CN116903982B - High-strength corrosion-resistant polypropylene composite material and preparation method thereof - Google Patents
High-strength corrosion-resistant polypropylene composite material and preparation method thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 114
- -1 polypropylene Polymers 0.000 title claims abstract description 114
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 230000007797 corrosion Effects 0.000 title claims abstract description 43
- 238000005260 corrosion Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 101
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052582 BN Inorganic materials 0.000 claims abstract description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 22
- 239000000600 sorbitol Substances 0.000 claims abstract description 22
- 229920001661 Chitosan Polymers 0.000 claims abstract description 18
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002927 oxygen compounds Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-strength corrosion-resistant polypropylene composite material and a preparation method thereof, wherein the high-strength corrosion-resistant polypropylene composite material is prepared from the following raw materials in parts by weight: 40-80 parts of polypropylene; 20-40 parts of maleic anhydride; 5-15 parts of styrene; 2-4 parts of an initiator; 20-30 parts of modified boron nitride; 10-20 parts of chitosan; the boron nitride is modified boron nitride, and the modified boron nitride is prepared by modifying the following raw materials: boron nitride, sorbitol and octadecyl trimethyl ammonium bromide. The polypropylene composite material has the effect of improving the tensile strength of the polypropylene composite material.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-strength corrosion-resistant polypropylene composite material and a preparation method thereof.
Background
Polypropylene is a semi-crystalline thermoplastic plastic, is one of the thermoplastic polymer materials with the most development prospect at present, is a polymer formed by the addition polymerization of propylene, and has the advantages of low density, easy processing, good stress bending resistance and the like; the product prepared from the polypropylene material can meet the development requirements of light weight, low cost, environmental protection and the like, and along with the development requirements of diversification and functionalization of the product, the product has higher requirements on the polypropylene material.
The existing polypropylene material has the common problems of poor toughness, very sensitive notch, outstanding low-temperature brittleness and large molding shrinkage, so that the tensile strength of the polypropylene material is poor, and the application range is limited.
Disclosure of Invention
In order to improve the tensile strength of the polypropylene composite material, the application provides a high-strength corrosion-resistant polypropylene composite material and a preparation method thereof.
In a first aspect, the present application provides a high strength corrosion resistant polypropylene composite.
The application provides a high-strength corrosion-resistant polypropylene composite material which is prepared from the following raw materials in parts by weight: 40-80 parts of polypropylene; 20-40 parts of maleic anhydride; 5-15 parts of styrene; 2-4 parts of an initiator; 20-30 parts of modified boron nitride; 10-20 parts of chitosan; the boron nitride is modified boron nitride, and the modified boron nitride is prepared by modifying the following raw materials: boron nitride, sorbitol and octadecyl trimethyl ammonium bromide.
By adopting the technical scheme, the initiator and the polar monomer maleic anhydride are added, the melt extrusion grafting polypropylene is carried out, the polypropylene is subjected to chain extension, the maleic anhydride and the polypropylene contain various functional groups, the double bonds of the polypropylene and the styrene are easy to carry out copolymerization reaction with other polymers, the styrene contains vinyl, the double bonds form stable free radicals in the components, the grafting rate of the maleic anhydride is further improved, the anhydride group activity of the maleic anhydride is stronger, the maleic anhydride is subjected to chemical reaction with the functional groups such as hydroxyl, and the compatibility and the cohesiveness of the polymer and the filler are improved, so that the mechanical property and the corrosion resistance of the polypropylene composite material are improved; the boron nitride modification is carried out to ensure that the boron oxide has better mechanical property and chemical stability, and the chitosan is added to improve the grafting rate of the polypropylene grafted maleic anhydride, thereby being beneficial to improving the compatibility between the polypropylene and the boron nitride and further improving the mechanical property of the boron nitride reinforced polypropylene composite material.
Preferably, the preparation method of the modified boron nitride comprises the following steps: and (3) carrying out vacuum drying on 10-20 parts by weight of boron nitride, grinding with 30-60 parts by weight of sorbitol, mixing and stirring with 5-10 parts by weight of octadecyl trimethyl ammonium bromide, washing and heating and drying filtered filter residues, and thus obtaining the modified boron nitride.
