CN113549304B - PET composite material and preparation method thereof - Google Patents
PET composite material and preparation method thereof Download PDFInfo
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- CN113549304B CN113549304B CN202010340564.5A CN202010340564A CN113549304B CN 113549304 B CN113549304 B CN 113549304B CN 202010340564 A CN202010340564 A CN 202010340564A CN 113549304 B CN113549304 B CN 113549304B
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 86
- 239000010456 wollastonite Substances 0.000 claims abstract description 86
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims abstract description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 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 abstract description 40
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims abstract description 31
- 229960004488 linolenic acid Drugs 0.000 claims abstract description 31
- 239000013067 intermediate product Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- -1 3, 5-di-t-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 83
- 239000005020 polyethylene terephthalate Substances 0.000 description 83
- 238000012360 testing method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 13
- 239000011258 core-shell material Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a PET composite material and a preparation method thereof, wherein the PET composite material is prepared from 80-100 parts of PET, 10-20 parts of modified wollastonite and 0.1-0.5 part of antioxidant according to parts by weight; the preparation method of the modified wollastonite comprises the following steps: adding wollastonite into ethanol solution, stirring, adding azodiisobutyronitrile and alpha-linolenic acid into the solution, and then carrying out high-temperature reaction to obtain an intermediate product; and fully mixing the intermediate product with Fischer-Tropsch wax at high temperature to obtain the modified wollastonite. The PET composite material has excellent mechanical properties, and expands the application in specific fields.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a PET composite material and a preparation method thereof.
Background
Thermoplastics are a class of plastics which have plasticity at a certain temperature, solidify after cooling and are capable of repeating this process. The molecular structure of the polymer is characterized in that the linear polymer compound is generally provided with no active group, and linear intermolecular crosslinking does not occur when heated. Generally, thermoplastics can be classified into general plastics, engineering plastics, special plastics, etc. according to performance characteristics, versatility of use, versatility of molding technology, etc. Wherein, engineering plastics's characteristics are: certain structures and properties of the high polymer are particularly outstanding, or the difficulty of molding processing technology is high, and the high polymer is often applied to professional engineering or special fields and occasions. The main engineering plastics are: nylon (Nylon), polycarbonate (PC), polyurethane (PU), polytetrafluoroethylene (teflon, PTFE), polyethylene terephthalate (PET), and the like.
Among them, polyethylene terephthalate (PET) is a widely used high molecular polyester resin, which has advantages of good fatigue resistance, good heat resistance, good dimensional stability, etc., but in some specific fields where the mechanical properties of PET are required to be high, the general PET composite material cannot meet the requirements, so that the application of the PET composite material in some specific fields is limited.
Disclosure of Invention
In view of the above, the invention is necessary to provide a PET composite material and a preparation method thereof, wherein the mechanical properties of the PET composite material are improved by adding modified wollastonite into a PET matrix resin, and the modified wollastonite connects fischer-tropsch wax to the surface of wollastonite through alpha-linolenic acid to obtain a core-shell filler taking wollastonite as a core and fischer-tropsch wax as a shell, so that the PET composite material has excellent mechanical properties, and the technical problem of poor mechanical properties of common PET composite materials is solved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a PET composite material is prepared from 80-100 parts of PET, 10-20 parts of modified wollastonite and 0.1-0.5 part of antioxidant according to parts by weight;
the preparation method of the modified wollastonite comprises the following steps:
adding wollastonite into ethanol solution, stirring, adding azodiisobutyronitrile and alpha-linolenic acid into the solution, and then carrying out high-temperature reaction to obtain an intermediate product;
and fully mixing the intermediate product with Fischer-Tropsch wax at high temperature to obtain the modified wollastonite.
