CN114149666B - PBT composite material and preparation method thereof - Google Patents
PBT composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114149666B CN114149666B CN202111630420.4A CN202111630420A CN114149666B CN 114149666 B CN114149666 B CN 114149666B CN 202111630420 A CN202111630420 A CN 202111630420A CN 114149666 B CN114149666 B CN 114149666B
- Authority
- CN
- China
- Prior art keywords
- temperature
- zone
- modified carbon
- parts
- screw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 39
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 37
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims abstract description 33
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 29
- 239000004917 carbon fiber Substances 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 57
- 238000002156 mixing Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 18
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical group C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 claims description 17
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- 230000002441 reversible effect Effects 0.000 claims description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- -1 4-tert-butyl-3-hydroxy-2, 6-dimethyl benzyl Chemical group 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 29
- 239000000463 material Substances 0.000 description 27
- 238000007747 plating Methods 0.000 description 19
- 238000005469 granulation Methods 0.000 description 14
- 230000003179 granulation Effects 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 5
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical group CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- WCMHCPWEQCWRSR-UHFFFAOYSA-J dicopper;hydroxide;phosphate Chemical compound [OH-].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O WCMHCPWEQCWRSR-UHFFFAOYSA-J 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/32—Phosphorus-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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a PBT composite material and a preparation method thereof, wherein the PBT composite material is synthesized by the following raw materials: PBT resin, modified carbon nano tubes, modified carbon fibers, basic copper phosphate, tin oxide, spherical calcium carbonate, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, a main antioxidant and an auxiliary antioxidant. The PBT composite material has excellent mechanical property and wave-absorbing property, can be directly formed by laser, and is applied to the field of electronic and electrical equipment affected by electromagnetic interference.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a PBT composite material and a preparation method thereof.
Background
Microwave absorbing materials have received increased attention in recent years and have become an important component of civilian, commercial and military stealth defense systems. Microwave absorbing materials are used primarily to destroy electromagnetic interference to reduce environmental pollution caused by industrial and commercial use of electrical and electronic equipment, absorb microwaves incident on the surface of the material, and convert electromagnetic energy into internal energy or other forms of energy through loss mechanisms within the material. Carbon-based materials such as carbon black, graphite, carbon fiber, carbon nanotube, and the like have been widely studied. Compared with a Carbon Nano Tube (CNTs) reinforced resin matrix composite material and a carbon fiber reinforced resin matrix composite material, the CNTs/carbon fibers jointly reinforce the resin matrix composite material, and fully utilize mutual interaction and synergistic action, so that the defect of performance improvement of a single reinforced relative composite material is overcome, the performance of the composite material is qualitatively changed, for example, the crack resistance of a matrix is improved, and the wave absorbing performance, the interlayer fracture toughness, the impact resistance, the wear resistance and the like of the composite material are improved.
The interconnection communication industry developing at a high speed requires flexible signal frequency band configuration, narrow frequency receiving and transmitting, miniaturization of components and three-dimensional integration design, the traditional processing mode cannot meet the industrial development requirements, and the Laser Direct Structuring (LDS) technology has obvious technical and performance advantages in the production of electronic devices with integrated circuit carriers and shells due to the fact that the miniaturization, circuit design flexibility and environment-friendly processing process of electronic circuits can be realized. The laser direct forming material is suitable for preparing high-frequency and ultrahigh-frequency information antenna transceiving devices, can replace the traditional plastic material and metal patch process and the functional high-dielectric ceramic sintering technology, improves the system integration design redundancy and the production and manufacturing efficiency, is used for the field of signal receiving devices such as mobile communication, intelligent Internet of things and the like, and has wide market prospect.
At present, some researches are made on a PBT composite material with wave-absorbing performance and an LDS technology in the prior art, such as: chinese patent CN 110205096A discloses a preparation method and application of an adjustable microporous wave-absorbing metamaterial, which is prepared from the following components in parts by weight: 30 parts of metal framework material, 20 parts of polymer resin powder, 20 parts of wave-absorbing and heat-dissipating material, 20 parts of carbon fiber, 1 part of polyhydric alcohol, 0.2.5 part of zinc sulfide and 0.2 part of lubricant; chinese patent CN 103467937A discloses a master batch with wave-absorbing and radiation-proof functions, which is prepared by a resin matrix and a functional additive in a blending and extruding manner; the raw material of the resin matrix is resin powder obtained by shunting polyester chips step by step through a water milling method; the functional additives are conductive microfibers, whiskers and conductive powder subjected to surface modification treatment, and are uniformly dispersed in the resin matrix; chinese patent CN 109627712A discloses a PBT composition and a preparation method and application thereof. The PBT composition comprises PBT, glass fibers, and hollow metal oxide particles; the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, wherein the metal oxide can be activated by laser to form metal cores. The PBT composition is prepared by a method of melt extruding PBT, glass fiber and hollow metal oxide particles by using an extruder; chinese patent CN 110317437A discloses a laser direct forming resin and a preparation method thereof, which is prepared by 40 parts of PBT resin, 5 parts of LDS additive, 20 parts of ABS resin, 5 parts of aluminum titanate, 5 parts of flexibilizer and 0.4 part of antioxidant through high-speed mixing, mixing and extrusion.
