CN115678166B - Fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN115678166B CN115678166B CN202211564054.1A CN202211564054A CN115678166B CN 115678166 B CN115678166 B CN 115678166B CN 202211564054 A CN202211564054 A CN 202211564054A CN 115678166 B CN115678166 B CN 115678166B
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- -1 polypropylene Polymers 0.000 title claims abstract description 88
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 87
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 87
- 239000000835 fiber Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000001746 injection moulding Methods 0.000 claims abstract description 29
- 239000012778 molding material Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 10
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 235000001968 nicotinic acid Nutrition 0.000 claims abstract description 6
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 6
- 229960003512 nicotinic acid Drugs 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- KTMJZMQYZGNYBQ-UHFFFAOYSA-L copper;pyridine-3-carboxylate Chemical group [Cu+2].[O-]C(=O)C1=CC=CN=C1.[O-]C(=O)C1=CC=CN=C1 KTMJZMQYZGNYBQ-UHFFFAOYSA-L 0.000 claims description 8
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 7
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 7
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 7
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 7
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 7
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- OGTPCWAHIVWKGI-UHFFFAOYSA-L cobalt(2+);pyridine-3-carboxylate Chemical compound [Co+2].[O-]C(=O)C1=CC=CN=C1.[O-]C(=O)C1=CC=CN=C1 OGTPCWAHIVWKGI-UHFFFAOYSA-L 0.000 claims description 2
- NUPHTAVBZFNOGK-UHFFFAOYSA-L nickel(2+) pyridine-3-carboxylate Chemical compound N1=CC(=CC=C1)C(=O)[O-].[Ni+2].N1=CC(=CC=C1)C(=O)[O-] NUPHTAVBZFNOGK-UHFFFAOYSA-L 0.000 claims description 2
- 229940068096 zinc nicotinate Drugs 0.000 claims description 2
- VYAAXNAPTXCMLY-UHFFFAOYSA-L zinc;pyridine-3-carboxylate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CN=C1.[O-]C(=O)C1=CC=CN=C1 VYAAXNAPTXCMLY-UHFFFAOYSA-L 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 2
- 238000005452 bending Methods 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012634 fragment Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003733 fiber-reinforced composite Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to a fiber reinforced polypropylene composite material and a preparation method thereof, wherein the preparation method comprises the following steps of injecting polypropylene into a silane coupling agent solution, and obtaining a first component after stirring and modifying; adding ethylene glycol and a tri-monomer into a polyester bottle chip for alcoholysis, and adding 5- (2-pyridine) isophthalic acid, isophthalic acid and nicotinic acid metal salt for reaction to obtain a second component; adding polyether and lignin-acrylamide-styrene graft copolymer into the mixture of the first component and the second component for reaction to obtain a reaction solution; and (3) uniformly mixing the reaction solution and the auxiliary agent, extruding by a double-screw extruder, and granulating to obtain the fiber reinforced polypropylene composite material. According to the preparation method, the polypropylene injection molding material and the polyester bottle chip are recovered, and the process is optimized to reduce the interfacial binding force between the polyester fiber and the polypropylene matrix, so that the obtained fiber reinforced polypropylene composite material has good mechanical properties.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a fiber reinforced polypropylene composite material and a preparation method thereof.
Background
The fiber reinforced composite material consists of reinforced fiber and polypropylene matrix, and the fiber has small diameter, generally below 10 microns, less defects and less fracture strain of about thirty thousandths, is a brittle material, and is easy to damage, fracture and erode. The polypropylene matrix has much lower strength and modulus than the fiber, but can withstand large strain, often has viscoelasticity and elastoplasticity, is a ductile material, and is classified into glass fiber reinforced composite plastic, carbon fiber reinforced composite plastic, boron fiber reinforced composite plastic and the like according to the adopted fiber. In recent years, polyester fiber reinforced polymer matrix composites have received attention for their excellent properties.