Fischer-Tropsch wax is a methylene polymer, an alkane polymer synthesized from hydrocarbon-based synthesis gas or natural gas, which contributes to dispersion of filler and excellent slip properties at the time of compounding during the production of modified plastics, and alpha-linolenic acid is a polyunsaturated fatty acid having three double bonds (C 18 H 30 O 2 ) The concrete structure is as follows:
the invention connects wollastonite with Fischer-Tropsch wax through alpha-linolenic acid, the Fischer-Tropsch wax is firmly coated on the surface of the wollastonite to obtain a core-shell type filler which takes the wollastonite as a core and takes the Fischer-Tropsch wax as a shell, thereby greatly improving the mechanical property of the PET composite material.
Further, in the modified wollastonite, the particle size of wollastonite has an influence on the performance of the final modified wollastonite, and therefore, in some embodiments of the present invention, it is preferable that the particle size of wollastonite is 6 to 10. Mu.m.
Furthermore, the ethanol solution is mainly used as a solvent of azodiisobutyronitrile and alpha-linolenic acid, and plays a role in uniform dispersion, so that wollastonite is better modified, and in some specific embodiments, the mass fraction of ethanol in the ethanol solution is 25% -35%.
Further, in some embodiments of the present invention, it is preferable that the wollastonite, the ethanol solution, the azobisisobutyronitrile, the α -linolenic acid have a mass ratio of (70 to 90): (280-320): (0.6-1): (6-10).
Further, the specific steps of the high-temperature reaction are as follows: reacting at 70-90 deg.C for 6-8h, filtering, and vacuum drying at 100-120 deg.C for 2-4h.
Further, specifically, the wollastonite is subjected to surface modification of alpha-linolenic acid under the action of an initiator azodiisobutyronitrile, so that an intermediate product, namely the wollastonite with the alpha-linolenic acid surface modified, is obtained, and as one end of the alpha-linolenic acid is carboxyl, one end of the alpha-linolenic acid is provided with a double bond, the carboxyl end of the alpha-linolenic acid can be chemically bonded with the surface of the wollastonite to generate octadecatrienoate to be combined with the surface of the wollastonite, and one end with the double bond can be subjected to copolymerization or grafting reaction with an unsaturated monomer or polymer, so that the wollastonite is similar to a bridge, and the wollastonite and the Fischer-Tropsch wax are connected. The difference of the proportion of core-shell components in the core-shell structure in the modified wollastonite has a certain influence on the performance of the final filler, so that the performance of the modified wollastonite is optimal, and therefore, in some specific embodiments of the invention, the mass ratio of the intermediate product to the Fischer-Tropsch wax is preferably (50-70): (8-12).
Further, the temperature of the high temperature condition is 100 to 120 ℃, it is understood that the mixing mode of the intermediate product and the fischer-tropsch wax may not be limited specifically, the mixing time of the intermediate product and the fischer-tropsch wax may be adjusted according to the need in the conventional mechanical blending mode in the art, so long as the purpose of uniform mixing can be achieved, and in some specific embodiments of the present invention, it is preferable to add the intermediate product and the fischer-tropsch wax into the high-speed mixer and mix for 15 to 25 minutes.
Further, the antioxidant of the present invention may be selected as usual in the art, preferably, the antioxidant of the present invention is selected from one or a mixture of two or more of phenyl tris (2, 4-di-t-butyl) phosphite, pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-trimethyl-2, 4,6- (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, and it is understood that specific examples of the antioxidant of the present invention include, but are not limited to, the above-mentioned ones.
The invention also provides a preparation method of the PET composite material, which comprises the following steps:
the PET, the modified wollastonite and the antioxidant are fully mixed according to the weight part ratio to obtain a uniform mixture, and it is understood that the mixing is mainly to uniformly mix the raw materials, so long as the purpose of uniform mixing can be realized, the mixing mode can be mechanical blending conventional in the art, and the mixing time, the rotating speed and the like can be adjusted according to the actual situation, so that the method is not particularly limited;
and adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material.
It will be appreciated that the processing parameters of the twin screw extruder may be adjusted depending on the matrix resin and the auxiliary agent, and preferably in some embodiments of the present invention, the processing temperature of the twin screw extruder is in the range of 240 to 260℃in the first zone, 280 to 300℃in the second zone, 280 to 300℃in the third zone, 280 to 300℃in the fourth zone, 280 to 300℃in the fifth zone, 280 to 300℃in the sixth zone, 280 to 300℃in the head of the extruder, and the screw speed is 200 to 280r/min.