Therefore, the PBT composite material disclosed in the prior art only has single function and wave-absorbing performance or laser direct forming performance, and the PBT composite material which has the wave-absorbing performance and can be directly formed by laser has no related patent publication for a while.
Disclosure of Invention
Based on the above, one of the purposes of the invention is to provide a PBT composite material with wave-absorbing performance and capable of being directly formed by laser, which is applied to the field of electronic and electrical equipment affected by electromagnetic interference.
The specific technical scheme for realizing the aim of the invention is as follows:
the PBT composite material is prepared from the following raw materials in parts by weight:
the modified carbon nano tube (m-CNTs) is obtained by modifying Carbon Nano Tubes (CNTs) by 1,3, 5-benzenetricarboxylic acid;
the modified carbon fiber (m-CF) is obtained by modifying Carbon Fiber (CF) with 3- (2, 3-epoxypropoxy) propyltrimethoxysilane.
In some embodiments, the PBT composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the PBT composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the method for preparing the modified carbon nanotube comprises the following steps: dispersing 100 parts by weight of carbon nano tubes in a polyphosphoric acid solution, adding 40-60 parts by weight of 1,3, 5-benzenetricarboxylic acid and 5-15 parts by weight of phosphorus pentoxide, heating to 90-110 ℃ under the protection of nitrogen, stirring for 1-3 hours, then dripping 5-15 parts by weight of phosphoric acid, then continuously heating to 120-140 ℃, stirring for 10-16 hours, cooling to normal temperature, filtering the modified carbon nano tubes by a microporous filter membrane and an acid-base resistant funnel, washing with acetone for 1-3 times, and then drying the obtained modified carbon nano tubes at 50-70 ℃.
In some embodiments, the method for preparing the modified carbon fiber comprises the following steps: putting 100 parts by weight of carbon fiber into a stirrer, then atomizing and spraying a mixed solution of ethanol and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane with a mass ratio of 1-13 onto the carbon fiber at normal temperature, stirring and scattering at 1000-2000 r/min, and heating and drying to obtain the modified carbon fiber; the dosage of the mixed liquid is 2-4% of the mass of the carbon fiber.
In some of these examples, the primary antioxidant is 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The invention also aims to provide a preparation method of the PBT composite material.
The specific technical scheme for realizing the aim of the invention is as follows:
a preparation method of a PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 100-120 ℃ for 2-4 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) Adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone), and adding the modified carbon fiber into the parallel double-screw extruder (totally eight zones) (for example, a third zone) in the other side direction (for example, the third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 220-240 ℃, the temperature of the second zone is 225-245 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 235-255 ℃, the temperature of the fifth zone is 235-255 ℃, the temperature of the sixth zone is 235-255 ℃, the temperature of the seventh zone is 230-250 ℃, the temperature of the eighth zone is 230-250 ℃, the temperature of the die head is 230-250 ℃, and the rotating speed of the screw is 200-600 rpm.
In some of these embodiments, a method of making the PBT composite includes the steps of:
(1) Drying the PBT resin at the temperature of 105-115 ℃ for 2.5-3.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) Adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone), and adding the modified carbon fiber into the parallel double-screw extruder (totally eight zones) (for example, a third zone) in the other side direction (for example, the third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 225-235 ℃, the temperature of the second zone is 230-240 ℃, the temperature of the third zone is 235-245 ℃, the temperature of the fourth zone is 240-250 ℃, the temperature of the fifth zone is 240-250 ℃, the temperature of the sixth zone is 240-250 ℃, the temperature of the seventh zone is 235-245 ℃, the temperature of the eighth zone is 235-245 ℃, the temperature of the die head is 235-245 ℃, and the rotating speed of the screw is 300-500 rpm.
In some of these embodiments, the screw shape of the parallel twin screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35-50; the screw is provided with more than 1 (including 1) meshing block area and more than 1 (including 1) reverse thread area.
In some of these embodiments, the ratio L/D of the length L of the screw to the diameter D is from 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
In some embodiments, in step (1) and/or step (2), the agitator is a high-speed agitator and the rotation speed is 500-1500 rpm.
