CN115873382A - Polybutylene terephthalate composition and preparation method thereof - Google Patents
Polybutylene terephthalate composition and preparation method thereof Download PDFInfo
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- CN115873382A CN115873382A CN202111154888.0A CN202111154888A CN115873382A CN 115873382 A CN115873382 A CN 115873382A CN 202111154888 A CN202111154888 A CN 202111154888A CN 115873382 A CN115873382 A CN 115873382A
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- metal oxide
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- -1 Polybutylene terephthalate Polymers 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 79
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 79
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000012545 processing Methods 0.000 claims abstract description 5
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical group [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000499 gel Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 9
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011240 wet gel Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 3
- 238000005516 engineering process Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004033 plastic Substances 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 238000007747 plating Methods 0.000 description 10
- 229960004106 citric acid Drugs 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 5
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229960002303 citric acid monohydrate Drugs 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010329 laser etching Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polybutylene terephthalate composition and a preparation method thereof. The polybutylene terephthalate composition is prepared from the following raw materials in percentage by weight: 83-98.5% of polybutylene terephthalate; 1.5 to 15 percent of hollow metal oxide; 0-2% of antioxidant; the hollow metal oxide is obtained by coating the metal oxide on the surface of POSS. The polybutylene terephthalate composition can be used for a laser direct forming technology, has good heat resistance and excellent mechanical property, is environment-friendly and nontoxic, and has low price and simple processing technology.
Description
Technical Field
The invention relates to the field of materials, in particular to a polybutylene terephthalate composition for laser forming and a preparation method thereof.
Background
The three-dimensional molding interconnection device (3D-MID), also known as a three-dimensional circuit or a three-dimensional circuit, is a three-dimensional molding interconnection device, in which a lead and a pattern having an electrical function are fabricated on an injection molded plastic housing, so that the electrical interconnection function, the function of supporting components, the support and protection functions of the plastic housing, and the like of a common circuit board are integrated into a whole to form a three-dimensional circuit carrier. The three-dimensional molding interconnection device has the design advantages that the shape and the function can be selected according to the design requirement, and the three-dimensional molding interconnection device is suitable for smaller and lighter development trends, and also has the advantages of reducing the installation level, reducing the number of components, improving the reliability, reducing the material quantity and variety investment, being beneficial to the economic environment aspect such as environmental protection treatment and the like. 3D-MID has already had a considerable number of applications in fields such as car, industry, computer, communication at present, will certainly become an important branch of circuit board trade in the future.
The 3D-MID mainly comprises two modes, namely 2ShotMID (dual-mode injection molding) and Laser Direct Structure MID (LDS MID for short), and mainly adopts LDS application at present. LDS (Laser-Direct-Structuring) is an english abbreviation for Laser-Direct-Structuring, and means that a computer controls the movement of a Laser according to the trajectory of a conductive pattern, and projects the Laser onto a molded three-dimensional plastic device, and a circuit pattern is activated within a few seconds.
The plastics for laser direct structuring disclosed in patents CN101784607A, CN102066473A, CN102066122A, etc. all add a non-conductive organometallic complex (such as copper salt or copper chromium compound) with spinel structure as LDS additive, and this organometallic complex is expensive and not beneficial to popularization and use of plastics for laser direct structuring.
Patent CN109694572A discloses a polyamide composition, a preparation method and use thereof, said polyamide composition comprising polyamide 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 polyamide composition is prepared by melt-extruding the polyamide and the hollow metal oxide particles with an extruder. However, when the hollow metal oxide is synthesized, high-temperature calcination is required, which easily causes agglomeration of powder, thereby resulting in poor product dispersibility and finally affecting the quality stability and the metal coating bonding force of the product.
Disclosure of Invention
Based on this, the invention aims to provide a polybutylene terephthalate composition which is low in price, good in mechanical property and capable of being directly formed by laser.
The specific technical scheme is as follows:
a polybutylene terephthalate composition is prepared from the following raw materials in percentage by weight:
83-98.5% of polybutylene terephthalate;
1.5 to 15 percent of hollow metal oxide;
0-2% of antioxidant;
the hollow metal oxide is obtained by coating the metal oxide on the surface of POSS.
In some of these embodiments, the hollow metal oxide is present in an amount of 2 to 8 weight percent.