Compared with the prior art, the PET composite material of the invention utilizes alpha-linolenic acidThe bridge function connects the Fischer-Tropsch wax and the wollastonite, so that the Fischer-Tropsch wax is firmly coated on the surface of the wollastonite to form a core-shell filler taking the wollastonite as a core and taking the Fischer-Tropsch wax as a shell. On the one hand, the wollastonite can be used as a nucleating agent in the PET crystallization process, is favorable for heterogeneous nucleation of PET and improves the mechanical property of PET, and on the other hand, because the Fischer-Tropsch wax has good compatibility with PET, the problem of the compatibility of the wollastonite and PET is solved, the wollastonite is more uniformly dispersed in a PET matrix, the mechanical property of the PET composite material is greatly improved, the tensile strength of the PET composite material is 74.2-79.2MPa, the flexural modulus is 3850-4270MPa, and the notch impact strength of a cantilever beam is 4.9-5.2KJ/m 2 The mechanical property is excellent, so that the application of the PET composite material in the specific field is expanded.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The following examples and comparative examples used the following raw materials:
PET (model 008L), aclo, canada; ethanol, henan Baiyue chemical industry; wollastonite, new Yu Donghui mining Co., ltd; azodiisobutyronitrile, jinan Rong chemical Co., ltd; alpha-linolenic acid, jinan Sheng and chemical Co., ltd; fischer-Tropsch wax, dande City Chen chemical industry Co., ltd; antioxidants (model Irganox168, irganox1010, irganox 1330), basv corporation; coupling agent KH550, mongolian, inc.
Specific dimensions of the test bars in the examples and comparative examples are:
tensile strength: spline type (170.0+ -5.0) mm (13.0+ -0.5) mm (3.2+ -0.2) mm, stretching rate 50mm/min;
flexural modulus: spline model (125.0+ -5.0) mm (13.0+ -0.5) mm (3.2+ -0.2) mm, bending rate 1.25mm/min;
notched Izod impact Strength: spline model is: (125.0+ -5.0) mm (13.0+ -0.5) mm (3.2+ -0.2) mm, notch machined, notch depth (2.6+ -0.2) mm.
Example 1
Preparation of modified wollastonite in this example:
700g of wollastonite (particle size 6 μm), 2.8kg of a 25% ethanol solution by mass fraction, 6g of Azobisisobutyronitrile (ABIN) as initiator and 60g of alpha-linolenic acid were weighed out;
adding wollastonite into a reaction vessel filled with ethanol solution, adding ABIN and alpha-linolenic acid under rapid stirring, reacting at 70 ℃ for 6 hours, filtering the product obtained by the reaction, and drying in a vacuum drying oven at 100 ℃ for 2 hours to obtain an intermediate product, namely the wollastonite with the alpha-linolenic acid surface modified;
500g of intermediate product and 80g of Fischer-Tropsch wax are added into a high-speed mixer to be heated to 100 ℃, and the mixture is mixed for 15min to prepare the modified wollastonite.
Preparation of PET composite material:
weighing 80 parts of PET, 10 parts of modified wollastonite and 0.1 part of Irganox1010 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as X1, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 240 ℃, the temperature of the second area is 280 ℃, the temperature of the third area is 280 ℃, the temperature of the fourth area is 280 ℃, the temperature of the fifth area is 280 ℃, the temperature of the sixth area is 280 ℃, the temperature of the machine head is 280 ℃, and the rotating speed of the screw is 200r/min.
Comparative example 1
Weighing 80 parts of PET, 10 parts of wollastonite (with the particle size of 6 mu m) and 0.1 part of Irganox1010 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as D1, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged, wherein the temperature of the first area is 240 ℃, the temperature of the second area is 280 ℃, the temperature of the third area is 280 ℃, the temperature of the fourth area is 280 ℃, the temperature of the fifth area is 280 ℃, the temperature of the sixth area is 280 ℃, the temperature of the machine head is 280 ℃, and the screw rotating speed is 200r/min.