The PBT composite material has the following functions of raw materials:
the principle of the conductive loss type wave absorbing agent is that under the action of an electric field, conductive carriers do directional drift motion, so that conductive current can be formed in a wave absorbing material, the current is thermally lost, namely, the conductive loss is obtained, and the wave absorbing agent belonging to the conductive loss type comprises carbon nano tubes, carbon fibers and the like. Compared with a Carbon Nano Tube (CNTs) reinforced resin matrix composite material and a carbon fiber reinforced resin matrix composite material, the CNTs/carbon fibers jointly reinforce the resin matrix composite material, and fully utilize mutual interaction and synergistic action, so that the defect of performance improvement of a single reinforced relative composite material is overcome, the performance of the composite material is qualitatively changed, for example, the crack resistance of a matrix is improved, and the wave absorbing performance, the interlayer fracture toughness, the impact resistance, the wear resistance and the like of the composite material are improved. The conductivity loss influence factor is conductivity, and the larger the conductivity is, the larger the current caused by the change of the electric field and the eddy current caused by the change of the magnetic field are, the larger the loss of the electromagnetic energy is. Therefore, more effective conductive networks can be formed by compounding and using the modified carbon nano tubes and the modified carbon fibers, and the conductivity is increased, so that the conductivity loss is increased, and the wave-absorbing performance is improved.
The basic copper phosphate can be used as a laser sensitive additive, and after laser irradiation, the basic copper phosphate can release metal copper atoms with reducibility, so that a catalytic activation center is provided for subsequent chemical plating, metal ions in chemical plating solution are promoted to be deposited in a laser region to form a conductive pattern, and the metal copper atoms also have the effect of increasing the bonding strength of a plating layer and a resin matrix. The Cu and Sn have high absorptivity to near infrared laser, based on the interaction theory of the Cu and Sn and laser and the rutile structure of tin oxide, when the near infrared laser irradiates the surface of a material, the laser energy initiates the physical and chemical reaction in the material, the valence bond of the tin oxide is broken, tin particles are exposed and deposited on the surface of the material, the relative density of tin atoms is higher, more catalytic activation seeds can be provided for chemical copper plating, and because the number of atoms on the surface of a nanoparticle is more, the coordination number of surface atoms is insufficient and the combination energy is different from that of internal atoms, the nanoparticle has high surface energy and high surface activity, and in the chemical copper plating process, the tin atoms on the surface of the material are more likely to react with other atoms in a chemical plating solution, so that the catalytic activity of the tin atoms as the activation seeds is improved. In addition, the spherical calcium carbonate is beneficial to improving the roughness of the surface of the LDS part, thereby being beneficial to copper deposition in the chemical copper plating process. Therefore, when the basic copper phosphate, the tin oxide and the spherical calcium carbonate are compounded and used as the laser sensitive additive, more activated seeds and catalytic activity can be provided, the chemical plating time of a sample is shorter, the speed is higher, the plating layer is finer and smoother, and the binding force of the plating layer and a matrix resin material is better.
The main antioxidant 1,3, 5-tri (4-tertiary butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -triketone and the auxiliary antioxidant bis (2, 4-dicumylphenyl) pentaerythritol diphosphite have higher heat resistance, are suitable for being used in blending preparation, and have good compatibility with PBT materials.
Compared with the prior art, the PBT composite material and the preparation method thereof provided by the invention have the following beneficial effects:
1. the modified carbon nano tube and the modified carbon fiber are compounded to form more effective conductive networks, so that the conductivity is increased, the conductivity loss is increased, and the wave-absorbing performance of the PBT composite material is improved.
2. When the copper hydroxide phosphate, the tin oxide and the spherical calcium carbonate are compounded and used as the laser sensitive additive, more activated seeds and catalytic activity can be provided, the chemical plating time of a sample is shorter, the speed is higher, the plating layer is finer and smoother, and the binding force of the plating layer and a matrix resin material is better.
3. The preparation method of the PBT composite material provided by the invention has the advantages of simple process, easiness in control and low requirements on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the preparation method is favorable for industrial production.
Drawings
FIG. 1 is a flow chart of a preparation process of the PBT composite material.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully hereinafter with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The reaction mechanism of the PBT composite material is as follows (see a preparation process flow chart in figure 1):
wherein R is modified carbon fiber, basic copper phosphate, tin oxide and spherical calcium carbonate.
Mechanism of reaction
As can be seen from the above reaction formula, (1) grafting 1,3, 5-benzenetricarboxylic acid on Carbon Nanotubes (CNTs) under the catalysis of polyphosphoric acid and phosphorus pentoxide to obtain modified carbon nanotubes (m-CNTs); (2) The terminal carboxyl of the modified carbon nano tube can react with the terminal hydroxyl of the PBT to obtain m-CNTs-g-PBT; (3) Epoxy groups in the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate coated with the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane can react with terminal hydroxyl groups of the PBT, so that the compatibility and the interface cohesiveness of the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate with PBT base material resin are improved.