The interfacial bonding between the polyester fibers and the polypropylene matrix is an important factor in obtaining a high performance composite. Good interfacial bonding facilitates efficient transfer of stresses and improves energy absorption by the polymer matrix. Because the thermoplastic resin matrix itself lacks reactive functional groups, it is difficult to create good chemical bonds with the fibers, and thus the polyester fiber surface typically needs to be modified to form good interfacial bonds with the polymer. The method for improving the interface bonding between the polyester fiber and the polymer matrix mainly comprises two steps of polyester fiber surface treatment and interfacial compatilizer addition. In recent years, there has been an increasing search for improvement of interfacial adhesion between polyester fibers and matrix resins.
The Chinese patent with the publication number of CN110922615B discloses a preparation method of waste polyester fabric reinforced polypropylene composite plastic, which comprises surface finishing, cleaning, crushing, modifying, blending extrusion and granulating. In the polyester fiber reinforced composite plastic, the interface combination between the polyester fiber and the polymer matrix is poor, and the traditional surface treatment and interfacial compatilizer adding method, such as maleic anhydride grafted polypropylene, is more beneficial to the 3 mechanical property indexes of tensile strength, bending strength and bending modulus, has no positive effect on the two mechanical property indexes of elongation at break and impact strength, is difficult to achieve good dispersing and compatibilizing effects on the material, and finally leads to poor comprehensive mechanical property of the composite material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a preparation method of a fiber reinforced polypropylene composite material, which achieves the aim of comprehensively improving the mechanical properties of the composite material by promoting the reinforcement, dispersion and compatibilization of polyester fibers and a polypropylene matrix.
The second object of the invention is to provide a fiber reinforced polypropylene composite material which has the advantage of good comprehensive mechanical properties.
In order to achieve the first object, the present invention provides the following technical solutions:
a preparation method of a fiber reinforced polypropylene composite material comprises the following steps,
s1, polypropylene injection molding material is put into 1-10wt% of silane coupling agent solution, and is dehydrated and dried after being stirred and modified to obtain a first component;
s2, adding 35-40 parts of ethylene glycol and 8-10 parts of a tri-monomer into 100 parts of polyester bottle flakes for alcoholysis, adding 8-10 parts of 5- (2-pyridine) isophthalic acid, 10-15 parts of isophthalic acid and 0.3-0.5 part of nicotinic acid metal salt for reaction after the alcoholysis is completed, and carrying out post-treatment after the reaction is completed to obtain a second component;
s3, adding 4-6 parts of polyether and 0.1-10 parts of lignin-acrylamide-styrene graft copolymer into 100 parts of a mixture of the first component and the second component for reaction to obtain a reaction solution;
and S4, uniformly mixing 100 parts of reaction liquid and 2-5 parts of auxiliary agent, extruding by a double-screw extruder, and granulating to obtain the fiber reinforced polypropylene composite material.
By adopting the technical scheme, the waste polypropylene injection molding material can replace polypropylene raw materials after being modified by the silane coupling agent; the waste polyester bottle chip can replace aromatic dicarboxylic acid and partial aliphatic dicarboxylic acid, when in alcoholysis, the introduced tri-monomer can improve the regularity of the original polyester molecular structure in the polyester bottle chip, improve the activity of molecular chains, reduce the crystallization rate and increase an amorphous area, and in the initial stage of adding tri-monomer, the copolyester T is caused by the steric hindrance effect of the tri-monomer and the polarity of sodium sulfonate groups g Rising, but with increasing tri-monomer content, copolyester T g Can be reduced, thereby improving the diffusion and absorption of alcoholysis products; then 5- (2-pyridine) isophthalic acid and isophthalic acid are added, and under the catalysis of nicotinic acid metal salt, alcoholysis products can fully perform esterification reaction with the components; in addition, the N atom of the pyridine unit has lone pair electrons and can form stable coordination with metal ions, so that the lignin-acrylamide-styrene graft copolymer and modified polypropylene are compatible and matched, and the obtained reaction solution and the auxiliary agent are blended to obtain the fiber reinforced polypropylene composite material with better mechanical property.
Further, in the step S1, the volume ratio of the polypropylene injection molding material to the silane coupling agent solution is controlled to be 1: (1-10), the rotation speed of stirring modification is 50-150 r/min, and the time is 20-40 min.