Through adopting above-mentioned technical scheme, this application is through sorbitol to the boron nitride modification, and boron nitride is oxygen compound, has higher thermal conductivity and mechanical properties, and sorbitol wraps up boron nitride, makes boron nitride surface grafted hydroxyl functional group, and octadecyl trimethyl ammonium bromide is as surfactant, helps the dispersion of boron nitride in the in-process of grinding, and the boron nitride after the modification is filled into polypropylene as the filler, reduces the phenomenon that appears agglomerating between the components, and sorbitol takes place thermolysis easily, makes boron nitride have good stability under high temperature condition, and then improves polypropylene composite's heat resistance.
Preferably, the maleic anhydride is modified maleic anhydride, and the preparation method of the modified maleic anhydride comprises the following steps: 10-20 parts of maleic anhydride, 1-3 parts of glycidyl methacrylate and 10-20 parts of N' -N-dimethylbenzoyl are heated in a mixed water bath, 1-2 parts of sodium persulfate is added for reaction for 15-20 hours, washing and drying are carried out after suction filtration, 2-4 parts of ethylenediamine is added for heating in a water bath, and the modified maleic anhydride is obtained after suction filtration and drying.
Through adopting above-mentioned technical scheme, this application is through carrying out the modification to maleic anhydride, and maleic anhydride carries out the reaction grafting with glycidyl methacrylate earlier, and ethylenediamine is carrying out the modification to maleic anhydride on, makes maleic anhydride have bigger specific surface area, and ethylenediamine and maleic anhydride's combination effect is good, and then improves maleic anhydride's stability, and modified boron nitride is adsorbed on maleic anhydride surface more easily simultaneously to improve polypropylene composite's mechanical strength and corrosion resistance.
Preferably, the weight ratio of the boron nitride to the sorbitol to the octadecyl trimethyl ammonium bromide is 1: (3-3.5): (0.4-0.54).
By adopting the technical scheme, when the boron nitride, the sorbitol and the octadecyl trimethyl ammonium bromide are mixed in a specific weight ratio, the sorbitol can better coat the boron nitride, so that the boron nitride has better dispersibility, the aggregation of components is reduced, and the mechanical property and the heat resistance of the polypropylene composite material are further improved.
Preferably, the polypropylene has a molecular weight of 1000 to 4000; the viscosity of the chitosan is 100-200 mPa.s.
By adopting the technical scheme, the polypropylene composite material with better mechanical strength can be prepared by selecting proper polypropylene and chitosan.
Preferably, the weight ratio of the polypropylene to the maleic anhydride to the styrene to the modified boron nitride is 1: (0.55-0.6): (0.1-0.14): (0.45-0.47).
By adopting the technical scheme, when the raw materials are in a specific proportion, the components contain a higher double bond structure, which is beneficial to the grafting reaction, so that the grafting rate of the polypropylene grafted maleic anhydride is improved; the modified boron nitride can be uniformly distributed in the components, can be used as a filler to tightly fill the pores of the components, and simultaneously tightly bonds the polypropylene and the styrene, so that the mechanical property of the polypropylene composite material is improved, the compactness of each component in the polypropylene composite material is improved, and the heat resistance of the polypropylene composite material is improved.
Preferably, the initiator comprises one of dicumyl peroxide and azobisisobutyronitrile.
By adopting the technical scheme, the performance of the polypropylene composite material can be improved by selecting a proper initiator.
Preferably, the particle size of the boron nitride is in the range of 4-20 μm.
By adopting the technical scheme, the particle size of the boron nitride is controlled, so that the boron nitride can be better filled on the polypropylene grafted maleic anhydride, and the tensile strength and the bending strength of the polypropylene composite material are effectively improved.
In a second aspect, the preparation method of the high-strength corrosion-resistant polypropylene composite material provided by the application adopts the following preparation method:
a preparation method of a high-strength corrosion-resistant polypropylene composite material comprises the following steps: firstly, mixing and stirring styrene and chitosan, then uniformly mixing polypropylene, maleic anhydride, an initiator and modified boron nitride, carrying out melt extrusion, and granulating to obtain the composite material.
By adopting the technical scheme, the polypropylene composite material prepared by extrusion granulation after melt blending has good tensile strength and corrosion resistance.
Preferably, the extrusion temperature is 160-200 ℃ and the rotating speed is 100-200r/min.
By adopting the technical scheme, the proper extrusion temperature is controlled, so that the polypropylene composite material with good tensile strength and corrosion resistance is prepared.