The raw materials used in the embodiment of the invention are as follows:
PBT resin, available from Changchun plastics, inc., taiwan, china.
Carbon nanotubes, purchased from Shenzhen nanogang GmbH.
Carbon fibers were purchased from shenzhou carbon fibers, llc of ji lin.
Copper hydroxide phosphate, available from western Asia chemical technology (Shandong) Inc.
Tin oxide, available from new materials science and technology ltd, wanshan, fluvial.
Spherical calcium carbonate purchased from Shenzhen Jinhaohui industry development Limited.
3- (2, 3-glycidoxy) propyltrimethoxysilane, available from Shanghai Georgi Silicone science, inc.
1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, available from Shih chemical Co., ltd.
Bis (2, 4-dicumylphenyl) pentaerythritol diphosphite available from Shanghai Ji to Biochemical technology, inc.
Polyphosphoric acid, purchased from Qing Chundong chemical Co., ltd.
1,3, 5-benzenetricarboxylic acid, available from Shandong Hao Shunhu chemical Co., ltd.
Phosphorus pentoxide, available from cyclolee chemical ltd, shandong.
Phosphoric acid, available from national pharmaceutical group chemical reagents, ltd.
Acetone, available from national pharmaceutical group chemical agents, ltd.
Ethanol, available from national pharmaceutical group chemical agents, ltd.
The preparation method of the modified carbon nanotubes (m-CNTs) used in the following examples comprises the following steps: dispersing 100g of carbon nano tube in a polyphosphoric acid solution, adding 50g of 1,3, 5-benzenetricarboxylic acid and 10g of phosphorus pentoxide, heating to 100 ℃ under the protection of nitrogen, stirring for 2 hours, then dripping 10g of phosphoric acid, continuing heating to 130 ℃, stirring for 13 hours, cooling to normal temperature, filtering the modified carbon nano tube by a microfiltration membrane and an acid-alkali resistant funnel, washing for 2 times by using acetone, and then drying the obtained modified carbon nano tube at 60 ℃.
The modified carbon fibers (m-CF) used in the following examples were prepared by a method comprising the steps of: putting 100g of carbon fiber into a stirrer, then atomizing and spraying a mixed solution of ethanol and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane with a mass ratio of 1; the dosage of the mixed liquid is 3% of the mass of the carbon fiber.
The present invention will be described in detail with reference to specific examples.
Example 1 PBT composite Material and Process for producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 120 ℃ for 2 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 240 ℃, the temperature in the second zone was 245 ℃, the temperature in the third zone was 250 ℃, the temperature in the fourth zone was 255 ℃, the temperature in the fifth zone was 255 ℃, the temperature in the sixth zone was 255 ℃, the temperature in the seventh zone was 250 ℃, the temperature in the eighth zone was 250 ℃, the temperature of the die head was 250 ℃ and the screw speed was 600rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 2 PBT composite Material and method for producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 220 ℃, the temperature in the second zone was 225 ℃, the temperature in the third zone was 230 ℃, the temperature in the fourth zone was 235 ℃, the temperature in the fifth zone was 235 ℃, the temperature in the sixth zone was 230 ℃, the temperature in the seventh zone was 230 ℃, the temperature in the eighth zone was 230 ℃, the temperature in the die head was 230 ℃ and the screw speed was 200rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 3 PBT composite Material and method for producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 115 ℃ for 2.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tubes, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 235 deg.C, the temperature in the second zone was 240 deg.C, the temperature in the third zone was 245 deg.C, the temperature in the fourth zone was 250 deg.C, the temperature in the fifth zone was 250 deg.C, the temperature in the sixth zone was 250 deg.C, the temperature in the seventh zone was 245 deg.C, the temperature in the eighth zone was 245 deg.C, the temperature in the die head was 245 deg.C, and the screw speed was 500rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 4 PBT composite Material and method of producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at 105 ℃ for 3.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 225 ℃, the temperature in the second zone was 230 ℃, the temperature in the third zone was 235 ℃, the temperature in the fourth zone was 240 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 240 ℃, the temperature in the seventh zone was 235 ℃, the temperature in the eighth zone was 235 ℃, the temperature in the die head was 235 ℃ and the screw speed was 300rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 5 PBT composite Material and method of making the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 6 PBT composite Material and method of producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone), and adding the modified carbon fiber into the parallel double-screw extruder (totally eight zones) in the other lateral direction (third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 7 PBT composite and Process for preparing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin for 3 hours at the temperature of 110 ℃, cooling, and adding the cooled PBT resin, the modified carbon nano tubes, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone), and adding the modified carbon fiber into the parallel double-screw extruder (totally eight zones) in the other lateral direction (third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 1
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin for 3 hours at the temperature of 110 ℃, cooling, and adding the cooled PBT resin, the modified carbon nano tubes, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 2
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin for 3 hours at the temperature of 110 ℃, cooling, and adding the cooled PBT resin, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 3
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, the spherical calcium carbonate and the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone), and adding the modified carbon fiber into the parallel double-screw extruder (totally eight zones) in the other lateral direction (third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 4
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, the tin oxide and the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 5
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) Drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) Adding the basic copper phosphate, the tin oxide and the spherical calcium carbonate into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
The following is a summary of the raw material compositions of examples 1-7 and comparative examples 1-5.