Further, in the step S2, the metal nicotinate is copper nicotinate, nickel nicotinate, cobalt nicotinate or zinc nicotinate.
Further, in the step S2, the alcoholysis temperature is controlled to be 225-235 ℃, the reaction time is controlled to be 10-20 min, the reaction temperature is controlled to be 240-260 ℃, and the reaction time is controlled to be 2.0-3.0 h.
Further, in the step S2, after the reaction is finished, the reaction solution is heated to 265 ℃ and kept for 10-20 min, the excess ethylene glycol is fractionated, and insoluble matters and oligomers are removed by filtration.
Further, in the step S1 and the step S2, the polypropylene injection molding material and the polyester bottle chip are respectively washed and crushed in advance.
Further, in the step S3, the mass ratio of the first component to the second component is controlled to be (2-3): (3-2), wherein the vacuum degree of the reaction is 80 Pa+/-5 Pa, the temperature is 240-260 ℃, the rotating speed is 50-150 r/min, and the reaction time is 1.5-2.5 h.
Further, in the S4, the auxiliary agent is composed of the following raw materials in parts by weight, 1-3 parts of zinc stearate, 0.5-1.0 parts of sodium metabisulfite and 0.5-1.0 parts of microcrystalline cellulose.
Further, in the step S4, the temperatures of the sections from the feed inlet to the machine head of the extruder are 160 ℃, 180 ℃, 210 ℃, 220 ℃, 200 ℃, 205 ℃, and the main machine rotating speed is 300-350 r/min, and the feeding rotating speed is 15-20 r/min.
In order to achieve the first object, the present invention provides the following technical solutions:
a fiber reinforced polypropylene composite made by any of the methods described above.
In summary, the beneficial technical effects of the invention are as follows: according to the method, the polypropylene injection molding material and the polyester bottle chip are recovered, the process is optimized to reduce the interfacial binding force between the polyester fiber and the polypropylene matrix, and the enhancement, dispersion and compatibilization of the polyester fiber and the polypropylene matrix are promoted, so that the obtained fiber-reinforced polypropylene composite material has better mechanical properties, the tensile strength is up to 111.249MPa, the bending strength is up to 99.637MPa, the bending modulus is up to 4268MPa, the breaking elongation is up to 975%, and the notched impact strength of the cantilever beam is up to 120.5 kJ/square meter.
Detailed Description
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the function of the invention more clear and easy to understand.
Example 1: the invention discloses a preparation method of a fiber reinforced polypropylene composite material, which comprises the following steps,
s1, recovering and cleaning the polypropylene injection molding material, crushing the polypropylene injection molding material into particles, immersing the polypropylene injection molding material in an 8wt% aqueous solution of a silane coupling agent, and controlling the volume ratio of the polypropylene injection molding material to the silane coupling agent solution to be 1:6, stirring and modifying for 35min at a rotating speed of 125r/min, and dehydrating and drying to obtain a first component;
s2, recycling and cleaning polyester bottle flakes, crushing the polyester bottle flakes into fragments, adding ethylene glycol accounting for 37 percent of the total weight of the polyester bottle flakes and three monomers accounting for 9 percent of the total weight of the polyester bottle flakes, pulping and mixing the mixture for 12 minutes at 230 ℃, adding 5- (2-pyridine) isophthalic acid accounting for 9.5 percent of the total weight of the polyester bottle flakes, isophthalic acid accounting for 12 percent of the total weight of the polyester bottle flakes and copper nicotinate accounting for 0.4 percent of the total weight of the polyester bottle flakes, reacting the mixture at 245 ℃ for 2.0 hours, heating the mixture to 265 ℃ and preserving heat for 12 minutes after the reaction is finished, fractionating out redundant ethylene glycol, filtering the mixture, and removing insoluble substances and oligomers to obtain a second component;
s3, 58 parts of the first component and 42 parts of the second component are mixed to obtain a mixture, 5 parts of polyether and 0.8 part of lignin-acrylamide-styrene graft copolymer are added, and the mixture is reacted for 2.0 hours under the conditions that the vacuum degree is 80 Pa+/-5 Pa, the temperature is 250 ℃ and the rotating speed is 80r/min, so that a reaction liquid is obtained;
s4, uniformly mixing 100 parts of reaction liquid and an auxiliary agent consisting of 2 parts of zinc stearate, 0.7 part of sodium metabisulfite and 0.8 part of microcrystalline cellulose, extruding the mixture by a double-screw extruder, granulating, the temperature of each section from the feed inlet to the machine head of the extruder is 160 ℃, 180 ℃, 210 ℃, 220 ℃, 200 ℃, 205 ℃ and the rotating speed of the main machine is 320r/min, and the feeding rotating speed is 16r/min, thus obtaining the fiber reinforced polypropylene composite material.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 112.156MPa, the bending strength is 103.146MPa, the bending modulus is 4385MPa, the elongation at break is 988.6%, and the notched impact strength of a cantilever beam is 121.6 kJ/-square meter.
