepared polypropylene modified plastic sample is poor, and the weather resistance and warping rate results are not ideal.
From the above data and experiments, we can conclude that:
the modified microspheres in the invention are beneficial to conducting heat conduction in three-dimensional directions in the polypropylene plastic substrate, so that the heat conduction of the polypropylene modified plastic in all directions is more uniform, and the warping problem of the polypropylene plastic is effectively improved; the activated carbon nano tubes on the modified microspheres can provide a large number of active sites for the modified microspheres, and are beneficial to modification of polyethyleneimine in the later period.
The modified glass fiber is mainly prepared by modifying flat glass fiber, styrene and polyethyleneimine are modified on the flat glass fiber to obtain the modified glass fiber, the styrene on the modified glass fiber is polymerized under the action of an initiator to generate polystyrene, a styrene molecular chain can be entangled with a polypropylene molecular chain in the polymerization process, a stable polymer network is formed by taking the modified glass fiber as the center, the polypropylene molecular chain can be effectively fixed, the flow of the polypropylene molecular chain in a high-temperature state is reduced, and the warping problem of polypropylene plastic is further reduced. The modified glass fiber can effectively improve the interface compatibility between polystyrene and polypropylene. The polystyrene has excellent chemical resistance and impact resistance, and the addition of the polystyrene can effectively improve the impact resistance of the polypropylene modified plastic and prevent breakage.
According to the invention, after the modified microspheres and the modified glass fibers are treated by polyethyleneimine, a large amount of tertiary amine is carried on the surfaces of the modified microspheres and the modified glass fibers, the tertiary amine reacts with part of benzyl chloride on 4-vinylbenzyl chloride to generate quaternary ammonium salt, so that the 4-vinylbenzyl chloride is fixed on the modified microspheres and the modified glass fibers, the 4-vinylbenzyl chloride is polymerized and generates poly-4-vinylbenzyl chloride under the action of an initiator, and the poly-4-vinylbenzyl chloride is further interwoven and entangled with polystyrene and polypropylene molecular chains, so that the polymer network in the polypropylene modified plastic is further strengthened, the weather resistance of the polypropylene modified plastic is further strengthened, and the problem of high warping is further improved; the modified glass fiber and the modified glass fiber of the invention are both provided with quaternary ammonium salt with positive charge characteristic, under the action of electrostatic repulsion, the dispersibility between the modified glass fiber and the modified glass fiber is enhanced, and the polypropylene modified plastic prepared by the invention also has certain sterilization and bacteriostasis effects due to the existence of the quaternary ammonium salt.
In the invention, n-hexane is particularly added to remove thioacetate on the poly-4-vinylbenzyl chloride, so that the original sulfydryl on the poly-4-vinylbenzyl chloride is exposed, the sulfydryl has a certain adsorption effect on calcium ions with positive charges, the calcium ions adsorbed by the sulfydryl generate nano calcium carbonate in situ on a polymer network molecular chain under the action of a carbonic acid solution, and the addition of the nano calcium carbonate can further enhance the impact resistance of the polypropylene modified plastic.
The preparation method disclosed by the invention is simple in preparation process and easy in material acquisition, and the prepared polypropylene modified plastic is good in weather resistance, excellent in mechanical property, uniform in heat conduction, low in warpage rate, wide in application range and very practical, and can be used in high-temperature and low-temperature environments without easily causing a fracture problem.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A low-warpage polypropylene modified plastic is characterized in that: the raw material components are as follows: 30-50 parts of modified glass fiber, 20-40 parts of modified microspheres, 20-30 parts of polyethyleneimine, 30-50 parts of modified liquid, 80-100 parts of polypropylene, 10-20 parts of initiator, 15-25 parts of n-hexane, 10-20 parts of dithiothreitol, 20-30 parts of carbonic acid solution and 20-30 parts of calcium lactate.
2. The low-warpage polypropylene modified plastic as claimed in claim 1, wherein the modified glass fiber comprises the following raw material components: 30-60 parts of mixed liquid of a silane coupling agent, 80-100 parts of flat glass fiber, 10-20 parts of a catalyst, 25-45 parts of dimethylbenzene, 10-16 parts of dibenzoyl peroxide and 20-30 parts of a styrene monomer.
3. The low warpage polypropylene modified plastic as claimed in claim 1, wherein the modified microspheres are three-dimensional silicon carbonitride microspheres loaded with activated carbon nanotubes.
4. The plastic modified by polypropylene with low warpage as claimed in claim 1, wherein the modification solution comprises 4-vinylbenzyl chloride and sodium thioacetate, and the mass ratio of the 4-vinylbenzyl chloride to the sodium thioacetate is (3-5): 2.
