CN114031939A - Nylon/titanic acid nanosheet composite material and preparation method thereof - Google Patents
Nylon/titanic acid nanosheet composite material and preparation method thereof Download PDFInfo
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- CN114031939A CN114031939A CN202111470861.2A CN202111470861A CN114031939A CN 114031939 A CN114031939 A CN 114031939A CN 202111470861 A CN202111470861 A CN 202111470861A CN 114031939 A CN114031939 A CN 114031939A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 55
- 229920001778 nylon Polymers 0.000 title claims abstract description 55
- 239000002135 nanosheet Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 23
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 230000036571 hydration Effects 0.000 claims abstract description 16
- 238000006703 hydration reaction Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000000887 hydrating effect Effects 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000002055 nanoplate Substances 0.000 claims 8
- 238000004898 kneading Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 150000001412 amines Chemical class 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 13
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 9
- 229910052901 montmorillonite Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000000138 intercalating agent Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
Abstract
The invention discloses a nylon/titanate nano-sheet composite material, which is prepared by uniformly mixing nylon and titanate nano-sheet powder according to a weight ratio of 1000: 1-1000: 10 and then extruding the mixture in a double-screw extruder; the titanium acid nano-sheet powder is prepared by taking potassium titanate whisker as a raw material through hydration and acid washing processes. The invention adopts a double-screw extruder to melt, blend and extrude the nylon/titanic acid nano-sheet composite material, so that the nano-sheets are uniformly dispersed in the nylon, thereby preparing the high-performance nano-composite material. The invention has simple operation, no need of organic amine intercalation agent, low production cost and excellent performance of the composite material.
Description
Technical Field
The invention belongs to the field of nylon manufacturing, relates to composite nylon and a preparation method thereof, and particularly relates to a nylon/titanium acid nanosheet composite material and a preparation method thereof.
Background
Nylon is an engineering plastic widely used in the industries of machinery, automobiles, ships and the like due to excellent physical and mechanical properties. However, due to the existence of amide groups, nylon has the defects of high water absorption, low heat distortion temperature, low modulus and the like, and with the technical progress, various industries put higher demands on the performance of nylon.
In the traditional process, inorganic filler with micron or millimeter level is used for reinforcing nylon, but the problems of large filler consumption, insufficient dispersibility and the like can obviously influence the reinforcing effect. Accordingly, the use of smaller sized nanoparticles with fewer structural defects to produce nylon composites has been considered. Due to the nanoscale effect and strong interface interaction, the nano composite material has more excellent mechanical property, heat resistance and good processing property compared with the traditional composite material.
At present, the montmorillonite nanosheet nylon composite material is the most representative. For example, in chinese patent CN1206028A, montmorillonite, intercalating agent and protonating agent undergo a cation exchange reaction to obtain intercalated montmorillonite, and then the intercalated montmorillonite and polyamide are extruded into a high-performance nylon/montmorillonite nanocomposite in a twin-screw extruder. Patent CN1687184A is to disperse the nanoclay modified by organic amine in polyamide monomer, and prepare high viscosity modified polyamide by anionic polymerization. Although the performance of nylon is improved by adding the montmorillonite nano-sheets in the above patents, toxic organic amine is required to be used as an intercalation agent in the preparation process, which may cause environmental problems.
By consulting the literature, the inventor finds that titanate with a layered structure like montmorillonite can also be stripped to obtain the titanate nanosheet through processes such as ion exchange, intercalation and the like. Sukpirom et al, Materials Science & Engineering 2002,333(1): 218-. Yuan et al examined the intercalation stripping effect of TMAOOH, TEAOH, TPAOH and TBAOH four organic amine solutions on type layered titanate in detail in ACS Applied Materials & Interfaces,2014,6(11): 8567-8574. Like modification of montmorillonite, stripping of titanate also requires the use of an organic amine solution with high toxicity and high price, so that environmental and cost problems caused by the organic amine solution restrict industrial application of titanate nanosheets, and no scholars try to use titanate nanosheets to reinforce nylon materials at home and abroad so far.