Example 2: the invention discloses a preparation method of a fiber reinforced polypropylene composite material, which comprises the following steps,
s1, recovering and cleaning the polypropylene injection molding material, crushing the polypropylene injection molding material into particles, immersing the polypropylene injection molding material in a 5wt% aqueous solution of a silane coupling agent, and controlling the volume ratio of the polypropylene injection molding material to the silane coupling agent solution to be 1:5, stirring and modifying for 20min at the rotating speed of 100r/min, and dehydrating and drying to obtain a first component;
s2, recycling and cleaning polyester bottle flakes, crushing the polyester bottle flakes into fragments, adding ethylene glycol accounting for 38% of the total weight of the polyester bottle flakes and three monomers accounting for 8% of the total weight of the polyester bottle flakes, pulping and mixing the mixture for 10 minutes at 225 ℃, adding 5- (2-pyridine) isophthalic acid accounting for 8.5% of the total weight of the polyester bottle flakes, isophthalic acid accounting for 13% of the total weight of the polyester bottle flakes and copper nicotinate accounting for 0.4% of the total weight of the polyester bottle flakes, reacting the mixture at 240 ℃ for 2.8 hours, heating the mixture to 265 ℃ and preserving heat for 15 minutes after the reaction is finished, fractionating out redundant ethylene glycol, filtering the mixture, and removing insoluble substances and oligomers to obtain a second component;
s3, mixing 52 parts of the first component and 48 parts of the second component to obtain a mixture, adding 4 parts of polyether and 5 parts of lignin-acrylamide-styrene graft copolymer, and reacting for 1.5 hours under the conditions of 80 Pa+/-5 Pa, 240 ℃ and 50r/min of rotation speed to obtain a reaction solution;
s4, uniformly mixing 100 parts of reaction liquid and an auxiliary agent consisting of 1 part of zinc stearate, 0.8 part of sodium metabisulfite and 0.6 part of microcrystalline cellulose, extruding the mixture by a double-screw extruder, granulating, the temperature of each section from the feed inlet to the machine head of the extruder is 160 ℃, 180 ℃, 210 ℃, 220 ℃, 200 ℃, 205 ℃ and the main machine rotating speed of 330r/min, and the feeding rotating speed of 15r/min in sequence, thus obtaining the fiber reinforced polypropylene composite material.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 111.249MPa, the bending strength is 100.235MPa, the bending modulus is 4268MPa, the elongation at break is 984.5%, and the notched impact strength of the cantilever beam is 123.7 kJ/-square meter.