TABLE 1 summary of the raw material compositions of examples 1-7 and comparative examples 1-5
Wherein the primary antioxidant 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione and the secondary antioxidant bis (2, 4-dicumylphenyl) pentaerythritol diphosphite of the above examples and comparative examples were added in amounts of 0.5 part each.
Examples 1 to 7 were prepared to prepare PBT composites by adjusting the addition amounts of modified carbon nanotubes, modified carbon fibers, basic copper phosphate, tin oxide, spherical calcium carbonate, and 3- (2, 3-glycidoxy) propyltrimethoxysilane, comparative examples 1 to 5 were prepared to prepare PBT composites on the basis of the raw materials of example 7, comparative example 1 was prepared without adding modified carbon fibers, comparative example 2 was prepared without adding modified carbon nanotubes, comparative example 3 was prepared without adding tin oxide, comparative example 4 was prepared without adding spherical calcium carbonate, and comparative example 5 was prepared without adding 3- (2, 3-glycidoxy) propyltrimethoxysilane. The PBT composite materials prepared by the above examples and comparative examples are subjected to the following performance tests:
tensile property: the tensile rate is 50mm/min according to the test of GB/T1040-2006 standard.
Wave-absorbing property: according to the GJB 5239-2004 standard test, a vector network analyzer of Agilent, USA is adopted for testing, and a sample is a coaxial ring sample with the thickness of 2mm, the outer diameter of 7mm and the inner diameter of 3 mm. The wider the width of the microwave frequency is, the better the coverage area is, and the higher the microwave frequency is, the better the coverage area is; the wave-absorbing performance reflects the wave-absorbing capacity of the material to electromagnetic waves, and the larger the absolute value of the numerical value of the wave-absorbing performance is, the more the electromagnetic waves are attenuated after passing through the material, the better the wave-absorbing performance is.
Adhesion test of metal coating on plastic part surface (hundred lattice test): testing according to ASTM D3359 standard, wherein under the conditions of room temperature 23 +/-2 ℃ and relative humidity 50 +/-5%, 10 multiplied by 10 small grids of 1 multiplied by 1mm are scribed on the surface of a test sample by a sharp blade (the blade angle is 15-30 ℃), and each scribing line is deep and a plating bottom layer is formed; the brush cleans the test area; firmly sticking the small tested grids by using a 3M600 adhesive tape, and forcibly wiping the adhesive tape by using an eraser to increase the contact area and force of the adhesive tape and the tested area; one end of the tape was grasped by hand and the scotch tape was quickly pulled off at an angle of 60 ° in the vertical direction and 2 identical tests were performed at the same location. And (4) judging a result: the adhesive force is qualified when the adhesive force is required to be more than or equal to 4B; 5B-the scribing edge is smooth, and no paint falls off at the scribing edge and the intersection; 4B-there is a small piece of paint falling off at the cross point of the scribe line, and the total area of the falling off is less than 5%; 3B-small pieces of paint fall off at the edge and the intersection of the scribing line, and the total falling area is between 5 and 15 percent; 2B-pieces of paint fall off at the edges and the cross points of the lines, and the total falling area is 15-35%; 1B-a piece of paint falls off at the edge and the intersection of the line, and the total area of the falling off is between 35 and 65 percent; 0B-there is a patch of paint falling off at the edge and intersection of the score line, and the total area of falling off is greater than 65%.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the PBT composites of examples 1-7 and comparative examples 1-5
As can be seen from table 2:
with the reduction of the addition amount of the modified carbon fiber, the tensile strength of the PBT composite material shows a reduced variation trend. This is mainly because the modified carbon fiber has high strength and high rigidity, and has a strong reinforcing effect on the base resin.