Disclosure of Invention
Aiming at the defects of modifying montmorillonite or titanate by using organic amine with higher toxicity and high price as an intercalating agent at present, the invention creatively successfully peels titanate nanosheets without using organic amine as the intercalating agent, and the method has the advantages of simple operation, economy and environmental protection; and titanate nanosheets are adopted to prepare the nylon/titanic acid nanocomposite, so that the mechanical property of nylon is greatly improved.
The purpose of the invention is realized by the following technical scheme:
a nylon/titanic acid nanometer sheet composite material is prepared by uniformly mixing nylon and titanic acid nanometer sheet powder according to a weight ratio of 1000: 1-1000: 10, and then extruding the mixture in a double-screw extruder; the titanium acid nano-sheet powder is prepared by taking potassium titanate whisker as a raw material through hydration and acid washing processes.
Preferably, the weight ratio of the nylon to the titanate nano-sheet powder is 1000: 3-1000: 5.
Preferably, the nylon is one or more of PA66, PA6, PA1010, PA11, PA12, PA610 and PA 612.
Preferably, the titanate nano-sheet powder is prepared by taking potassium titanate whiskers as a raw material, hydrating the potassium titanate whiskers in the steam atmosphere of an inorganic salt solution at 100-150 ℃ to obtain a hydration product, washing the hydration product with a protonating agent to obtain a washing product, dispersing the washing product in a dispersion medium, stirring, filtering and drying.
Specifically, the nanosheet powder is prepared by the following method, including:
preparing inorganic salt and a dispersion medium into an inorganic salt solution according to a weight ratio of 1-10: 1-50;
step (2), taking potassium titanate whiskers, and hydrating for 5-10 hours at 100-150 ℃ in the steam atmosphere of an inorganic salt solution to obtain a hydration product;
step (3), washing the hydration product with a protonating agent according to the weight ratio of the potassium titanate whisker to the protonating agent of 1-60: 500-2000, filtering and drying to obtain a washing product;
and (4) dispersing the washing product in a dispersion medium according to the weight ratio of the potassium titanate whisker to the dispersion medium of 1-60: 1-200, stirring for 0.5-3 hours, filtering, and drying to obtain the titanate nanosheet powder.
Preferably, the weight ratio of the inorganic salt to the dispersion medium is 1: 1-2.
Preferably, the inorganic salt is one or more of potassium chloride, sodium chloride and calcium chloride.
The weight ratio of the potassium titanate whisker to the inorganic salt is 1-60: 1-10; preferably, the weight ratio of the potassium titanate whisker to the water is 1-3: 1.
Preferably, the potassium titanate whisker is one of potassium dititanate, potassium tetratitanate, potassium hexatitanate and potassium octatitanate. The potassium titanate whisker has a diameter of 0.1 to 10 μm and a length of 1 to 1000 μm.
Preferably, the weight ratio of the potassium titanate whisker to the protonating agent is 1: 60-70.
Preferably, the protonating agent is one or more of phenol, hydrochloric acid, formic acid and acetic acid. Specifically, the concentration of the hydrochloric acid is 0.1 mol/L.
Typically, the hydration product is washed three times with a protonating agent to ensure that the potassium ions in the titanate are completely exchanged.
Preferably, the weight ratio of the potassium titanate whiskers to the dispersion medium is 1: 10-15.
Preferably, the dispersion medium is one or more of water, ethanol, propanol or chloroform.
Another object of the present invention is to provide a method for preparing a nylon/titanate nanosheet composite, comprising: uniformly mixing nylon and titanate nano-sheet powder in a kneader, extruding in a double-screw extruder at the temperature of 190-250 ℃, and granulating.
Preferably, granulating and drying by using a double-screw extruder, and performing injection molding by using an injection machine at the injection temperature of 235 ℃ and the injection pressure of 80Mpa to obtain the mechanical property sample band of the nylon titanate nanosheet composite material.
The invention has the beneficial effects that:
the invention strips the layered titanate into titanic acid nano-sheets by hydration and acid washing processes without adding an intercalation agent. The method comprises the steps of adjusting the concentration of an inorganic salt solution, controlling the generation speed of water vapor, further controlling the hydration process, carrying out the hydration process under the condition of high temperature and high pressure, reducing the vapor pressure of the solution through the inorganic salt, and enabling water molecules to permeate into the layers of layered titanate to enlarge the interlayer spacing. The acid washing process is to exchange potassium ions among titanate layers by using hydrogen ions, and further realize the complete stripping of layered titanate under the condition of not adding an intercalation agent.