Example 3: the invention discloses a preparation method of a fiber reinforced polypropylene composite material, which comprises the following steps,
s1, recovering and cleaning the polypropylene injection molding material, crushing the polypropylene injection molding material into particles, immersing the polypropylene injection molding material in a 3wt% aqueous solution of a silane coupling agent, and controlling the volume ratio of the polypropylene injection molding material to the silane coupling agent solution to be 1:10, stirring and modifying for 40min at a rotating speed of 150r/min, and dehydrating and drying to obtain a first component;
s2, recycling and cleaning the polyester bottle flakes, crushing the polyester bottle flakes into fragments, adding ethylene glycol accounting for 35 percent of the total weight of the polyester bottle flakes and three monomers accounting for 10 percent of the total weight of the polyester bottle flakes, pulping and mixing the mixture for 15 minutes at 235 ℃, adding 5- (2-pyridine) isophthalic acid accounting for 8 percent of the total weight of the polyester bottle flakes, isophthalic acid accounting for 14 percent of the total weight of the polyester bottle flakes and copper nicotinate accounting for 0.3 percent of the total weight of the polyester bottle flakes, reacting the mixture for 2.6 hours at 250 ℃, heating the mixture to 265 ℃ after the reaction is finished, preserving the heat for 18 minutes, fractionating out redundant ethylene glycol, filtering the mixture, and removing insoluble substances and oligomers to obtain a second component;
s3, mixing 46 parts of the first component and 54 parts of the second component to obtain a mixture, adding 6 parts of polyether and 10 parts of lignin-acrylamide-styrene graft copolymer, and reacting for 2.5 hours under the conditions of 80 Pa+/-5 Pa, 260 ℃ and 150r/min of rotation speed to obtain a reaction solution;
s4, uniformly mixing 100 parts of reaction liquid and an auxiliary agent consisting of 3 parts of zinc stearate, 0.6 part of sodium metabisulfite and 0.5 part of microcrystalline cellulose, extruding the mixture by a double-screw extruder, granulating, the temperature of each section from the feed inlet to the machine head of the extruder is 160 ℃, 180 ℃, 210 ℃, 220 ℃, 200 ℃, 205 ℃ and the rotating speed of the main machine is 300r/min, and the feeding rotating speed is 18r/min, thus obtaining the fiber reinforced polypropylene composite material.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 113.358MPa, the bending strength is 99.637MPa, the bending modulus is 4375MPa, the elongation at break is 983.2%, and the notched impact strength of a cantilever beam is 120.5 kJ/-square meter.
Example 4: the invention discloses a preparation method of a fiber reinforced polypropylene composite material, which comprises the following steps,
s1, recovering and cleaning the polypropylene injection molding material, crushing the polypropylene injection molding material into particles, immersing the polypropylene injection molding material in a 1wt% aqueous solution of a silane coupling agent, and controlling the volume ratio of the polypropylene injection molding material to the silane coupling agent solution to be 1:8, stirring and modifying for 25min at a rotating speed of 75r/min, and dehydrating and drying to obtain a first component;
s2, recycling and cleaning polyester bottle flakes, crushing the polyester bottle flakes into fragments, adding ethylene glycol accounting for 40 percent of the total weight of the polyester bottle flakes and a trisonomer accounting for 8.5 percent of the total weight of the polyester bottle flakes, pulping and mixing the mixture for 20 minutes at 228 ℃, adding 5- (2-pyridine) isophthalic acid accounting for 10 percent of the total weight of the polyester bottle flakes, isophthalic acid accounting for 10 percent of the total weight of the polyester bottle flakes and copper nicotinate accounting for 0.5 percent of the total weight of the polyester bottle flakes, reacting the mixture at 260 ℃ for 2.3 hours, heating the mixture to 265 ℃ and preserving heat for 10 minutes after the reaction is finished, fractionating out redundant ethylene glycol, filtering the mixture, and removing insoluble substances and oligomers to obtain a second component;
s3, mixing 40 parts of the first component and 60 parts of the second component to obtain a mixture, adding 5 parts of polyether and 0.1 part of lignin-acrylamide-styrene graft copolymer, and reacting for 1.8 hours under the conditions that the vacuum degree is 80 Pa+/-5 Pa, the temperature is 245 ℃ and the rotating speed is 120r/min to obtain a reaction solution;
s4, uniformly mixing 100 parts of reaction liquid and an auxiliary agent consisting of 2 parts of zinc stearate, 0.5 part of sodium metabisulfite and 0.7 part of microcrystalline cellulose, extruding the mixture by a double-screw extruder, granulating, the temperature of each section from the feed inlet to the machine head of the extruder is 160 ℃, 180 ℃, 210 ℃, 220 ℃, 200 ℃, 205 ℃ and the rotating speed of the main machine is 350r/min, and the feeding rotating speed is 15r/min, thus obtaining the fiber reinforced polypropylene composite material.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 112.182MPa, the bending strength is 100.988MPa, the bending modulus is 4332MPa, the elongation at break is 976.5%, and the notched impact strength of a cantilever beam is 122.6 kJ/-square meter.