In summary, the present application includes the following beneficial technical effects:
1. according to the preparation method, the initiator and the polar monomer maleic anhydride are added, the grafted polypropylene is melt extruded, the polypropylene is subjected to chain extension, the maleic anhydride and the polypropylene contain various functional groups, double bonds of the polypropylene and styrene are easy to carry out copolymerization reaction with other polymers, the styrene contains vinyl groups, the double bonds form stable free radicals in the components, the grafting rate of the maleic anhydride is further improved, the anhydride group of the maleic anhydride is high in activity and chemically reacts with the functional groups such as hydroxyl groups, the compatibility and the cohesiveness of the polymer and the filler are improved, and therefore the mechanical property and the corrosion resistance of the polypropylene composite material are improved; the boron nitride modification is carried out to ensure that the boron oxide has better mechanical property and chemical stability, and the chitosan is added to improve the grafting rate of the polypropylene grafted maleic anhydride, thereby being beneficial to improving the compatibility between the polypropylene and the boron nitride and further improving the mechanical property of the boron nitride reinforced polypropylene composite material.
2. According to the modified boron nitride composite material, the sorbitol is used for modifying the boron nitride, the boron nitride is an oxygen compound, the higher thermal conductivity and the higher mechanical property are achieved, the sorbitol wraps the boron nitride, the surface of the boron nitride is grafted with hydroxyl functional groups, the octadecyl trimethyl ammonium bromide is used as a surfactant, the boron nitride is dispersed in the grinding process, the modified boron nitride is used as a filler to be filled into polypropylene, the phenomenon of agglomeration among components is reduced, the sorbitol is easy to thermally decompose, the boron nitride has good stability under the high-temperature condition, and the heat resistance of the polypropylene composite material is improved.
3. According to the modified polypropylene composite material, the maleic anhydride is modified, the maleic anhydride is firstly subjected to reaction grafting with the glycidyl methacrylate, the ethylenediamine is modified on the maleic anhydride, so that the maleic anhydride has larger specific surface area, the combination effect of the ethylenediamine and the maleic anhydride is good, the stability of the maleic anhydride is further improved, and meanwhile, the modified boron nitride is easier to adsorb on the surface of the maleic anhydride, so that the mechanical strength and the corrosion resistance of the polypropylene composite material are improved.
Detailed Description
The present application is described in further detail below in connection with examples and comparative examples.
Preparation example
Preparation example 1
A preparation method of modified boron nitride comprises the following steps:
putting 10kg of boron nitride into a vacuum drying oven, vacuum drying for 24 hours at the temperature of 60 ℃, uniformly mixing the dried boron nitride with 30kg of sorbitol, putting into a planetary ball mill, ball milling for 6 hours at the rotating speed of 500r/min, mixing with 5kg of octadecyl trimethyl ammonium bromide, dissolving in water at the temperature of 80 ℃, stirring for 30 minutes, filtering, putting filter residues into the vacuum drying oven, and vacuum drying for 24 hours at the temperature of 80 ℃ to obtain modified boron nitride; wherein the particle size of the boron nitride is 50 μm.
Preparation example 2
A preparation method of modified boron nitride comprises the following steps:
putting 20kg of boron nitride into a vacuum drying oven, vacuum drying for 24 hours at the temperature of 60 ℃, uniformly mixing the dried boron nitride with 60kg of sorbitol, putting into a planetary ball mill, ball milling for 6 hours at the rotating speed of 500r/min, mixing with 10kg of octadecyl trimethyl ammonium bromide, dissolving in water at the temperature of 80 ℃, stirring for 30 minutes, filtering, putting filter residues into the vacuum drying oven, and vacuum drying for 24 hours at the temperature of 80 ℃ to obtain modified boron nitride; wherein the particle size of the boron nitride is 20 μm.
Preparation example 3
A method for producing modified boron nitride was different from that of production example 2 in that the amount of boron nitride to be charged was 15kg, the amount of sorbitol to be charged was 45kg, and the amount of octadecyl trimethyl ammonium bromide to be charged was 6kg.
Preparation example 4
A method for producing modified boron nitride was different from that of production example 2 in that the amount of boron nitride to be charged was 15kg, the amount of sorbitol to be charged was 52kg, and the amount of octadecyl trimethyl ammonium bromide to be charged was 8kg.