The invention adopts a double-screw extruder to melt, blend and extrude the nylon/titanic acid nano-sheet composite material, so that the nano-sheets are uniformly dispersed in the nylon, thereby preparing the high-performance nano-composite material. Compared with the traditional clay/polyamide composite process, the method has the advantages of simple operation, no need of using an organic amine intercalating agent, low production cost and excellent performance of the composite material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and more complete description of the technical solutions of the present invention will be given below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
4.7331g of calcium chloride was weighed and dissolved in 7.0944g of water to prepare a 40% calcium chloride solution.
Weighing 20g of potassium dititanate whisker (the diameter is 2 mu m, the length is 10 mu m) and placing the potassium dititanate whisker into a hydrothermal kettle, placing a beaker filled with calcium chloride solution, distributing the potassium dititanate whisker between the beaker and the hydrothermal kettle, and hydrating the potassium dititanate whisker at 200 ℃ for 8h in the steam atmosphere of the calcium chloride solution to obtain a hydration product.
Dispersing the hydrated product by adopting 1350g hydrochloric acid with the concentration of 0.1mol/L, stirring for 2h, filtering, pickling for 3 times, completely exchanging potassium ions in the titanate, and drying to obtain a washing product.
And dispersing the washing product in 200g of deionized water, stirring at a high speed for 0.5 hour, filtering and drying to obtain the titanic acid nanosheet powder.
Weighing 3g of titanic acid nanosheet powder and 1000g of nylon PA6, mixing in a kneader for 10min to obtain a uniformly mixed material, and extruding the mixed material in a double-screw extruder at 235 ℃; and (3) after granulation and drying, performing injection molding on the mixture on an injection machine (the injection temperature is 235 ℃, and the injection pressure is 80Mpa) to obtain the nylon/titanate nanosheet composite material, wherein the mechanical properties of the material are shown in Table 1.
Example 2
Adjusting the using amount of the titanic acid nano-sheet powder (same as example 1) to be 5g, mixing the titanic acid nano-sheet powder and 1000g of nylon PA6 in a kneader for 10min, and then extruding the mixed material in a double-screw extruder at the extrusion temperature of 235 ℃; and (3) after granulation and drying, performing injection molding on the mixture on an injection machine (the injection temperature is 235 ℃, and the injection pressure is 80Mpa) to obtain the nylon/titanate nanosheet composite material. The mechanical properties of the materials are shown in Table 1.
Example 3
Adjusting the using amount of the titanic acid nano-sheet powder (same as example 1) to 10g, mixing the titanic acid nano-sheet powder and 1000g of nylon PA6 in a kneader for 10min, and then extruding the mixed material in a double-screw extruder at the extrusion temperature of 235 ℃; and (3) after granulation and drying, performing injection molding on the mixture on an injection machine (the injection temperature is 235 ℃, and the injection pressure is 80Mpa) to obtain the nylon/titanate nanosheet composite material. The mechanical properties of the materials are shown in Table 1.
Comparative example 1
1000g of nylon PA6 was weighed into a kneader and stirred for 10min, and the blend was extruded in a twin-screw extruder at 235 ℃. Granulating, drying, and injection molding at 235 deg.C under 80 Mpa. The mechanical properties of the material are shown in Table 1.
TABLE 1 mechanical Properties of the materials
The result shows that the nylon/titanate nano-sheet composite material prepared from the nylon and the titanate nano-sheet powder according to the weight ratio of 1000: 3-1000: 5 has the most obvious effect of improving the mechanical property of nylon.
Claims (10)
1. A nylon/titanic acid nanometer sheet composite material is characterized in that: uniformly mixing nylon and titanate nano-sheet powder according to a weight ratio of 1000: 1-1000: 10, and extruding in a double-screw extruder to obtain a nylon/titanate nano-sheet composite material; the titanium acid nano-sheet powder is prepared by taking potassium titanate whisker as a raw material through hydration and acid washing processes.