Example 5: the invention discloses a preparation method of a fiber reinforced polypropylene composite material, which comprises the following steps,
s1, recovering and cleaning the polypropylene injection molding material, crushing the polypropylene injection molding material into particles, immersing the polypropylene injection molding material in a 10wt% aqueous solution of a silane coupling agent, and controlling the volume ratio of the polypropylene injection molding material to the silane coupling agent solution to be 1:1, stirring and modifying for 30min at a rotating speed of 50r/min, and dehydrating and drying to obtain a first component;
s2, recycling and cleaning polyester bottle flakes, crushing the polyester bottle flakes into fragments, adding ethylene glycol accounting for 36% of the total weight of the polyester bottle flakes and a tri-monomer accounting for 9.5% of the total weight of the polyester bottle flakes, pulping and mixing the mixture for 18 minutes at 234 ℃, adding 5- (2-pyridine) isophthalic acid accounting for 9% of the total weight of the polyester bottle flakes, isophthalic acid accounting for 15% of the total weight of the polyester bottle flakes and copper nicotinate accounting for 0.4% of the total weight of the polyester bottle flakes, reacting the mixture at 255 ℃ for 3.0 hours, heating the mixture to 265 ℃ and preserving heat for 20 minutes after the reaction is finished, fractionating out redundant ethylene glycol, filtering the mixture, and removing insoluble substances and oligomers to obtain a second component;
s3, mixing 60 parts of the first component and 40 parts of the second component to obtain a mixture, adding 4 parts of polyether and 1 part of lignin-acrylamide-styrene graft copolymer, and reacting for 2.4 hours under the conditions of 80 Pa+/-5 Pa, 255 ℃ and 100r/min of rotation speed to obtain a reaction solution;
s4, uniformly mixing 100 parts of reaction liquid and an auxiliary agent consisting of 2 parts of zinc stearate, 1.0 part of sodium metabisulfite and 1.0 part of microcrystalline cellulose, extruding the mixture by a double-screw extruder, granulating, the temperature of each section from the feed inlet to the machine head of the extruder is 160 ℃, 180 ℃, 210 ℃, 220 ℃, 200 ℃, 205 ℃ and the main machine rotating speed 340r/min, and the feeding rotating speed 20r/min in sequence, thus obtaining the fiber reinforced polypropylene composite material.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 112.457MPa, the bending strength is 101.721MPa, the bending modulus is 4288MPa, the elongation at break is 975.8%, and the notched impact strength of a cantilever beam is 122.5 kJ/-square meter.
Comparative example 1: the preparation method of the fiber reinforced polypropylene composite material disclosed by the invention is different from that of the embodiment 1 in that a silane coupling agent is not used.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 68.601MPa, the bending strength is 59.299MPa, the bending modulus is 398MPa, the elongation at break is 871.240%, and the notched impact strength of a cantilever beam is 104.4 kJ/-square meter.
Comparative example 2: the preparation method of the fiber reinforced polypropylene composite material disclosed by the invention is different from that of the embodiment 1 in that 5- (2-pyridine) isophthalic acid is not used.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 99.379MPa, the bending strength is 94.295MPa, the bending modulus is 3589MPa, the elongation at break is 781.4%, and the notched impact strength of a cantilever beam is 84.4 kJ/-square meter.
Comparative example 3: the preparation method of the fiber reinforced polypropylene composite material disclosed by the invention is different from that of the embodiment 1 in that copper nicotinate is not used.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 35.492MPa, the bending strength is 56.303MPa, the bending modulus is 337MPa, the elongation at break is 845.2%, and the notched impact strength of a cantilever beam is 88.0 kJ/-square meter.
Comparative example 4: the preparation method of the fiber reinforced polypropylene composite material disclosed by the invention is different from that of the embodiment 1 in that maleic anhydride grafted polypropylene is used for replacing lignin-acrylamide-styrene grafted copolymer.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 48.269MPa, the bending strength is 58.910MPa, the bending modulus is 450MPa, the elongation at break is 401.8%, and the notch impact strength of the cantilever beam is 35.6 kJ/-square meter.