Examples
Example 1
A preparation method of a high-strength corrosion-resistant polypropylene composite material comprises the following steps:
firstly, putting 5kg of styrene and 10kg of chitosan into a high-speed mixer, uniformly mixing at the rotating speed of 100r/min, then putting 40kg of polypropylene, 20kg of maleic anhydride, 2kg of dicumyl peroxide initiator and 20kg of modified boron nitride prepared in preparation example 1 into the high-speed mixer, continuously stirring uniformly, and then putting the mixture into a double-screw extruder for melt extrusion, wherein the extrusion temperature of the screw extruder is 120 ℃, the rotating speed is 250r/min, and granulating to obtain the composite material.
The molecular weight of polypropylene is 1000 and the viscosity of chitosan is 200 mPas.
Example 2
A preparation method of a high-strength corrosion-resistant polypropylene composite material comprises the steps of firstly putting 15kg of styrene and 20kg of chitosan into a high-speed mixer, uniformly mixing at the rotating speed of 100r/min, putting 80kg of polypropylene, 40kg of maleic anhydride, 4kg of azodiisobutyronitrile initiator and 30kg of modified boron nitride prepared in preparation example 1 into the high-speed mixer, continuously stirring uniformly, putting the mixture into a double-screw extruder, performing melt extrusion, wherein the extrusion temperature of the screw extruder is 120 ℃, and the rotating speed of the screw extruder is 250r/min, and granulating to obtain the composite material.
Wherein the molecular weight of the polypropylene is 4000, and the viscosity of the chitosan is 100 mPa.s.
Example 3
A preparation method of a high-strength corrosion-resistant polypropylene composite material comprises the steps of firstly putting 10kg of styrene and 15kg of chitosan into a high-speed mixer, uniformly mixing at the rotating speed of 100r/min, putting 60kg of polypropylene, 30kg of maleic anhydride, 3kg of dicumyl peroxide initiator and 25kg of modified boron nitride prepared in preparation example 1 into the high-speed mixer, continuously stirring uniformly, and putting the mixture into a double-screw extruder for melt extrusion, wherein the extrusion temperature of the screw extruder is 120 ℃, the rotating speed of 250r/min, and granulating to obtain the composite material.
Wherein the molecular weight of the polypropylene is 4000 and the viscosity of the chitosan is 200 mPa.s.
Example 4
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 3 in that: the modified boron nitride produced in production example 1 was replaced with the modified boron nitride produced in production example 2 in equal amount.
Example 5
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 3 in that the modified boron nitride prepared in preparation example 1 is replaced with the modified boron nitride prepared in preparation example 3 in equal amount.
Example 6
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 3 in that the modified boron nitride prepared in preparation example 1 is replaced with the modified boron nitride prepared in preparation example 4 in equal amount.
Example 7
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 6 in that: the maleic anhydride is modified maleic anhydride, and the preparation method of the modified maleic anhydride comprises the following steps: 10kg of maleic anhydride, 10kg of N' N-dimethylbenzoyl and 1kg of glycidyl methacrylate are heated in a water bath at 50 ℃ for 30min, then 1kg of ammonium persulfate is added for graft polymerization reaction for 18h, the mixture is washed by acetone, then the mixture is kept stand and dried for 24h at 60 ℃, then 2kg of ethylenediamine is added for heating in a water bath at 90 ℃ for 8h, the mixture is washed by water and then the mixture is put into a baking oven for drying for 6h at 80 ℃ to obtain the modified maleic anhydride.
Example 8
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 6 in that: the maleic anhydride is modified maleic anhydride, and the preparation method of the modified maleic anhydride comprises the following steps: 20kg of maleic anhydride, 20kg of N' N-dimethylbenzoyl and 3kg of glycidyl methacrylate are heated in a water bath at 50 ℃ for 30min, then 2kg of ammonium persulfate is added for graft polymerization reaction for 18h, the mixture is washed by acetone, then the mixture is kept stand and dried for 24h at 60 ℃, then 4kg of ethylenediamine is added for heating in a water bath at 90 ℃ for 8h, the mixture is washed by water and then the mixture is put into a baking oven for drying for 6h at 80 ℃ to obtain the modified maleic anhydride.
Example 9
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 8 in that: the polypropylene was charged in an amount of 60kg, the modified maleic anhydride was charged in an amount of 33kg, the styrene was charged in an amount of 6kg, and the modified boron nitride produced in production example 4 was charged in an amount of 27kg.