With the reduction of the addition amount of the modified carbon nanotube and the modified carbon fiber, the wave absorbing capability of the PBT composite material is reduced. The carbon nanotube and the carbon fiber belong to a conductive loss type wave absorber, the conductivity is the conductive loss influencing factor, and the larger the conductivity is, the larger the eddy current caused by the change of the current and the magnetic field caused by the change of the electric field is, and the larger the loss of the electromagnetic energy is. Because the addition amount of the modified carbon nano tube and the modified carbon fiber is reduced, the formed effective conductive network is less, and the conductivity is reduced, so that the conductivity loss is reduced, and the wave-absorbing performance is reduced.
With the reduction of the addition of the basic copper phosphate, the tin oxide and the spherical calcium carbonate, the adhesive force of the metal coating on the surface of the plastic part of the PBT composite material is not changed greatly. When the addition amount of the basic copper phosphate is 3 parts, the addition amount of the tin oxide is 0.5 part and the addition amount of the spherical calcium carbonate is 1 part, the adhesion force of the metal plating layer on the surface of the plastic part is reduced from 5B to 4B.
In conclusion, by adjusting the addition amounts of the modified carbon nanotube, the modified carbon fiber, the basic copper phosphate, the tin oxide, the spherical calcium carbonate and the 3- (2, 3-glycidoxy) propyltrimethoxysilane and under the synergistic cooperation of the assistants, the PBT composite material which has excellent mechanical properties and wave absorption properties and can be directly formed by laser can be obtained.
Compared with the comparative example 1, the tensile strength and the wave-absorbing performance of the modified carbon fiber are lower than those of the modified carbon fiber in the example 7 in the comparative example 1. This is because the carbon fiber has high strength and high rigidity, and is higher than the carbon nanotube, so the tensile strength of example 7 is higher than that of comparative example 1; in addition, because the modified carbon nano tubes and the modified carbon fibers are not used in a compounding manner, an effective conductive network formed by the modified carbon nano tubes and the modified carbon fibers is less, and the conductivity is reduced, so that the conductivity loss is reduced, and the wave-absorbing performance is reduced, so that the wave-absorbing performance of the embodiment 7 is higher than that of the comparative example 1.
Compared with the comparative example 2, the comparative example 2 does not add the modified carbon nano tube, and the wave absorbing performance of the modified carbon nano tube is lower than that of the example 7. Because the modified carbon nano tube and the modified carbon fiber are not used in a compounding way, an effective conductive network formed by the modified carbon nano tube and the modified carbon fiber is less, and the conductivity is reduced, so that the conductivity loss is reduced, and the wave absorbing performance is reduced.
Example 7 compared to comparative example 3, comparative example 3 was conducted without tin oxide and the adhesion of the metal coating on the surface of the plastic part was reduced from 5B to 4B. The absorption rate of Cu and Sn to near infrared laser is high, based on the interaction theory of Cu and Sn and laser and the rutile structure of tin oxide, when near infrared laser irradiates the surface of a material, laser energy initiates a physical and chemical reaction in the material, the valence bond of tin oxide is broken, tin particles are exposed and deposited on the surface of the material, the relative density of tin atoms is high, more catalytic activation seeds can be provided for chemical copper plating, and the surface of a nanoparticle has high surface energy and high surface activity because the number of atoms on the surface of the nanoparticle is large, the coordination number of surface atoms is insufficient and the binding energy is different from that of internal atoms, the tin atoms on the surface of the material are easy to react with other atoms in chemical plating solution in the chemical copper plating process, and the catalytic activity of the tin atoms as the activation seeds is improved. Thus, comparative example 3, which did not contain tin oxide, had a plastic part surface with a metallic coating with poorer adhesion than example 7.
Example 7 compared to comparative example 4, comparative example 4 had no spherical calcium carbonate added and the adhesion of the metal coating on the surface of the plastic part decreased from 5B to 4B. This is because spherical calcium carbonate is beneficial to improving the roughness of the surface of the LDS part, thereby being beneficial to copper deposition during electroless copper plating. Thus, comparative example 4, which did not contain spherical calcium carbonate, had a plastic part surface with a metal coating having a poorer adhesion than example 7.