Comparative example 5: the preparation method of the fiber reinforced polypropylene composite material disclosed by the invention is different from that of the embodiment 1 in that no auxiliary agent is used.
After the prepared fiber reinforced polypropylene composite material is injection molded to form a plate, mechanical property detection is carried out, wherein the tensile strength is 80.215MPa, the bending strength is 81.208MPa, the bending modulus is 2417MPa, the elongation at break is 625%, and the notched impact strength of a cantilever beam is 76.8 kJ/-square meter.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (8)
1. A preparation method of a fiber reinforced polypropylene composite material is characterized by comprising the following steps: comprises the steps of,
s1, polypropylene injection molding material is put into 1-10wt% of silane coupling agent solution, and is dehydrated and dried after being stirred and modified to obtain a first component;
s2, adding 35-40 parts of ethylene glycol and 8-10 parts of a tri-monomer into 100 parts of polyester bottle flakes for alcoholysis, adding 8-10 parts of 5- (2-pyridine) isophthalic acid, 10-15 parts of isophthalic acid and 0.3-0.5 part of nicotinic acid metal salt for reaction after the alcoholysis is completed, and carrying out post-treatment after the reaction is completed to obtain a second component;
s3, adding 4-6 parts of polyether and 0.1-10 parts of lignin-acrylamide-styrene graft copolymer into 100 parts of a mixture of the first component and the second component for reaction to obtain a reaction solution;
s4, uniformly mixing 100 parts of reaction liquid and 2-5 parts of auxiliary agent, and extruding and granulating by a double-screw extruder to obtain a fiber reinforced polypropylene composite material;
in the step S2, the nicotinic acid metal salt is copper nicotinate, nickel nicotinate, cobalt nicotinate or zinc nicotinate;
in the step S3, the mass ratio of the first component to the second component is controlled to be (2-3): (3-2);
in the S4, the auxiliary agent comprises the following raw materials in parts by weight, 1-3 parts of zinc stearate, 0.5-1.0 part of sodium metabisulfite and 0.5-1.0 part of microcrystalline cellulose.
2. The method for preparing a fiber reinforced polypropylene composite according to claim 1, wherein: in the step S1, the volume ratio of the polypropylene injection molding material to the silane coupling agent solution is controlled to be 1: (1-10), the rotation speed of stirring modification is 50-150 r/min, and the time is 20-40 min.
3. The method for preparing a fiber reinforced polypropylene composite according to claim 1, wherein: in the step S2, the alcoholysis temperature is controlled to be 225-235 ℃, the reaction time is controlled to be 10-20 min, the reaction temperature is controlled to be 240-260 ℃, and the reaction time is controlled to be 2.0-3.0 h.
4. The method for preparing a fiber reinforced polypropylene composite according to claim 1, wherein: in the step S2, after the reaction is finished, the temperature of the reaction solution is raised to 265 ℃ and kept for 10-20 min, the excessive glycol is fractionated, and insoluble matters and oligomers are removed by filtration.
5. The method for preparing a fiber reinforced polypropylene composite according to claim 1, wherein: in the step S1 and the step S2, the polypropylene injection molding material and the polyester bottle chip are respectively washed and crushed in advance.
6. The method for preparing a fiber reinforced polypropylene composite according to claim 1, wherein: in the step S3, the vacuum degree of the reaction is controlled to be 80Pa plus or minus 5Pa, the temperature is 240-260 ℃, the rotating speed is 50-150 r/min, and the reaction time is controlled to be 1.5-2.5 h.
7. The method for preparing a fiber reinforced polypropylene composite according to claim 1, wherein: in the step S4, the temperatures of the sections from the feed inlet to the machine head of the extruder are 160 ℃, 180 ℃, 210 ℃, 220 ℃, 200 ℃, 205 ℃ and 300-350 r/min of the main machine, and the feeding rotating speed is 15-20 r/min.
8. A fiber reinforced polypropylene composite material characterized by: the method according to any one of claims 1 to 7.
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