Example 10
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 8 in that: the polypropylene was charged in an amount of 60kg, the modified maleic anhydride was charged in an amount of 36kg, the styrene was charged in an amount of 8kg, and the modified boron nitride produced in production example 4 was charged in an amount of 28kg.
Comparative example
Comparative example 1
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from the embodiment 1 in that: the modified boron nitride produced in production example 1 was replaced with boron nitride in equal amounts.
Comparative example 2
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from the embodiment 1 in that: the modified boron nitride produced in production example 1 was replaced with graphene in equal amount.
Comparative example 3
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from example 1 in that modified boron nitride is not added.
Comparative example 4
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from the embodiment 1 in that: no chitosan was added.
Comparative example 5
A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is different from the embodiment 1 in that: the maleic anhydride was replaced with acrylic acid in equal amounts.
Performance test:
tensile strength test: the polypropylene composites prepared in examples 1-10 and comparative examples 1-5 were tested for tensile strength according to the method specified in GB/T1040-2018 at a tensile rate of 10 mm/min.
Corrosion resistance test: the polypropylene composites prepared in examples 1 to 10 and comparative examples 1 to 5 were immersed in seawater for 240 hours at a stretching rate of 10mm/min according to the method specified in GB/T1040-2018, and the polypropylene composites were subjected to a tensile strength test.
Heat resistance test: the polypropylene composites prepared in examples 1-10 and comparative examples 1-5 were placed in a thermo-oxidative aging oven and heated at a temperature of 150℃for 30d, after which the tensile strength test was carried out according to the method specified in GB/T1040-2018.
According to the data comparison of the examples 1-4 and the comparative examples 1-5, the initiator and the polar monomer maleic anhydride are added, the grafted polypropylene is melt extruded, the polypropylene is chain-extended, and the mechanical property and the corrosion resistance of the polypropylene composite material are improved; the modified boron nitride has better mechanical property and chemical stability, and the chitosan can improve the grafting rate of the polypropylene grafted maleic anhydride, thereby being beneficial to improving the compatibility between the polypropylene and the boron nitride and further improving the mechanical property of the boron nitride reinforced polypropylene composite material.
According to the data comparison of the examples 3-6, the modified boron nitride is modified by sorbitol, the boron nitride is an oxygen compound, the boron nitride has higher thermal conductivity and mechanical property, the sorbitol wraps the boron nitride, the surface of the boron nitride is grafted with hydroxyl functional groups, octadecyl trimethyl ammonium bromide is used as a surfactant, the dispersion of the boron nitride is facilitated in the grinding process, the modified boron nitride is used as a filler to be filled into polypropylene, the phenomenon of agglomeration among components is reduced, the sorbitol is easy to thermally decompose, the boron nitride has good stability under the high-temperature condition, and the heat resistance of the polypropylene composite material is further improved.
According to the data comparison of the examples 6-8, the maleic anhydride is modified, the maleic anhydride is firstly subjected to reaction grafting with the glycidyl methacrylate, and the ethylenediamine is modified on the maleic anhydride, so that the maleic anhydride has larger specific surface area, the combination effect of the ethylenediamine and the maleic anhydride is good, the stability of the maleic anhydride is further improved, and meanwhile, the modified boron nitride is easier to be adsorbed on the surface of the maleic anhydride, so that the mechanical strength and the corrosion resistance of the polypropylene composite material are improved.
According to the data comparison of examples 8-10, when the polypropylene, the maleic anhydride, the styrene and the modified boron nitride are in a specific proportion, the components contain a higher double bond structure, which is beneficial to the grafting reaction, so that the grafting rate of the polypropylene to the maleic anhydride is improved; the modified boron nitride can be uniformly distributed in the components, can be used as a filler to tightly fill the pores of the components, and simultaneously tightly bonds the polypropylene and the styrene, so that the mechanical property of the polypropylene composite material is improved, the compactness of each component in the polypropylene composite material is improved, and the heat resistance of the polypropylene composite material is improved.
The specific embodiments are illustrative only and not intended to be limiting, as modifications would be required to the embodiments after reading the present specification without inventive contribution, but would be protected by the patent laws within the scope of the claims of the present application.