The PET composites of example 1 and comparative example 1 were subjected to performance testing after being injection molded into corresponding bars using an injection molding machine, and the test results are shown in table 1:
table 1 results of PET composite performance test in example 1 and comparative example 1
| Test item | Test standard | Unit (B) | X1 | D1 |
| Tensile Strength | ASTM D638 | MPa | 74.2 | 65.3 |
| Flexural modulus | ASTM D790 | MPa | 3850 | 3200 |
| Cantilever beam notch impactStrength of | ASTM D256 | kJ/m 2 | 5.1 | 2.8 |
As can be seen from the test results in Table 1, the mechanical properties of X1 are significantly better than those of D1, which indicates that under the same conditions, the mechanical properties of the PET core-shell wollastonite system are more excellent.
Example 2
Preparation of modified wollastonite in this example:
900g of wollastonite (particle size 10 μm), 3.2kg of a 35% ethanol solution by mass fraction, 10g of Azobisisobutyronitrile (ABIN) as initiator and 100g of alpha-linolenic acid were weighed out;
adding wollastonite into a reaction vessel filled with ethanol solution, adding ABIN and alpha-linolenic acid under rapid stirring, reacting at 90 ℃ for 8 hours, filtering the product obtained by the reaction, and drying in a vacuum drying oven at 120 ℃ for 4 hours to obtain an intermediate product, namely the wollastonite with the alpha-linolenic acid surface modified;
700g of intermediate product and 120g of Fischer-Tropsch wax are added into a high-speed mixer to be heated to 120 ℃, and the mixture is mixed for 25 minutes to prepare the modified wollastonite.
Preparation of PET composite material:
weighing 100 parts of PET, 20 parts of modified wollastonite, 0.1 part of Irganox1010, 0.2 part of Irganox168 and 0.2 part of Irganox1330 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as X2, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 260 ℃, the temperature of the second area is 300 ℃, the temperature of the third area is 300 ℃, the temperature of the fourth area is 300 ℃, the temperature of the fifth area is 300 ℃, the temperature of the sixth area is 300 ℃, the temperature of the machine head is 300 ℃, and the rotating speed of the screw is 280r/min.
Comparative example 2
100 parts of PET, 20 parts of wollastonite (with the particle size of 10 mu m), 0.1 part of Irganox1010, 0.2 part of Irganox168 and 0.2 part of Irganox1330 are weighed according to parts by weight, mixed and stirred uniformly to obtain a mixture;
adding the PET composite material into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as D2, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 260 ℃, the temperature of the second area is 300 ℃, the temperature of the third area is 300 ℃, the temperature of the fourth area is 300 ℃, the temperature of the fifth area is 300 ℃, the temperature of the sixth area is 300 ℃, the temperature of the machine head is 300 ℃, and the rotating speed of the screw is 280r/min.
The PET composites of example 2 and comparative example 2 were subjected to performance testing after being injection molded into corresponding bars using an injection molding machine, and the test results are shown in table 2:
table 2 results of PET composite performance test in example 2 and comparative example 2
| Test item | Test standard | Unit (B) | X2 | D2 |
| Tensile Strength | ASTM D638 | MPa | 79.2 | 69.3 |
| Flexural modulus | ASTM D790 | MPa | 4270 | 3520 |
| Notched impact strength of cantilever beam | ASTM D256 | kJ/m 2 | 4.9 | 2.5 |
As can be seen from the test results in Table 2, the mechanical properties of X2 are significantly better than those of D2, which indicates that under the same conditions, the mechanical properties of the PET core-shell wollastonite system are more excellent.