In some of these embodiments, the hollow metal oxide is present in an amount of 2-4% by weight.
In some of these embodiments, the weight percent of the hollow metal oxide is 2.5-3.5%.
In some of these embodiments, the hollow metal oxide is 3% by weight.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 35-70%.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 45-65%.
In some of these embodiments, the weight percentage of the metal oxide in the hollow metal oxide is 50-60%.
In some of these embodiments, the metal element in the metal oxide is one or more of copper, silver, gold, zinc, cadmium, gallium, titanium, chromium, cobalt, manganese, cerium, niobium, and iron.
In some of these embodiments, the metal oxide is copper chromium black.
In some of these embodiments, the hollow metal oxide has a density of 1g/cm 3 -6g/cm 3 。
In some of these embodiments, the hollow metal oxide has a density of 1.2g/cm 3 -4g/cm 3 。
In some of these embodiments, the hollow metal oxide has a density of 1.5g/cm 3 -2.7g/cm 3 。
In some of these embodiments, the hollow metal oxide has a particle size of 0.1 μm to 100 μm.
In some of these embodiments, the hollow metal oxide has a particle size of 0.5 μm to 50 μm.
In some embodiments, the hollow metal oxide is prepared from a metal salt corresponding to the metal oxide and amine phenyl POSS by a sol-gel method or a hydrothermal method.
In some of these embodiments, the metal oxide corresponds to a metal salt and an aminophenyl POSS in a mass ratio of 1 to 5.
In some of these embodiments, the metal oxide corresponds to a metal salt and an aminophenyl POSS in a 3 to 4 mass ratio.
In some of these embodiments, the metal salts corresponding to the metal oxides are copper nitrate trihydrate and chromium nitrate nonahydrate.
In some of these embodiments, the mass ratio of copper nitrate trihydrate and chromium nitrate nonahydrate is 1.5 to 2.5.
In some of these embodiments, the method of making the hollow metal oxide comprises the steps of:
(1) Mixing the aminophenyl POSS with metal salt corresponding to the metal oxide, and adding water to dissolve;
(2) Heating the mixed solution prepared in the step (1), dropwise adding a citric acid aqueous solution under stirring, adding a sol stabilizer after dropwise adding is finished, and continuously stirring until the sol is converted into gel, and stopping stirring;
(3) Drying the wet gel prepared in the step (2), and grinding into powder to obtain precursor powder;
(4) And adding water into the precursor powder for crystallization to obtain the hollow metal oxide.
In some embodiments, the ratio of the total mass of the aminophenyl POSS and the metal salt to water in step (1) is 1g:4mL-8mL.
In some of these embodiments, the heating temperature in step (2) is from 70 ℃ to 90 ℃.
In some embodiments, the stirring speed in the step (2) is 1000r/min-1400r/min.
In some embodiments, the stirring speed in the step (2) is 1100r/min-1300r/min.
In some embodiments, the concentration of the aqueous citric acid solution is 0.07g/mL to 0.10g/mL, and the amount of the aqueous citric acid solution added is the same as the amount of water added in step (1).
In some of the embodiments, the sol stabilizer is ethylene glycol, and the addition volume of the ethylene glycol is 0.1% -0.3% of the total volume of the citric acid aqueous solution and the water in the step (1).
In some embodiments, the drying in the step (3) is constant temperature drying under the conditions that the vacuum degree is-0.5 MPa to-0.7 MPa and the temperature is 70 ℃ to 90 ℃.
In some embodiments, step (4) comprises: and (2) putting the precursor powder into a reaction kettle, adding water, uniformly stirring, screwing a kettle cover, crystallizing for 2-7 days under the conditions that the pressure is 15-20 MPa and the temperature is 280-320 ℃, filtering, washing and drying a product to obtain the hollow metal oxide.
In some embodiments, the drying conditions in step (4) comprise: the temperature is 90-110 ℃ and the time is 6-10 hours.
In some of these embodiments, the antioxidant is present in an amount of 0.2 to 0.5 weight percent.
In some of these embodiments, the antioxidant consists of a hindered phenolic antioxidant and a phosphite antioxidant.
In some of these embodiments, the hindered phenolic antioxidant and the phosphite antioxidant are present in the same weight percentage.