Claims (8)
1. A high-strength corrosion-resistant polypropylene composite material is characterized in that: the composite material is prepared from the following raw materials in parts by weight: 40-80 parts of polypropylene; 20-40 parts of maleic anhydride; 5-15 parts of styrene; 2-4 parts of an initiator; 20-30 parts of modified boron nitride; 10-20 parts of chitosan; the boron nitride is modified boron nitride, and the modified boron nitride is prepared by modifying the following raw materials: boron nitride, sorbitol and octadecyl trimethyl ammonium bromide; the preparation method of the modified boron nitride comprises the following steps: grinding 10-20 parts by weight of boron nitride with 30-60 parts by weight of sorbitol after vacuum drying, mixing and stirring with 5-10 parts by weight of octadecyl trimethyl ammonium bromide, and washing and heating and drying filtered residues to obtain the modified boron nitride; the maleic anhydride is modified maleic anhydride, and the preparation method of the modified maleic anhydride comprises the following steps: mixing 10-20 parts by weight of maleic anhydride, 1-3 parts by weight of glycidyl methacrylate and 10-20 parts by weight of N' -N-dimethylbenzamide, heating in a water bath, adding 1-2 parts by weight of sodium persulfate, reacting for 15-20 hours, filtering, washing, drying, adding 2-4 parts by weight of ethylenediamine, heating in a water bath, filtering, and drying to obtain the modified maleic anhydride.
2. The high strength corrosion resistant polypropylene composite of claim 1, wherein: the weight ratio of the boron nitride to the sorbitol to the octadecyl trimethyl ammonium bromide is 1: (3-3.5): (0.4-0.54).
3. The high strength corrosion resistant polypropylene composite of claim 1, wherein: the molecular weight of the polypropylene is 1000-4000; the viscosity of the chitosan is 100-200 mPa.s.
4. The high strength corrosion resistant polypropylene composite of claim 2, wherein: the weight ratio of the polypropylene to the modified maleic anhydride to the styrene to the modified boron nitride is 1: (0.55-0.6): (0.1-0.14): (0.45-0.47).
5. The high strength corrosion resistant polypropylene composite of claim 1, wherein: the initiator comprises one of dicumyl peroxide and azobisisobutyronitrile.
6. The high strength corrosion resistant polypropylene composite of claim 1, wherein: the particle size of the boron nitride ranges from 4 to 20 mu m.
7. A method for preparing a high-strength corrosion-resistant polypropylene composite material, which is characterized by being used for preparing the high-strength corrosion-resistant polypropylene composite material according to any one of claims 1 to 6, and comprising the following steps: firstly, mixing and stirring styrene and chitosan, then uniformly mixing polypropylene, maleic anhydride, an initiator and modified boron nitride, carrying out melt extrusion, and granulating to obtain the composite material.
8. The method for preparing the high-strength corrosion-resistant polypropylene composite material according to claim 7, wherein the method comprises the following steps: the extrusion temperature is 160-200 ℃ and the rotating speed is 100-200r/min.
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Citations (4)
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|---|---|---|---|---|
| CN101143946A (en) * | 2007-09-04 | 2008-03-19 | 浙江大学 | Method for extruding and preparing maleation polypropylene by supercritical reaction |
| WO2014000654A1 (en) * | 2012-06-27 | 2014-01-03 | 深圳市科聚新材料有限公司 | Low-odour polypropene grafted maleic anhydride extruded in twin-screw extruder and method for preparing same |
| CN103755878A (en) * | 2013-12-31 | 2014-04-30 | 广州鹿山新材料股份有限公司 | High-grating-rate and low-odor polypropylene resin composition and preparation method thereof |
| CN115286740A (en) * | 2022-08-08 | 2022-11-04 | 山东天风新材料有限公司 | Method for preparing polypropylene grafted maleic anhydride suitable for industrial production |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143946A (en) * | 2007-09-04 | 2008-03-19 | 浙江大学 | Method for extruding and preparing maleation polypropylene by supercritical reaction |
| WO2014000654A1 (en) * | 2012-06-27 | 2014-01-03 | 深圳市科聚新材料有限公司 | Low-odour polypropene grafted maleic anhydride extruded in twin-screw extruder and method for preparing same |
| CN103755878A (en) * | 2013-12-31 | 2014-04-30 | 广州鹿山新材料股份有限公司 | High-grating-rate and low-odor polypropylene resin composition and preparation method thereof |
| CN115286740A (en) * | 2022-08-08 | 2022-11-04 | 山东天风新材料有限公司 | Method for preparing polypropylene grafted maleic anhydride suitable for industrial production |
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