2. The nylon/titanate nanoplate composite of claim 1, characterized in that: the weight ratio of the nylon to the titanate nano-sheet powder is 1000: 3-1000: 5.
3. The nylon/titanate nanoplate composite of claim 1, characterized in that: the nylon is one or more of PA66, PA6, PA1010, PA11, PA12, PA610 and PA 612.
4. The nylon/titanate nanoplate composite of claim 1, characterized in that: the method comprises the following steps of using potassium titanate whiskers as a raw material, hydrating the raw material in an inorganic salt solution steam atmosphere at 100-150 ℃ to obtain a hydration product, washing the hydration product with a protonating agent to obtain a washing product, dispersing the washing product in a dispersion medium, stirring, filtering and drying to obtain the titanate nanosheet powder.
5. The nylon/titanate nanoplate composite of claim 1 or 4, characterized in that: the nano-sheet powder is prepared by the following method, including:
preparing inorganic salt and a dispersion medium into an inorganic salt solution according to a weight ratio of 1-10: 1-50;
step (2), taking potassium titanate whiskers, and hydrating for 5-10 hours at 100-150 ℃ in the steam atmosphere of an inorganic salt solution to obtain a hydration product;
step (3), washing the hydration product with a protonating agent according to the weight ratio of the potassium titanate whisker to the protonating agent of 1-60: 500-2000, filtering and drying to obtain a washing product;
and (4) dispersing the washing product in a dispersion medium according to the weight ratio of the potassium titanate whisker to the dispersion medium of 1-60: 1-200, stirring for 0.5-3 hours, filtering, and drying to obtain the titanate nanosheet powder.
6. The nylon/titanate nanoplate composite of claim 4, wherein: the inorganic salt is one or more of potassium chloride, sodium chloride and calcium chloride.
7. The nylon/titanate nanoplate composite of claim 4, wherein: the potassium titanate whisker is one of potassium dititanate, potassium tetratitanate, potassium hexatitanate and potassium octatitanate; the potassium titanate whisker has a diameter of 0.1-10 μm and a length of 1-1000 μm.
8. The nylon/titanate nanoplate composite of claim 4, wherein: the protonating agent is one or more of phenol, hydrochloric acid, formic acid and acetic acid.
9. The nylon/titanate nanoplate composite of claim 4, wherein: the dispersion medium is one or more of water, ethanol, propanol or chloroform.
10. A method for preparing the nylon/titanate nanosheet composite of claim 1, wherein: the method comprises the following steps: uniformly mixing nylon and titanate nanosheet powder in a kneading machine, and extruding in a double-screw extruder at the temperature of 190-250 ℃ to obtain the nylon/titanate nanosheet composite material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678262A (en) * | 2022-11-08 | 2023-02-03 | 江苏博云塑业股份有限公司 | Preparation method of composite titanate modified nylon material |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1307399A (en) * | 1969-10-30 | 1973-02-21 | Freeport Sulphur Co | Inorganic-organo titanate compositions and process for providing the same |
| JPH07157312A (en) * | 1993-12-08 | 1995-06-20 | Kubota Corp | Production of flaky titanium dioxide |
| JP2003138146A (en) * | 2001-08-20 | 2003-05-14 | Otsuka Chem Co Ltd | Resin composition |
| CN1526474A (en) * | 2003-09-22 | 2004-09-08 | 南京工业大学 | Method for synthesizing titanium oxide with high specific surface area |
| CN1910239A (en) * | 2004-01-16 | 2007-02-07 | 大塚化学株式会社 | Flame-retardant and flame-retardant resin composition |
| CN101045816A (en) * | 2007-03-22 | 2007-10-03 | 辽宁大学 | Preparation process of whisher reinforced nylon composite |
| CN101139109A (en) * | 2007-08-07 | 2008-03-12 | 南京工业大学 | Method for rapidly preparing easily-controlled micropore-mesopore structure titanium oxide or precursor thereof |