In some of these embodiments, the hindered phenolic antioxidant is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the phosphite ester antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
Another object of the present invention is to provide a process for preparing the above polybutylene terephthalate composition.
The specific technical scheme is as follows:
the preparation method of the polybutylene terephthalate composition comprises the following steps:
(a) Drying the polybutylene terephthalate, and mixing the dried polybutylene terephthalate with an antioxidant to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow metal oxide into the parallel double-screw extruder from the side direction, and performing melt extrusion;
(c) And (c) bracing, cooling and dicing the extruded material obtained in the step (b) to obtain the polybutylene terephthalate composition.
In some of these embodiments, the drying conditions of step (a) comprise: the temperature is 100-110 ℃, and the time is 3-5 h.
In some of these embodiments, the processing conditions of the parallel twin screw extruder include: the temperature of the first zone is 200-210 ℃, the temperature of the second zone is 240-255 ℃, the temperature of the third zone is 240-255 ℃, the temperature of the fourth zone is 240-255 ℃, the temperature of the fifth zone is 240-260 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 240-260 ℃, the temperature of the ninth zone is 240-250 ℃, the temperature of the die head is 240-250 ℃, and the retention time of materials in a charging barrel of the parallel double-screw extruder is controlled to be 1-3 minutes.
The present invention has been made to obtain a hollow metal oxide coated with a metal oxide on the surface of POSS, and has found that the resulting polybutylene terephthalate composition can be used for laser direct structuring and has good binding force with a metal plating layer by adding the hollow metal oxide coated with a metal oxide on the surface of POSS as an LDS additive to the polybutylene terephthalate composition. Compared with a material directly taking metal oxide as an LDS additive, the polybutylene terephthalate composition provided by the invention has the advantages that less LDS additive is added, the adhesion of a metal coating after laser etching is higher, the mechanical property is better, the cost is lower, the adhesion of the metal coating can meet the requirement when the addition of hollow metal oxide particles is 2wt%, and the adhesion of the metal coating can reach 5B grade when the addition of hollow metal oxide particles is 3 wt%; and has the advantages of environmental protection, no toxicity, low price, simple processing technology and the like.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
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.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or apparatus that comprises a list of steps is not limited to only those steps or modules recited, but may alternatively include other steps not recited, or may alternatively include other steps inherent to such process, method, article, or apparatus.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The raw materials used in the examples and comparative examples of the present invention were as follows:
polybutylene terephthalate, manufactured by the blue star company under the designation 1100HQ;
amine phenyl POSS, shanghai vasica chemical co;
copper nitrate trihydrate, san Yang chemical trade, inc., tianjin;
chromium nitrate nonahydrate, kepler biotechnology limited, shandong;
citric acid monohydrate, kapler biotechnology limited, shandong;
ethylene glycol, nicoti Henxin chemical technology Co., ltd;
copper-chromium black, domadex 42-303B.
The following are specific examples.
The content of copper-chromium black in the hollow copper-chromium black particles in the following examples was calculated by the following method: firstly, measuring the contents of copper and chromium in the obtained hollow copper-chromium black particles, and then, according to the contents of copper and chromium and the molecular formula CuCr of copper-chromium black 2 O 4 And calculating the mass of the corresponding copper chromium black, and dividing the mass of the copper chromium black by the mass of the obtained hollow copper chromium black particles to obtain the content of the copper chromium black in the hollow copper chromium black particles.