Example 3
Preparation of modified wollastonite in this example:
800g of wollastonite (particle size 8 μm), 3.0kg of a 30% ethanol solution by mass fraction, 8g of Azobisisobutyronitrile (ABIN) as initiator and 80g of alpha-linolenic acid are weighed;
adding wollastonite into a reaction vessel filled with ethanol solution, adding ABIN and alpha-linolenic acid under rapid stirring, reacting at 80 ℃ for 7h, filtering the product obtained by the reaction, and drying in a vacuum drying oven at 110 ℃ for 3h to obtain an intermediate product, namely the wollastonite with the alpha-linolenic acid surface modified;
600g of the intermediate product and 100g of Fischer-Tropsch wax are added into a high-speed mixer, heated to 110 ℃, and mixed for 20 minutes to prepare the modified wollastonite.
Preparation of PET composite material:
90 parts of PET, 15 parts of modified wollastonite, 0.1 part of Irganox168 and 0.2 part of Irganox1010 are weighed according to parts by weight, mixed and stirred uniformly to obtain a mixture;
adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as X3, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 250 ℃, the temperature of the second area is 290 ℃, the temperature of the third area is 290 ℃, the temperature of the fourth area is 290 ℃, the temperature of the fifth area is 290 ℃, the temperature of the sixth area is 290 ℃, the temperature of the machine head is 290 ℃, and the rotating speed of the screw is 240r/min.
Comparative example 3
90 parts of PET, 15 parts of wollastonite (with the particle size of 8 mu m), 0.1 part of Irganox168 and 0.2 part of Irganox1010 are weighed according to parts by weight, mixed and stirred uniformly to obtain a mixture;
adding the PET composite material into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as D3, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 250 ℃, the temperature of the second area is 290 ℃, the temperature of the third area is 290 ℃, the temperature of the fourth area is 290 ℃, the temperature of the fifth area is 290 ℃, the temperature of the sixth area is 290 ℃, the temperature of the machine head is 290 ℃, and the rotating speed of the screw is 240r/min.
The PET composites of example 3 and comparative example 3 were subjected to performance testing after being injection molded into corresponding bars using an injection molding machine, and the test results are shown in table 3:
table 3 results of PET composite performance tests in example 3 and comparative example 3
| Test item | Test standard | Unit (B) | X3 | D3 |
| Tensile Strength | ASTM D638 | MPa | 76.5 | 66.7 |
| Flexural modulus | ASTM D790 | MPa | 4090 | 3310 |
| Notched impact strength of cantilever beam | ASTM D256 | kJ/m 2 | 5.2 | 3.1 |
As can be seen from the test results in Table 3, the mechanical properties of X3 are significantly better than those of D3, which indicates that under the same conditions, the mechanical properties of the PET core-shell wollastonite system are more excellent.
Example 4
Preparation of modified wollastonite in this example:
750g of wollastonite (particle size 7 μm), 3.1kg of 28% ethanol solution by mass, 9g of Azobisisobutyronitrile (ABIN) as initiator and 85g of alpha-linolenic acid are weighed out;
adding wollastonite into a reaction vessel filled with ethanol solution, adding ABIN and alpha-linolenic acid under rapid stirring, reacting at 75 ℃ for 6 hours, filtering the product obtained by the reaction, and drying in a vacuum drying oven at 120 ℃ for 3 hours to obtain an intermediate product, namely the wollastonite with the alpha-linolenic acid surface modified;
650g of intermediate product and 110g of Fischer-Tropsch wax are added into a high-speed mixer, heated to 105 ℃, and mixed for 18min to prepare modified wollastonite.
Preparation of PET composite material:
weighing 85 parts of PET, 13 parts of modified wollastonite, 0.1 part of Irganox1010 and 0.2 part of Irganox1330 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as X4, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first zone is 245 ℃, the temperature of the second zone is 285 ℃, the temperature of the third zone is 285 ℃, the temperature of the fourth zone is 285 ℃, the temperature of the fifth zone is 285 ℃, the temperature of the sixth zone is 285 ℃, the temperature of the machine head is 285 ℃, and the rotating speed of the screw is 205r/min.
Comparative example 4
Weighing 85 parts of PET, 13 parts of wollastonite (with the particle size of 7 mu m) 0.1 part of Irganox1010 and 0.2 part of Irganox1330 according to parts by weight, mixing and uniformly stirring to obtain a mixture;
adding the PET composite material into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as D4, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first zone is 245 ℃, the temperature of the second zone is 285 ℃, the temperature of the third zone is 285 ℃, the temperature of the fourth zone is 285 ℃, the temperature of the fifth zone is 285 ℃, the temperature of the sixth zone is 285 ℃, the temperature of the machine head is 285 ℃, and the rotating speed of the screw is 205r/min.
The PET composites of example 4 and comparative example 4 were subjected to performance testing after being injection molded into corresponding bars using an injection molding machine, and the test results are shown in table 4:
table 4 results of PET composite performance test in example 4 and comparative example 4
| Test item | Test standard | Unit (B) | X4 | D4 |
| Tensile Strength | ASTM D638 | MPa | 75.1 | 65.5 |
| Flexural modulus | ASTM D790 | MPa | 4120 | 3470 |
| Notched impact strength of cantilever beam | ASTM D256 | kJ/m 2 | 5.2 | 2.8 |
As can be seen from the test results in Table 4, the mechanical properties of X4 are significantly better than those of D4, which indicates that under the same conditions, the mechanical properties of the PET core-shell wollastonite system are more excellent.
Example 5
Preparation of modified wollastonite in this example:
850g of wollastonite (particle size 9 μm), 3.2kg of a 32% strength by mass ethanol solution, 7g of Azobisisobutyronitrile (ABIN), an initiator, and 95g of alpha-linolenic acid were weighed out;
adding wollastonite into a reaction vessel filled with ethanol solution, adding ABIN and alpha-linolenic acid under rapid stirring, reacting at 85 ℃ for 7h, filtering the product obtained by the reaction, and drying in a vacuum drying oven at 115 ℃ for 2h to obtain an intermediate product, namely the wollastonite with the alpha-linolenic acid surface modified;
560g of intermediate product and 110g of Fischer-Tropsch wax are added into a high-speed mixer, heated to 115 ℃, and mixed for 21min to prepare modified wollastonite.
Preparation of PET composite material:
weighing 95 parts of PET, 16 parts of modified wollastonite and 0.1 part of Irganox1010 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as X5, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 255 ℃, the temperature of the second area is 295 ℃, the temperature of the third area is 295 ℃, the temperature of the fourth area is 295 ℃, the temperature of the fifth area is 295 ℃, the temperature of the sixth area is 295 ℃, the temperature of the machine head is 295 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 5
Weighing 95 parts of PET, 16 parts of wollastonite (with the particle size of 9 mu m) and 0.1 part of Irganox1010 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the PET composite material into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as D5, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 255 ℃, the temperature of the second area is 295 ℃, the temperature of the third area is 295 ℃, the temperature of the fourth area is 295 ℃, the temperature of the fifth area is 295 ℃, the temperature of the sixth area is 295 ℃, the temperature of the machine head is 295 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 6
Weighing 95 parts of PET, 16 parts of wollastonite (with the particle size of 9 mu m), 1 part of coupling agent KH550 and 0.1 part of Irganox1010 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the PET composite material into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as D6, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 255 ℃, the temperature of the second area is 295 ℃, the temperature of the third area is 295 ℃, the temperature of the fourth area is 295 ℃, the temperature of the fifth area is 295 ℃, the temperature of the sixth area is 295 ℃, the temperature of the machine head is 295 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 7
Weighing 95 parts of PET, 12 parts of wollastonite (with the particle size of 9 mu m), 1.3 parts of alpha-linolenic acid, 2.7 parts of Fischer-Tropsch wax and 0.1 part of Irganox1010 according to parts by weight, mixing and stirring uniformly to obtain a mixture;
adding the PET composite material into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material, which is marked as D7, wherein the double-screw extruder comprises six temperature areas which are sequentially arranged: the temperature of the first area is 255 ℃, the temperature of the second area is 295 ℃, the temperature of the third area is 295 ℃, the temperature of the fourth area is 295 ℃, the temperature of the fifth area is 295 ℃, the temperature of the sixth area is 295 ℃, the temperature of the machine head is 295 ℃, and the rotating speed of the screw is 245r/min.
The PET composites of example 5 and comparative examples 5 to 7 were subjected to performance testing after being injection molded into respective bars by an injection molding machine, and the test results are shown in Table 5:
TABLE 5 results of performance testing of PET composites in example 5, comparative examples 5-7
| Test item | Test standard | Unit (B) | X5 | D5 | D6 | D7 |
| Tensile Strength | ASTM D638 | MPa | 76.5 | 66.5 | 69.1 | 68.2 |
| Flexural modulus | ASTM D790 | MPa | 4210 | 3580 | 3763 | 3641 |
| Notched impact strength of cantilever beam | ASTM D256 | kJ/m 2 | 5.0 | 3.1 | 4.0 | 3.7 |
As can be seen from the test results in Table 5, the mechanical properties of X5 are significantly better than those of the PET composites in D5, D6 and D7, indicating that under the same conditions, the mechanical properties of the PET core-shell wollastonite system are more excellent.
From the above, the PET composite material has excellent mechanical properties, and can meet the requirements of the fields of IT, communication, electronics, automobiles and the like on engineering parts.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The PET composite material is characterized by being prepared from 80-100 parts of PET, 10-20 parts of modified wollastonite and 0.1-0.5 part of antioxidant according to parts by weight;
the preparation method of the modified wollastonite comprises the following steps:
adding wollastonite into ethanol solution, stirring, adding azodiisobutyronitrile and alpha-linolenic acid into the solution, and then carrying out high-temperature reaction to obtain an intermediate product;
fully mixing the intermediate product with Fischer-Tropsch wax at a high temperature to obtain modified wollastonite;
the preparation method of the PET composite material comprises the following steps:
fully mixing PET, modified wollastonite and an antioxidant according to the weight part ratio to obtain a uniform mixture;
adding the mixture into a double-screw extruder, and carrying out melting, extrusion and granulation to obtain the PET composite material;
wherein the processing temperature of the double-screw extruder is 240-260 ℃ in the first area, 280-300 ℃ in the second area, 280-300 ℃ in the third area, 280-300 ℃ in the fourth area, 280-300 ℃ in the fifth area, 280-300 ℃ in the sixth area, 280-300 ℃ in the head, and the screw rotating speed is 200-280 r/min.
2. The PET composite of claim 1 wherein the wollastonite has a particle size of 6 to 10 μm.
3. The PET composite of claim 1, wherein the mass fraction of ethanol in the ethanol solution is 25% -35%.
4. The PET composite material according to claim 1, wherein the wollastonite, the ethanol solution, the azobisisobutyronitrile, the α -linolenic acid have a mass ratio of (70-90): (280-320): (0.6-1): (6-10).
5. The PET composite material of claim 1, wherein the specific steps of the high temperature reaction are: reacting at 70-90 deg.C for 6-8h, filtering, and vacuum drying at 100-120 deg.C for 2-4h.
6. PET composite material according to claim 1, wherein the mass ratio of the intermediate product to the fischer-tropsch wax is (50-70): (8-12).
7. The PET composite of claim 1, wherein the high temperature condition has a temperature of 100-120 ℃.
8. The PET composite material of claim 1, wherein the antioxidant is selected from one or a mixture of two or more of phenyl tris (2, 4-di-t-butyl) phosphite, pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-trimethyl-2, 4,6- (3, 5-di-t-butyl-4-hydroxybenzyl) benzene.
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| CN108715673A (en) * | 2018-06-20 | 2018-10-30 | 安徽江淮汽车集团股份有限公司 | A kind of PET composite material and preparation method thereof |
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| CN108715673A (en) * | 2018-06-20 | 2018-10-30 | 安徽江淮汽车集团股份有限公司 | A kind of PET composite material and preparation method thereof |
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