5. the low warpage polypropylene modified plastic as claimed in claim 2, wherein the silane coupling agent mixture comprises, by weight, 30-50 parts of vinyl silane coupling agent, 25-35 parts of epoxy hydrocarbon silane coupling agent, and 15-25 parts of carboxyl silane coupling agent.
6. The preparation method of the low-warpage polypropylene modified plastic is characterized by comprising the following steps of:
s1, preparing modified microspheres:
A. preparing modified three-dimensional boron carbonitride powder;
B. preparing activated carbon nanotubes;
C. synthesizing modified microspheres;
s2, preparing modified glass fiber:
A. placing the silane coupling agent mixed solution into ethanol, stirring and dispersing, adding flat glass fiber and a catalyst, stirring, taking out and drying to obtain a material B;
B. placing the material B in a dimethylbenzene solution, stirring and dispersing, adding dibenzoyl peroxide and a styrene monomer, and stirring to obtain a modified glass fiber;
s3, preparing a modification liquid: under the protection of nitrogen, 4-vinyl benzyl chloride is placed in N-methyl pyrrolidone to be stirred and dissolved, sodium thioglycolate is added, and stirring is continued to obtain a modified solution;
s4, synthesizing polypropylene modified plastic:
A. placing the modified glass fiber and the modified microspheres in a polyethyleneimine solution for ultrasonic dispersion, centrifuging, filtering, washing and drying to obtain a material C;
B. and mixing and stirring the material C, the modified solution, the polypropylene and the initiator, adding n-hexane and dithiothreitol, adding carbonic acid solution and calcium lactate, stirring, extruding and granulating to obtain the polypropylene modified plastic.
7. The preparation method of the low-warpage polypropylene modified plastic as claimed in claim 6, is characterized by comprising the following steps:
s1, preparing modified microspheres:
A. preparing modified three-dimensional boron carbonitride powder;
B. preparing activated carbon nanotubes;
C. synthesizing modified microspheres: placing the activated carbon nano tube and the modified three-dimensional boron carbonitride powder in deionized water for ultrasonic dispersion for 2-3h, rolling, carrying out suction filtration and drying to obtain modified microspheres;
s2, preparing modified glass fiber:
A. placing the mixed solution of the silane coupling agent in ethanol, stirring and dispersing, adding flat glass fiber and a catalyst, stirring and reacting at the rotating speed of 200-400r/min for 40-80min, taking out and drying to obtain a material B;
B. placing the material B in a xylene solution, stirring and dispersing, adding dibenzoyl peroxide and styrene monomers at the temperature of 70-90 ℃, and stirring and reacting for 50-60min at the speed of 400r/min under 200-;
s3, preparing a modification liquid: dissolving 4-vinylbenzyl chloride in N-methylpyrrolidone under stirring, adding sodium thioacetate under the heating condition of 45-65 ℃, and continuously stirring for reacting for 4-6 hours to obtain a modified solution;
s4, synthesizing polypropylene modified plastic:
A. placing the modified glass fiber and the modified microspheres in a polyethyleneimine solution for ultrasonic dispersion for 1-2h, centrifuging, filtering, washing and drying to obtain a material C;
B. mixing the material C, the modification solution, polypropylene and an initiator, stirring and reacting for 1-2h at the temperature of 80-110 ℃, adding n-hexane and dithiothreitol, continuing to stir and react for 2-4h, adding carbonic acid solution and calcium lactate, stirring and reacting for 2-3h at the rotating speed of 600r/min with 400-.
8. The preparation method of the low-warpage polypropylene modified plastic according to claim 7, wherein the preparation method of the modified three-dimensional boron carbonitride powder in the step S1. comprises the following steps: (1) heating the three-dimensional boron carbonitride powder at the temperature of 900-1000 ℃ for 1-2h, cooling to room temperature, placing in deionized water, performing ultrasonic dispersion, performing suction filtration, washing and drying to obtain a material A; (2) and (3) placing the polyvinyl alcohol into deionized water, stirring and dissolving, adding the material A, continuously stirring and reacting for 2-3h, and performing suction filtration and drying to obtain the modified three-dimensional boron carbonitride powder.
9. The method for preparing the low-warpage polypropylene modified plastic as claimed in claim 7, wherein the method for preparing the activated carbon nanotubes in the step S1. comprises the following steps: and (3) placing the carbon nano tube in concentrated nitric acid, stirring and reacting for 1-2h, and filtering, washing and drying to obtain the activated carbon nano tube.
10. The method for preparing low warpage polypropylene modified plastic as claimed in claim 8, wherein the ultrasonic dispersion power is 100-; temperature: 40-60 ℃; time: 1-2 h.
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