EXAMPLE 1 preparation of hollow copper chromium Black particles
Mixing 20g of aminophenyl POSS, 20g of copper nitrate trihydrate and 40g of chromium nitrate nonahydrate, adding 500ml of distilled water to fully dissolve the mixture, and transferring the mixture into a flask; weighing 45g of citric acid monohydrate, and preparing 500mL of citric acid aqueous solution; placing the flask in a constant-temperature water bath kettle, setting a stirring device, slowly dripping the citric acid aqueous solution into the flask through a dropping funnel under strong stirring (the rotating speed is 1200 r/min), and adding 2ml of ethylene glycol for stabilizing sol after finishing dripping; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain dry gel, and grinding the dry gel into powder to obtain precursor powder; however, the device is not suitable for use in a kitchenAnd then putting the precursor powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding deionized water, uniformly stirring, screwing a kettle cover, setting the pressure to be 18MPa, and crystallizing at 300 ℃ for 5 days. Filtering and washing the obtained product, and drying in the air at 100 ℃ for 8 hours to obtain the hollow copper-chromium black particles, wherein the copper-chromium black content is 50wt%, the particle size is 0.5-50 mu m, and the density is 1.9g/cm 3 。
Preparation example 2 preparation of hollow copper-chromium black granules
15g of aminophenyl POSS, 20g of copper nitrate trihydrate, 40g of chromium nitrate nonahydrate were mixed, 500ml of distilled water was added to make them sufficiently dissolved, and they were transferred to a flask; weighing 45g of citric acid monohydrate, and preparing 500mL of citric acid aqueous solution; placing the flask in a constant-temperature water bath kettle, setting a stirring device, slowly dripping the citric acid aqueous solution into the flask through a dropping funnel under strong stirring (the rotating speed is 1200 r/min), and adding 2ml of ethylene glycol for stabilizing sol after finishing dripping; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain dry gel, and grinding the dry gel into powder to obtain precursor powder; and then putting the precursor powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding deionized water, uniformly stirring, screwing a kettle cover, setting the pressure to be 18MPa, and crystallizing for 5 days at 300 ℃. Filtering and washing the obtained product, and drying in the air at 100 ℃ for 8 hours to obtain hollow copper-chromium black particles, wherein the copper-chromium black content is 60wt%, the particle size is 0.5-50 mu m, and the density is 2.2g/cm 3 。
Preparation example 3 preparation of hollow copper chromium Black particles
Mixing 40g of aminophenyl POSS, 20g of copper nitrate trihydrate, and 40g of chromium nitrate nonahydrate, adding 500ml of distilled water to sufficiently dissolve the mixture, and transferring the mixture into a flask; weighing 45g of citric acid monohydrate, and preparing 500mL of citric acid aqueous solution; placing the flask in a constant temperature water bath, setting a stirring device, slowly dripping citric acid water solution into the flask through a dropping funnel under strong stirring (rotation speed of 1200 r/min) at a water bath temperature of 80 deg.CBottling, and adding 2ml of glycol for stabilizing sol after the dropwise addition is finished; continuously stirring until the sol is converted into gel, stopping stirring, placing the obtained wet gel in a vacuum drying oven with the vacuum degree of-0.6 Mpa, drying at the constant temperature of 80 ℃ to obtain dry gel, and grinding the dry gel into powder to obtain precursor powder; and then putting the precursor powder into a stainless steel reaction kettle with a polytetrafluoroethylene lining, adding deionized water, uniformly stirring, screwing a kettle cover, setting the pressure to be 18MPa, and crystallizing for 5 days at 300 ℃. Filtering and washing the obtained product, and drying in the air at 100 ℃ for 8 hours to obtain the hollow copper-chromium black particles, wherein the copper-chromium black content is 35wt%, the particle size is 0.5-50 mu m, and the density is 1.6g/cm 3 。
Examples 4-8 preparation of polybutylene terephthalate compositions
(a) Drying polybutylene terephthalate at 100-110 ℃ for 3-5h, and then putting the dried polybutylene terephthalate, antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and tris (2, 4-di-tert-butylphenyl) phosphite into a mixer for mixing for 20 minutes to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the idle copper-chromium black granules prepared in the example 2 into a sixth zone of the parallel double-screw extruder, and performing melt extrusion, wherein the processing technology of the parallel double-screw extruder is as follows: the temperature of the first zone is 200-210 ℃, the temperature of the second zone is 240-255 ℃, the temperature of the third zone is 240-255 ℃, the temperature of the fourth zone is 240-255 ℃, the temperature of the fifth zone is 240-260 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 240-260 ℃, the temperature of the ninth zone is 240-250 ℃, the temperature of a die head is 240-250 ℃, and the retention time of materials in a cylinder of a parallel double-screw extruder is controlled to be 1-3 minutes;
(c) And (c) bracing, cooling and dicing the extruded material obtained in the step (b) to obtain the polybutylene terephthalate composition.
The raw material components of each example are used in the following amounts:
EXAMPLE 9 preparation of polybutylene terephthalate composition
This example differs from example 6 in that: the hollow copper chromium black granules provided in example 1 were replaced with the hollow copper chromium black granules, and the other raw materials and the amounts of the raw materials and the preparation method were the same as those in example 6.
EXAMPLE 10 preparation of polybutylene terephthalate composition
This example differs from example 6 in that: the hollow copper chromium black granules provided in example 3 were replaced with the hollow copper chromium black granules provided in example 6, and the other raw materials and the amounts of the raw materials and the preparation method were the same as those of example 6.
Comparative example 1 preparation of polybutylene terephthalate composition
This comparative example differs from example 6 in that: the hollow copper-chromium black particles were replaced with copper-chromium black powder, and the other raw materials and the amounts of the raw materials and the preparation method were the same as those in example 6.
Comparative example 2 preparation of polybutylene terephthalate composition
This comparative example differs from example 7 in that: the hollow copper-chromium black granules were replaced with copper-chromium black powder, and the other raw materials and the amounts of the raw materials and the preparation method were the same as in example 7.
Comparative example 3 preparation of polybutylene terephthalate composition
This comparative example differs from example 5 in that: the hollow copper-chromium black particles were replaced with hollow glass microsphere copper-chromium black, and the other raw materials and the amounts of the raw materials and the preparation method were the same as those in example 5.
The preparation process of the hollow glass bead copper-chromium black comprises the following steps:
(1) Adding 9g of hollow glass beads, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dispersing to form a mixed solution;
(2) Placing the mixed solution obtained in the step (1) on a constant-temperature magnetic stirrer, stirring and heating to 60 ℃, then dropwise adding urea, adjusting the pH of the mixed solution to 6-7 under the stirring condition, and continuously stirring and heating until the water evaporation is finished to obtain a hollow copper-chromium black precursor;
(3) Placing the hollow copper-chromium black precursor obtained in the step (2) in an electric furnace, calcining for 2h at 550 ℃ to obtain hollow copper-chromium black particles, wherein the content of the copper-chromium black is 60wt%, the particle size is 1-50 mu m, and the density is 2.0g/cm 3 。
Comparative example 4 preparation of polybutylene terephthalate composition
This comparative example differs from example 6 in that: the hollow copper chromium black particles were replaced with hollow glass microbead copper chromium black, and other raw materials, the amounts of the raw materials, and the preparation method were the same as those in example 6. The preparation method of the hollow glass bead copper-chromium black is the same as that of comparative example 3.
The polybutylene terephthalate compositions obtained in the examples and comparative examples were injection-molded into plastic parts having a predetermined shape. According to conventional method, the wavelength is 900-1080nm, and the energy is 150-300mJ/cm 2 The laser carries out laser etching on the preset area of the plastic part according to the set shape at the scanning speed of 0.1-1mm/s, the plastic part after laser etching is chemically plated, and a metal plating layer is formed in the laser etching area of the plastic part to obtain a plastic part sample.
The plastic part specimens produced above were subjected to the following performance tests (results shown in table 1):
tensile property: the tensile rate is 50mm/min according to the test of ASTM-D638;
impact properties: the thickness of the sample strip is 3.2mm according to the test of ASTM-D256 standard;
bending property: the bending rate is 10mm/min according to the test of ASTM-D790;
adhesion test of metal coating on plastic part surface (Baige test): testing according to ASTM D3359 Standard
Under the conditions that the room temperature is 23 +/-2 ℃ and the relative humidity is 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 angle of the blade is 15-30 degrees), and each scribing line is deep and a plating bottom layer is formed; brushing the test area clean by a brush; firmly sticking the small tested grids by using a No. 3M600 adhesive tape, and forcibly wiping the adhesive tape by using an eraser to increase the contact area and force between the adhesive tape and the tested area; one end of the tape was grasped by hand, and the tape was quickly pulled off at an angle of 60 ° in the vertical direction, and 2 identical tests were performed at the same position.
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 metal coating falls off at the scribing edge and the intersection point;
4B-small metal-free coatings fall off at the cross points of the scribing lines, and the total falling area is less than 5%;
3B-small metal-free coating layers fall off at the edge and the cross point of the scribing line, and the total falling area is between 5 and 15 percent;
2B-a plurality of metal-free coating layers fall off at the edge and the intersection of the scribing line, and the total falling area is 15-35%;
1B-the metal coating layers which are formed into pieces fall off at the edge and the intersection point of the scribing line, and the total falling area is between 35 and 65 percent;
0B-there is a piece of non-metal coating falling off at the edge and the cross point of the scribing line, and the total falling area is more than 65%.
TABLE 1 results of Performance test of examples 4 to 10 and comparative examples 1 to 4
As can be seen from the table above, the butylene terephthalate composition provided by the invention can be directly formed by laser, and has good metal plating adhesion and mechanical properties.
Comparing examples 6-7 and comparative examples 1-2, it can be seen that the polybutylene terephthalate composition provided by the invention has higher metal plating adhesion, and the metal plating adhesion of the polybutylene terephthalate composition can reach the optimal effect of 5B by adding 3wt% of hollow copper chromium black particles; the adhesive force of the metal coating of the butylene terephthalate composition added with 3wt% of metal oxide powder cannot meet the requirement, and when the addition amount of the metal oxide powder reaches 8%, the adhesive force of the metal coating can meet the qualified requirement of 4B, but the impact performance of the metal coating is greatly influenced; the butylene terephthalate composition provided by the invention requires fewer hollow metal oxide particles than common metal oxide powder, and the impact performance of the obtained butylene terephthalate composition is better.
Comparing examples 5-6 with comparative examples 3-4, it can be seen that the polybutylene terephthalate composition provided by the invention has higher metal plating adhesion and impact performance, the adhesion of the metal plating of the polybutylene terephthalate composition can reach the qualified requirement of 4B by adding 2wt% of the hollow copper-chromium black particles, and the adhesion of the metal plating of the polybutylene terephthalate composition can reach the optimal effect of 5B by adding 3wt% of the hollow copper-chromium black particles; the adhesive force of the metal coating is only 2B and the impact performance is poorer than that of the embodiment 5 by adding 2wt% of hollow glass bead copper-chromium black, and the adhesive force of the metal coating is much poorer than that of the embodiment 6 by adding 3wt% of hollow glass bead copper-chromium black although the adhesive force of the metal coating can also reach 5B; the reason is that high-temperature calcination is needed during synthesis of the hollow metal oxide, which easily causes agglomeration of powder, thus resulting in poor dispersion and finally affecting the adhesion and impact properties of the metal plating layer of the butylene terephthalate composition.
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 specific and detailed, but not to be understood 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 (10)
1. The polybutylene terephthalate composition is characterized by being prepared from the following raw materials in percentage by weight:
83-98.5% of polybutylene terephthalate;
1.5 to 15 percent of hollow metal oxide;
0-2% of antioxidant;
the hollow metal oxide is obtained by coating the metal oxide on the surface of POSS.
2. The polybutylene terephthalate composition of claim 1, wherein the hollow metal oxide is present in an amount of 2-8% by weight; and/or the presence of a gas in the atmosphere,
the weight percentage of the antioxidant is 0.2-0.5%;
preferably, the weight percentage of the hollow metal oxide is 2-4%;
preferably, the weight percentage of the hollow metal oxide is 2.5-3.5%;
preferably, the hollow metal oxide is present in an amount of 3% by weight.
3. The polybutylene terephthalate composition of claim 1, wherein the metal oxide is present in the hollow metal oxide in an amount ranging from 35 to 70% by weight;
preferably, the weight percentage of the metal oxide in the hollow metal oxide is 45-65%;
preferably, the weight percentage of the metal oxide in the hollow metal oxide is 50-60%.
4. The polybutylene terephthalate composition of claim 1, wherein the metal element in the metal oxide is one or more of copper, silver, gold, zinc, cadmium, gallium, titanium, chromium, cobalt, manganese, cerium, niobium, and iron; and/or the presence of a gas in the atmosphere,
the antioxidant consists of hindered phenol antioxidant and phosphite antioxidant;
preferably, the metal oxide is copper chromium black;
preferably, the hindered phenol antioxidant and the phosphite antioxidant are the same in weight percentage;
preferably, the hindered phenol antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, and the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
5. Polybutylene terephthalate composition according to claim 1, wherein the density of the hollow metal oxide is 1g/cm 3 -6g/cm 3 (ii) a And/or the presence of a gas in the atmosphere,
the particle size of the hollow metal oxide is 0.1-100 mu m;
preferably, the density of the hollow metal oxide is 1.5g/cm 3 -2.7g/cm 3 ；
Preferably, the hollow metal oxide has a particle size of 0.5 μm to 50 μm.
6. The polybutylene terephthalate composition according to any one of claims 1 to 5, wherein the hollow metal oxide is prepared from a metal salt corresponding to the metal oxide and amine phenyl POSS by a sol-gel method or a hydrothermal method;
preferably, the mass ratio of the metal salt corresponding to the metal oxide to the aminophenyl POSS is 1-5;
preferably, the metal salts corresponding to the metal oxides are copper nitrate trihydrate and chromium nitrate nonahydrate;
preferably, the mass ratio of the copper nitrate trihydrate to the chromium nitrate nonahydrate is 1.5-2.5.
7. The polybutylene terephthalate composition of claim 6, wherein the hollow metal oxide is prepared by a process comprising the steps of:
(1) Mixing the aminophenyl POSS with metal salt corresponding to the metal oxide, and adding water to dissolve;
(2) Heating the mixed solution prepared in the step (1), dropwise adding a citric acid aqueous solution under stirring, adding a sol stabilizer after dropwise adding is finished, and continuously stirring until the sol is converted into gel, and stopping stirring;
(3) Drying the wet gel prepared in the step (2), and grinding the wet gel into powder to obtain precursor powder;
(4) And adding water into the precursor powder for crystallization to obtain the hollow metal oxide.
8. The polybutylene terephthalate composition according to claim 7,
the ratio of the total mass of the aminophenyl POSS and the metal salt to the water in the step (1) is 1g:4mL-8mL; and/or the presence of a gas in the atmosphere,
the heating temperature in the step (2) is 70-90 ℃; and/or the presence of a gas in the gas,
the rotating speed of stirring in the step (2) is 1000r/min-1400r/min; and/or the presence of a gas in the atmosphere,
the concentration of the citric acid aqueous solution is 0.07g/mL-0.10g/mL, and the dripping amount of the citric acid aqueous solution is the same as the amount of the water added in the step (1); and/or the presence of a gas in the gas,
the sol stabilizer is ethylene glycol, and the addition volume of the ethylene glycol is 0.1-0.3% of the total volume of the citric acid aqueous solution and the water in the step (1); and/or the presence of a gas in the gas,
the drying in the step (3) is constant temperature drying under the conditions that the vacuum degree is-0.5 Mpa to-0.7 Mpa and the temperature is 70 ℃ to 90 ℃; and/or the presence of a gas in the atmosphere,
the step (4) comprises the following steps: and (2) putting the precursor powder into a reaction kettle, adding water, uniformly stirring, screwing a kettle cover, crystallizing for 2-7 days under the conditions that the pressure is 15-20 MPa and the temperature is 280-320 ℃, filtering, washing and drying a product to obtain the hollow metal oxide.
9. A process for preparing a polybutylene terephthalate composition according to any one of claims 1-8, comprising the steps of:
(a) Drying the polybutylene terephthalate, and mixing the dried polybutylene terephthalate with an antioxidant to obtain a premix;
(b) Adding the premix obtained in the step (a) into a parallel double-screw extruder through a main feeder, adding the hollow metal oxide into the parallel double-screw extruder from the side direction, and performing melt extrusion;
(c) And (c) bracing, cooling and dicing the extruded material obtained in the step (b) to obtain the polybutylene terephthalate composition.
10. The method of preparing a polybutylene terephthalate composition according to claim 9, wherein the drying conditions of step (a) include: the temperature is 100-110 ℃, and the time is 3-5 h; and/or the presence of a gas in the gas,
the processing conditions of the parallel double-screw extruder comprise: the temperature of the first zone is 200-210 ℃, the temperature of the second zone is 240-255 ℃, the temperature of the third zone is 240-255 ℃, the temperature of the fourth zone is 240-255 ℃, the temperature of the fifth zone is 240-260 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 240-260 ℃, the temperature of the ninth zone is 240-250 ℃, the temperature of the die head is 240-250 ℃, and the retention time of materials in a charging barrel of the parallel double-screw extruder is controlled to be 1-3 minutes.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0581919A (en) * | 1991-09-19 | 1993-04-02 | Toshiba Silicone Co Ltd | Electric conductive powder and manufacture thereof |
| WO2003082465A1 (en) * | 2002-04-03 | 2003-10-09 | Avantium International B.V. | Method of preparation of calcined supported catalysts using metallosilsesquioxanes |
| CN104987349A (en) * | 2015-07-17 | 2015-10-21 | 广西经正科技开发有限责任公司 | Preparation method of POSS material and alkaline metal oxide composite flame retardation material |
| CN106479134A (en) * | 2016-09-21 | 2017-03-08 | 沈阳化工大学 | A kind of isomerism cross-linking method modification polybutylene terephthalate (PBT) of the cross-linking agent of POSS containing L（PBT）And preparation method thereof |
| KR20180000247A (en) * | 2016-06-22 | 2018-01-02 | (주)정훈엘앤이 | Photo curable hard coating composition and hard coating film using the same |
| CN109232826A (en) * | 2018-07-18 | 2019-01-18 | 西南石油大学 | A kind of pre-crosslinked gel particle and preparation method thereof of POSS base hydridization |
| CN110452385A (en) * | 2019-08-29 | 2019-11-15 | 北京理工大学 | A kind of incomplete polycondensation cage type phenyl silsesquioxane of alkali metal containing sodium and preparation method thereof |
| CN110699071A (en) * | 2019-10-30 | 2020-01-17 | 南开大学 | Multi-metal oxygen cluster-naphthalimide-cage silsesquioxane cluster functional hybrid molecule and preparation method thereof |
| CN112028929A (en) * | 2019-06-03 | 2020-12-04 | 华东理工大学 | Preparation method and application of polyhedral oligomeric silsesquioxane-loaded substituted aryl heterocyclic phosphate or salt nucleating agent |
-
2021
- 2021-09-29 CN CN202111154888.0A patent/CN115873382A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0581919A (en) * | 1991-09-19 | 1993-04-02 | Toshiba Silicone Co Ltd | Electric conductive powder and manufacture thereof |
| WO2003082465A1 (en) * | 2002-04-03 | 2003-10-09 | Avantium International B.V. | Method of preparation of calcined supported catalysts using metallosilsesquioxanes |
| CN104987349A (en) * | 2015-07-17 | 2015-10-21 | 广西经正科技开发有限责任公司 | Preparation method of POSS material and alkaline metal oxide composite flame retardation material |
| KR20180000247A (en) * | 2016-06-22 | 2018-01-02 | (주)정훈엘앤이 | Photo curable hard coating composition and hard coating film using the same |
| CN106479134A (en) * | 2016-09-21 | 2017-03-08 | 沈阳化工大学 | A kind of isomerism cross-linking method modification polybutylene terephthalate (PBT) of the cross-linking agent of POSS containing L（PBT）And preparation method thereof |
| CN109232826A (en) * | 2018-07-18 | 2019-01-18 | 西南石油大学 | A kind of pre-crosslinked gel particle and preparation method thereof of POSS base hydridization |
| CN112028929A (en) * | 2019-06-03 | 2020-12-04 | 华东理工大学 | Preparation method and application of polyhedral oligomeric silsesquioxane-loaded substituted aryl heterocyclic phosphate or salt nucleating agent |
| CN110452385A (en) * | 2019-08-29 | 2019-11-15 | 北京理工大学 | A kind of incomplete polycondensation cage type phenyl silsesquioxane of alkali metal containing sodium and preparation method thereof |
| CN110699071A (en) * | 2019-10-30 | 2020-01-17 | 南开大学 | Multi-metal oxygen cluster-naphthalimide-cage silsesquioxane cluster functional hybrid molecule and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| AMBROZEWICZ, DAMIAN: "New POSS/magnesium silicate nano-hybrids obtained by chemical or mechanical methods", 《CHEMICAL ENGINEERING JOURNAL》, vol. 210, 1 November 2012 (2012-11-01), pages 229 - 236, XP055113413, DOI: 10.1016/j.cej.2012.08.075 * |
| 梁全禧: "倍半硅氧烷组装型负载手性金属催化剂的制备及其性能研究", 《中国优秀硕士论文数据库 工程科技Ⅰ辑》, 15 November 2015 (2015-11-15), pages 1 - 104 * |
| 王文平: "POSS/PMMA纳米复合粒子的制备与表征", 《高分子材料科学与工程》, vol. 23, no. 2, 30 March 2007 (2007-03-30), pages 96 - 98 * |
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