Example 7 in comparison with comparative example 5, which did not add 3- (2, 3-glycidoxy) propyltrimethoxysilane, had a poorer tensile strength than example 7. The epoxy groups in the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate coated with the 3- (2, 3-epoxypropoxy) propyltrimethoxysilane can react with the terminal hydroxyl groups of the PBT, so that the compatibility and the interface cohesiveness of the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate with the PBT base material resin are improved, and the tensile strength of the PBT composite material is improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. The PBT composite material is characterized by being prepared from the following raw materials in parts by weight:
100 parts of PBT resin,
5 to 15 parts of modified carbon nano-tube,
10-20 parts of modified carbon fiber,
3-11 parts of basic copper phosphate,
0.5 to 2.5 portions of tin oxide,
1 to 5 parts of spherical calcium carbonate,
0.2 to 2 portions of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane,
0.1 to 1 portion of main antioxidant,
0.1-1 part of auxiliary antioxidant;
the modified carbon nano tube is obtained by modifying the carbon nano tube by 1,3, 5-benzene tricarboxylic acid; the preparation method of the modified carbon nano tube comprises the following steps: dispersing 100 parts by weight of carbon nano tubes in a polyphosphoric acid solution, adding 40-60 parts by weight of 1,3, 5-benzenetricarboxylic acid and 5-15 parts by weight of phosphorus pentoxide, heating to 90-110 ℃ under the protection of nitrogen, stirring for 1-3 hours, dripping 5-15 parts by weight of phosphoric acid, then continuously heating to 120-140 ℃, stirring for 10-16 hours, cooling to normal temperature, filtering the modified carbon nano tubes by a microporous filter membrane and an acid-base-resistant funnel, washing for 1-3 times by acetone, and then drying the obtained modified carbon nano tubes at 50-70 ℃;
the modified carbon fiber is obtained by modifying carbon fiber with 3- (2, 3-epoxypropoxy) propyl trimethoxy silane; the preparation method of the modified carbon fiber comprises the following steps: putting 100 parts by weight of carbon fiber into a stirrer, then atomizing and spraying a mixed solution of ethanol and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane with a mass ratio of 1-13 onto the carbon fiber at normal temperature, stirring and scattering at 1000-2000 r/min, and heating and drying to obtain the modified carbon fiber; the amount of the mixed liquid is 2-4% of the mass of the carbon fiber;
the main antioxidant is 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethyl benzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, and the auxiliary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite;
the preparation method of the PBT composite material is characterized by comprising the following steps:
(1) Drying the PBT resin at the temperature of 100-120 ℃ for 2-4 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, adding the modified carbon fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 220-240 ℃, the temperature of the second zone is 225-245 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 235-255 ℃, the temperature of the fifth zone is 235-255 ℃, the temperature of the sixth zone is 235-255 ℃, the temperature of the seventh zone is 230-250 ℃, the temperature of the eighth zone is 230-250 ℃, the temperature of the die head is 230-250 ℃, and the rotating speed of the screw is 200-600 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35-50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
2. The PBT composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
100 parts of PBT resin,
7-13 parts of modified carbon nano-tube,
12 to 18 portions of modified carbon fiber,
4 to 10 parts of basic copper phosphate,
1-2 parts of tin oxide,
2 to 4 parts of spherical calcium carbonate,
0.5 to 1.5 portions of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane,
0.2 to 0.8 portion of main antioxidant,
0.2 to 0.8 portion of auxiliary antioxidant.
3. The PBT composite material according to claim 2, which is prepared from the following raw materials in parts by weight:
100 parts of PBT resin (100 parts),
8 to 12 parts of modified carbon nano-tube,
14-16 parts of modified carbon fiber,
6 to 8 parts of basic copper phosphate,
1.2 to 1.8 portions of tin oxide,
2.5 to 3.5 portions of spherical calcium carbonate,
0.7 to 1.3 portions of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane,
0.4 to 0.6 portion of main antioxidant,
0.4-0.6 part of auxiliary antioxidant.
4. A process for the preparation of a PBT composite according to any one of claims 1 to 3, comprising the steps of:
(1) Drying the PBT resin at the temperature of 100-120 ℃ for 2-4 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, adding the modified carbon fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 220-240 ℃, the temperature of the second zone is 225-245 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 235-255 ℃, the temperature of the fifth zone is 235-255 ℃, the temperature of the sixth zone is 235-255 ℃, the temperature of the seventh zone is 230-250 ℃, the temperature of the eighth zone is 230-250 ℃, the temperature of the die head is 230-250 ℃, and the rotating speed of the screw is 200-600 rpm.
5. The process for the preparation of the PBT composite material according to claim 4, comprising the steps of:
(1) Drying the PBT resin at the temperature of 105-115 ℃ for 2.5-3.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) Adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, adding the modified carbon fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 225-235 ℃, the temperature of the second zone is 230-240 ℃, the temperature of the third zone is 235-245 ℃, the temperature of the fourth zone is 240-250 ℃, the temperature of the fifth zone is 240-250 ℃, the temperature of the sixth zone is 240-250 ℃, the temperature of the seventh zone is 235-245 ℃, the temperature of the eighth zone is 235-245 ℃, the temperature of the die head is 235-245 ℃, and the rotating speed of the screw is 300-500 rpm.