| CN101506285A (en) * | 2006-08-21 | 2009-08-12 | 大塚化学株式会社 | Compatibilizing agent for polymer alloy, polymer alloy and masterbatch for preparation of polymer alloy |
| US20110033371A1 (en) * | 2007-08-07 | 2011-02-10 | Nanjing University Of Technology | Rapid Method for Preparing Titania or Precursor Thereof with Controllable Microporous-Mesoporous Structure |
| CN102094243A (en) * | 2010-12-07 | 2011-06-15 | 浙江师范大学 | Preparation method of nano titanic acid tablets |
| CN103803644A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for controlling product crystal form and morphology of titanium-based nanometer material |
| CN103806087A (en) * | 2014-02-27 | 2014-05-21 | 南京大学医学院附属鼓楼医院 | Preparation method for novel TiO2 nano crystal whisker materials commonly-loaded with gambogic acid |
| CN108585037A (en) * | 2018-08-07 | 2018-09-28 | 天能工程复合材料制品(昆山)有限公司 | A kind of preparation method of high pure gold redrock type titanium dioxide crystal whisker |
| CN112920595A (en) * | 2021-01-26 | 2021-06-08 | 南京捷纳思新材料有限公司 | Nano potassium titanate whisker reinforced high-temperature-resistant nylon composite material and preparation method thereof |
-
2021
- 2021-12-03 CN CN202111470861.2A patent/CN114031939B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1307399A (en) * | 1969-10-30 | 1973-02-21 | Freeport Sulphur Co | Inorganic-organo titanate compositions and process for providing the same |
| JPH07157312A (en) * | 1993-12-08 | 1995-06-20 | Kubota Corp | Production of flaky titanium dioxide |
| JP2003138146A (en) * | 2001-08-20 | 2003-05-14 | Otsuka Chem Co Ltd | Resin composition |
| CN1526474A (en) * | 2003-09-22 | 2004-09-08 | 南京工业大学 | Method for synthesizing titanium oxide with high specific surface area |
| CN1910239A (en) * | 2004-01-16 | 2007-02-07 | 大塚化学株式会社 | Flame-retardant and flame-retardant resin composition |
| US20090326153A1 (en) * | 2006-08-21 | 2009-12-31 | Ryoichi Hiroi | Compatibilizing agent for polymer alloy, polymer alloy, and master batch for preparation of polymer alloy |
| CN101506285A (en) * | 2006-08-21 | 2009-08-12 | 大塚化学株式会社 | Compatibilizing agent for polymer alloy, polymer alloy and masterbatch for preparation of polymer alloy |
| CN101045816A (en) * | 2007-03-22 | 2007-10-03 | 辽宁大学 | Preparation process of whisher reinforced nylon composite |
| CN101139109A (en) * | 2007-08-07 | 2008-03-12 | 南京工业大学 | Method for rapidly preparing easily-controlled micropore-mesopore structure titanium oxide or precursor thereof |
| US20110033371A1 (en) * | 2007-08-07 | 2011-02-10 | Nanjing University Of Technology | Rapid Method for Preparing Titania or Precursor Thereof with Controllable Microporous-Mesoporous Structure |
| CN102094243A (en) * | 2010-12-07 | 2011-06-15 | 浙江师范大学 | Preparation method of nano titanic acid tablets |
| CN103803644A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for controlling product crystal form and morphology of titanium-based nanometer material |
| CN103806087A (en) * | 2014-02-27 | 2014-05-21 | 南京大学医学院附属鼓楼医院 | Preparation method for novel TiO2 nano crystal whisker materials commonly-loaded with gambogic acid |
| CN108585037A (en) * | 2018-08-07 | 2018-09-28 | 天能工程复合材料制品(昆山)有限公司 | A kind of preparation method of high pure gold redrock type titanium dioxide crystal whisker |
| CN112920595A (en) * | 2021-01-26 | 2021-06-08 | 南京捷纳思新材料有限公司 | Nano potassium titanate whisker reinforced high-temperature-resistant nylon composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678262A (en) * | 2022-11-08 | 2023-02-03 | 江苏博云塑业股份有限公司 | Preparation method of composite titanate modified nylon material |
| CN115678262B (en) * | 2022-11-08 | 2023-12-05 | 江苏博云塑业股份有限公司 | Preparation method of composite titanate modified nylon material |
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