6. The process for preparing a PBT composite according to claim 4, wherein the screw shape of the parallel twin-screw extruder is a single-thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35-50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
7. The process for preparing a PBT composite material according to claim 6, wherein the ratio L/D of the screw length L and the diameter D is 35 to 45; 2 meshing block areas and 1 reverse thread area are arranged on the screw rod; in the step (1) and/or the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 500-1500 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111630420.4A CN114149666B (en) | 2021-12-28 | 2021-12-28 | PBT composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111630420.4A CN114149666B (en) | 2021-12-28 | 2021-12-28 | PBT composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114149666A CN114149666A (en) | 2022-03-08 |
| CN114149666B true CN114149666B (en) | 2023-04-18 |
Family
ID=80449358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111630420.4A Active CN114149666B (en) | 2021-12-28 | 2021-12-28 | PBT composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114149666B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140124918A (en) * | 2013-04-02 | 2014-10-28 | 김한주 | Composition for laser direct structuring process |
| US20190322861A1 (en) * | 2016-04-29 | 2019-10-24 | Sabic Global Technologies B.V. | Engineering thermoplastic compositions with high nano molding bonding strength and laser direct structuring function |
| CN108250692A (en) * | 2016-12-28 | 2018-07-06 | 珠海万通特种工程塑料有限公司 | A kind of polyester molding compounds and its preparation method and application |
| WO2018130970A1 (en) * | 2017-01-11 | 2018-07-19 | Sabic Global Technologies B.V. | Laser platable thermoplastic compositions with a laser activatable metal compound and shaped articles therefrom |
| CN108587085A (en) * | 2018-05-25 | 2018-09-28 | 邹峰 | A kind of preparation method of carbon nano-fiber base polyester film |
| CN110128799A (en) * | 2019-05-31 | 2019-08-16 | 珠海格力新材料有限公司 | PBT composite material and preparation method thereof |
-
2021
- 2021-12-28 CN CN202111630420.4A patent/CN114149666B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114149666A (en) | 2022-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Sustainable wood-based composites for microwave absorption and electromagnetic interference shielding | |
| CN100405886C (en) | Polyethylene composite film for shielding wideband electromagnetic wave and its preparing method | |
| CN102120891A (en) | Thermoplastic resin composition with EMI shielding properties and EMI shielding product prepared thereby | |
| CN103451762B (en) | A kind of amorphous nano-crystalline improves the self-cleaning shielding fiber preparation method of terylene | |
| KR101771899B1 (en) | The fabrication method of metal/carbon hybrid particles for coating the electromagnetic wave shielding fabric | |
| CN108358505B (en) | Fluororesin intermediate medium layer filled with microwave dielectric ceramic powder and preparation method thereof | |
| CN110883337A (en) | Spray granulation Fe-Al2O3Preparation method of spraying composite powder | |
| CN110205096A (en) | A kind of controllable micropore absorbing meta-material and its preparation method and application | |
| CN103390479B (en) | A kind of inorganic compounding micropowder of high electromagnet shield effect and preparation method thereof | |
| CN114149666B (en) | PBT composite material and preparation method thereof | |
| CN108342077B (en) | Three-phase double-percolation electromagnetic shielding material and preparation method thereof | |
| CN104194299A (en) | Electromagnetic shielding PC (polycarbonate)-based composite resin material and interphone shell | |
| CN105199564A (en) | Thermoset electromagnetic shielding powder coating | |
| CN108659506A (en) | A kind of nanometer of cuprous sulfide composite electromagnetic shield materials and preparation method thereof | |
| KR20030019527A (en) | Electromagnetic Wave Shielding Material using Carbon Nano-Composites and Preparation Method Thereof | |
| CN116144102B (en) | High-toughness polypropylene material and preparation method thereof | |
| CN108384177B (en) | Four-phase double-percolation electromagnetic shielding material and preparation method thereof | |
| KR101402437B1 (en) | The method of silver coated flake copper powder used membrane sheet circuit printing conductive paste | |
| CN116144145B (en) | Polyethylene terephthalate-1, 4-cyclohexanedimethanol ester composition and preparation method thereof | |
| CN105199563A (en) | Electromagnetic shielding material adopting thermoset powder | |
| CN115873382B (en) | Polybutylene terephthalate composition and preparation method thereof | |
| CN116178938B (en) | Flame-retardant polyamide 6 composite material and preparation method thereof | |
| Kim et al. | Carbon fiber-reinforced composites for EMI shielding | |
| CN117089200A (en) | PPS-based LDS composition and preparation method thereof | |
| CN115403924B (en) | Heat-absorbing polyamide composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |