CN108285551B - Method for preparing nano-silica composite auxiliary antioxidant through in-situ modification - Google Patents
Method for preparing nano-silica composite auxiliary antioxidant through in-situ modification Download PDFInfo
- Publication number
- CN108285551B CN108285551B CN201810380191.7A CN201810380191A CN108285551B CN 108285551 B CN108285551 B CN 108285551B CN 201810380191 A CN201810380191 A CN 201810380191A CN 108285551 B CN108285551 B CN 108285551B
- Authority
- CN
- China
- Prior art keywords
- auxiliary antioxidant
- ethyl alcohol
- absolute ethyl
- placing
- solution
- 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
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing a nano-silica composite auxiliary antioxidant through in-situ modification, which improves the use temperature of the auxiliary antioxidant 168 and overcomes the defects of poor self-dispersibility, complex secondary dispersion modification process, high energy consumption and high pollution of nano-silica. On the basis of a sol-gel technology, the nano silicon dioxide composite auxiliary antioxidant with uniform particle size and excellent appearance is prepared by utilizing the technology of in-situ modification of auxiliary antioxidant 168 self functional groups, dosage, adding temperature, adding time, reaction conditions and the like. The preparation and modification method has advanced process and precise data, the product is white powder particle with particle diameter of 80-120nm, can be applied in various fields of high molecular antioxidation, strengthening and toughening, industrial coating and the like, and is an ideal preparation method of the nano silicon dioxide composite auxiliary antioxidant.
Description
Technical Field
The invention relates to a method for preparing a nano-silica composite auxiliary antioxidant by in-situ modification, belonging to the technical field of preparation and application of inorganic nano-materials.
Background
The antioxidant 168 is a good phosphite ester auxiliary antioxidant, is white powder in appearance, is easily soluble in organic solvents such as benzene, chloroform and cyclohexane, is slightly soluble in ethanol and acetone, is not soluble in polar solvents such as water and alcohol, and is slightly soluble in esters. Low toxicity, low volatility and excellent hydrolysis resistance, and can effectively decompose hydroperoxide generated in the thermal processing process of the polymer material. It is widely used in polyolefin (such as polyethylene and polypropylene) and olefin copolymer, polyamide, polycarbonate, PS resin, PVC, engineering plastic, rubber and petroleum products, ABS resin and other polymer materials.
The nano silicon dioxide has good thermal stability, thickening property, reinforcing property and the like. The method is widely applied to modification of composite materials such as rubber, engineering plastics, biomedicine, ceramics, building materials, resin matrix and the like, and is one of extremely important high-tech superfine inorganic new materials. However, because the particle size of the nano-silica is smaller and the surface activity is higher, soft and hard agglomeration is easily generated in the production and application processes, so that the application performance is reduced.
Disclosure of Invention
The invention provides a method for preparing a nano-silica composite auxiliary antioxidant by in-situ modification, aiming at solving the technical problems of hard aggregate phenomenon and complex process existing in the processes of high-temperature decomposition and nano-silica preparation in the use process of the conventional auxiliary antioxidant 168.
The invention is realized by adopting the following technical scheme: a method for preparing a nano silicon dioxide composite auxiliary antioxidant by in-situ modification uses the following chemical substance materials: ethyl orthosilicate, ammonia water with the concentration of 25% calculated by mass fraction, absolute ethyl alcohol, acetone, auxiliary antioxidant 168 and deionized water, wherein the dosage of the liquid chemical substance material is calculated by volume fraction; wherein, the basic chemical properties of the auxiliary antioxidant 168 are as follows:
chemical name: tris (2, 4-di-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butyl) phenyl phosphite
The molecular formula is as follows: c42H63O3P
Molecular weight: 646.9
The molecular structural formula is as follows:
the preparation method comprises the following steps:
(1) selecting each chemical material
(2) In-situ modification preparation of nano silicon dioxide composite auxiliary antioxidant
Firstly, preparing solution
Measuring 49-51 parts of absolute ethyl alcohol, and placing the absolute ethyl alcohol in a beaker for later use; measuring 24-36 parts of ammonia water, and placing the ammonia water in a conical flask with a rubber plug for later use; measuring 5.0-5.2 parts of ethyl orthosilicate and 49-51 parts of absolute ethyl alcohol, placing the ethyl orthosilicate and the absolute ethyl alcohol in a beaker for mixing, and stirring the mixture by using a glass rod to uniformly mix the ethyl orthosilicate and the absolute ethyl alcohol for later use; weighing and dissolving the auxiliary antioxidant 168 in 150 parts of 145-acetone, uniformly stirring to prepare an acetone solution, wherein the mass-volume ratio of the auxiliary antioxidant 168 to the acetone is 5-6: 29-30 mg/ml, and placing the solution into a conical flask with a glass plug for later use after the auxiliary antioxidant 168 and the acetone are completely dissolved;
② process for preparing nano silicon dioxide composite auxiliary antioxidant by in-situ modification
Placing absolute ethyl alcohol and an ammonia water solution into a three-neck flask, then placing the three-neck flask into a magnetic stirring heating sleeve, starting a stirrer, starting heating, setting the rotating speed of the stirrer to be 200r/min, setting the heating temperature to be 65 ℃, and configuring a condensation reflux device; adding the tetraethoxysilane solution into a three-neck flask at the speed of 0.5 part/min when the temperature reaches 45 ℃ during the temperature rise; after the condensation reflux reaction is carried out for 2 hours, the acetone solution is dripped into the three-neck flask at the speed of 0.5 part/min; condensing and refluxing for 5 h;
③ ultrasonic water bath dispersion reaction
After the reaction is finished, placing the three-neck flask in an ultrasonic water bath pool for continuous reaction, wherein the water bath temperature is 60 ℃, the ultrasonic frequency is 80KHz, the power is 90W, and the reaction time is 2 h;
fourthly, washing and suction filtration
Putting the product solution obtained in the step (III) into a beaker, adding 150 parts of anhydrous ethanol, and stirring for 3min to obtain a washing solution; filtering the washing liquid to obtain a filter cake, placing the filter cake in 200 and 250 parts of absolute ethyl alcohol, stirring to obtain washing liquid, and filtering; performing the above steps for 5 times to obtain a filter cake;
adding the filter cake into 200 parts of deionized water, stirring and washing for 5min to obtain a washing solution; filtering and washing until the filtrate is neutral to obtain a product filter cake;
drying, grinding and sieving
Putting the product filter cake into a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the vacuum degree is 0.1MPa, and the drying time is 2 h;
and grinding the dried powder by using an agate mortar and a pestle, and then sieving by using a 400-mesh sieve to obtain the nano silicon dioxide composite auxiliary antioxidant product.
Detecting, analyzing and characterizing the shape, color, components and chemical and physical properties of the prepared nano silicon dioxide composite auxiliary antioxidant:
carrying out morphology analysis on the nano silicon dioxide composite auxiliary antioxidant by using a JSM-6700F type field emission scanning electron microscope;
performing thermal stability analysis on the product by using a TGA4000 thermogravimetric analyzer;
and (4) conclusion: the nano silicon dioxide composite auxiliary antioxidant prepared by the method is white powder particles, the particle diameter is 80-120nm, the appearance is regular, the particle size is uniform, the dispersion is good, and the chemical and physical properties are stable.
The nano silicon dioxide is stored in a brown transparent glass container, and is stored in a closed and dark way, and is waterproof, sun-proof and acid, alkali and salt corrosion resistant, the storage temperature is 25 ℃, and the relative humidity is less than or equal to 10%.
The invention has the beneficial effects that:
compared with the prior art, the method has obvious advancement, aims at the defects that the auxiliary antioxidant 168 is easy to decompose at high temperature in the using process, the nano-silica has poor dispersibility, more aggregates, complex secondary dispersion modification process and energy consumption, and prepares the nano-silica composite auxiliary antioxidant with excellent appearance and uniform particle size by in-situ modification by utilizing the technologies such as the dosage of a modifier, the adding time, the adding temperature, the reaction condition and the like on the basis of the original sol-gel technology. The preparation and modification method has advanced process and accurate data, the product is white powder particles with the particle diameter of 80-120nm, can be applied to various fields such as macromolecule anti-oxidation enhancement, industrial coating and the like, and is an ideal preparation method of the nano silicon dioxide composite auxiliary antioxidant.
Further, the step (1) is to select the chemical material for preparation, and control the quality purity and concentration: the purity of the ethyl orthosilicate is 99.9 percent, and the purity of the absolute ethyl alcohol is 99.9 percent; the purity of the acetone is 99.9 percent; the purity of the auxiliary antioxidant 168 is 99.9 percent; the purity of the deionized water is 99.9%.
Further, in the second step, firstly, condensing and refluxing for reaction for 2 hours, and then dropwise adding an acetone solution for condensing and refluxing for reaction for 5 hours; the dropping speed of the ethyl orthosilicate solution is 0.5 part/min, and the dropping speed of the acetone solution is 0.5 part/min.
And further, washing with absolute ethyl alcohol and performing suction filtration in the step IV, and then washing with deionized water and performing suction filtration until the filtrate is neutral.
The raw materials with the purity, the dropping time and speed of the materials and the times of washing and suction filtration can effectively ensure better quality of the nano silicon dioxide composite auxiliary antioxidant.
Drawings
FIG. 1 is a state diagram of in-situ modification for preparing nano-silica composite antioxidant.
FIG. 2 is an ultrasonic state diagram of the preparation of nano-silica composite antioxidant by in-situ modification.
FIG. 3 is a microscopic morphology of the nano-silica composite antioxidant.
FIG. 4 is a thermogravimetric plot of nano-silica composite auxiliary antioxidant.
1-magnetic stirring heating sleeve seat, 2-three-neck flask, 3-liquid adding funnel, 4-liquid adding control valve, 5-condensing reflux device, 6-temperature sensor, 7-temperature sensor fixing frame, 8-in-situ modification preparation of nano silicon dioxide composite auxiliary antioxidant mixed liquid, 9-liquid adding funnel fixing frame, 10-condensing reflux device fixing frame, 11-magnetic stirring rotor, 12-first temperature control button, 13-rotating speed control button, 14-ultrasonic emission module, 15-numerical control ultrasonic cleaner water bath seat, 16-pure liquid water, 17-power control button and 18-second temperature control button.
Detailed Description
Embodiment 1 a method for preparing a nano-silica composite antioxidant by in-situ modification, which uses the following chemical materials: ethyl orthosilicate, ammonia water with the concentration of 25 percent calculated by mass fraction, absolute ethyl alcohol, acetone, auxiliary antioxidant 168 and deionized water.
The preparation method comprises the following steps:
(1) selecting each chemical material
(2) In-situ modification preparation of nano silicon dioxide composite auxiliary antioxidant
Firstly, preparing solution
Measuring 51ml of absolute ethyl alcohol, and placing the absolute ethyl alcohol in a beaker for later use; measuring 29ml of ammonia water, and placing the ammonia water in a conical flask with a rubber plug for later use; measuring 5ml of ethyl orthosilicate and 50ml of absolute ethyl alcohol, placing the ethyl orthosilicate and the absolute ethyl alcohol in a beaker for mixing, and stirring the mixture by using a glass rod to uniformly mix the mixture for later use; 25mg of the auxiliary antioxidant 168 is measured and dissolved in 150ml of acetone, the acetone solution is prepared by stirring evenly, and the acetone solution is placed in a conical flask with a glass stopper for standby after being completely dissolved.
② process for preparing nano silicon dioxide composite auxiliary antioxidant by in-situ modification
Placing absolute ethyl alcohol and an ammonia water solution into a three-neck flask, then placing the three-neck flask into a magnetic stirring heating sleeve, starting a stirrer, starting heating, setting the rotating speed of the stirrer at 200r/min, setting the heating temperature at 65 ℃, and configuring a condensation reflux device. Adding the tetraethoxysilane solution into a three-neck flask at the speed of 0.5ml/min when the temperature reaches 45 ℃ during the temperature rise; after the condensation reflux reaction is carried out for 2 hours, the acetone solution is dripped into the three-neck flask at the speed of 0.5 ml/min; the reaction was refluxed for 5 h.
③ ultrasonic water bath dispersion reaction
And step II, after the reaction is finished, placing the three-neck flask in an ultrasonic water bath pool for continuous reaction, wherein the water bath temperature is 60 ℃, the ultrasonic frequency is 80KHz, the power is 90W, and the reaction time is 2 h.
Fourthly, washing and suction filtration
Putting the product solution obtained in the step (III) into a beaker, adding 150ml of absolute ethyl alcohol, and stirring for 3min to obtain a washing solution; filtering the washing liquid to obtain a filter cake, placing the filter cake in 200ml of absolute ethyl alcohol, stirring to obtain washing liquid, and filtering; performing the above steps for 5 times to obtain a filter cake;
adding the filter cake into 200ml of deionized water, stirring and washing for 5min to obtain a washing liquid; and (4) performing suction filtration and washing until the filtrate is neutral to obtain a product filter cake.
Drying, grinding and sieving
Putting the product filter cake into a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the vacuum degree is 0.1MPa, and the drying time is 2 h;
and grinding the dried powder by using an agate mortar and a pestle, and then sieving by using a 400-mesh sieve to obtain the nano silicon dioxide composite auxiliary antioxidant product.
The invention is further described below with reference to the accompanying drawings:
FIG. 1 shows a state diagram of in-situ modification for preparing nano-silica composite antioxidant, wherein the positions of all parts are correct, and the operations are carried out according to the proportion and the sequence.
The amount of chemical substance used for preparation is determined in a predetermined range, and is measured in grams and milliliters.
The three-neck flask 2 is arranged on the magnetic stirring heating sleeve 1, and the heating temperature of the magnetic stirring heating sleeve 1 is controlled by a first temperature control button 12; a liquid adding funnel 3, a condensing reflux device 5 and a temperature sensor 6 are sequentially arranged on the upper part of the three-neck flask 2 from left to right; the lower part of the liquid feeding funnel 3 is provided with a liquid feeding control valve 4 which is fixed by a liquid feeding funnel fixing frame 9; the condensing reflux device 5 is fixed by a condensing reflux device control frame 10; the temperature sensor 6 is fixed by a sensor fixing frame 7; preparing a nano silicon dioxide composite auxiliary antioxidant mixed solution 8 by in-situ modification in the three-neck flask 2; the bottom of the three-mouth flask 2 is provided with a magnetic stirring rotor 11; the rotation speed of the magnetic stirring rotor 11 is controlled by a rotation speed control knob 13.
FIG. 2 is an ultrasonic water bath diagram of the preparation of nano-silica composite antioxidant by in-situ modification, wherein the positions of all parts are correct, and the parts are proportioned according to the amount and operated in sequence.
The three-neck flask 2 is arranged on a water bath seat 15 of the numerical control ultrasonic cleaner, pure liquid water 16 is added into a water bath pool, the water bath temperature of the water bath seat 15 of the numerical control ultrasonic cleaner is controlled by a second temperature control button 18, and the power of an ultrasonic emission module 14 is controlled and adjusted by a power control button 17; a liquid adding funnel 3, a condensing reflux device 5 and a temperature sensor 6 are sequentially arranged on the upper part of the three-neck flask 2 from left to right; the lower part of the liquid feeding funnel 3 is provided with a liquid feeding control valve 4 which is fixed by a liquid feeding funnel fixing frame 9; the condensing reflux device 5 is fixed by a condensing reflux device control frame 10; the temperature sensor 6 is fixed by a sensor fixing frame 7; the three-neck flask 2 is internally provided with a mixed solution 8 of nano-silica composite auxiliary antioxidant prepared by in-situ modification.
FIG. 3 is a microscopic morphology of the in-situ modified nano-silica composite antioxidant, in which: the nano silicon dioxide has smooth and round surface appearance, uniform and full particle size of 80-120nm, monodispersity, and no hard agglomeration or soft agglomeration.
FIG. 4 is a thermogravimetric plot of in-situ modification of the nano-silica composite antioxidant and the pure auxiliary antioxidant 168, the weight loss temperature in the comparative plot is visible, the initial decomposition temperature of the nano-silica composite antioxidant is delayed, the weight loss temperature is significantly higher than that of the pure auxiliary antioxidant 168, and the thermal stability is improved.
Claims (2)
1. A method for preparing a nano silicon dioxide composite auxiliary antioxidant by in-situ modification is characterized in that the used chemical substance materials are as follows: ethyl orthosilicate, ammonia water with the concentration of 25 percent calculated by mass fraction, absolute ethyl alcohol, acetone, auxiliary antioxidant 168 and deionized water; wherein, the basic chemical properties of the auxiliary antioxidant 168 are as follows:
chemical name: tris (2, 4-di-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butyl) phenyl phosphite
The molecular formula is as follows: c42H63O3P
Molecular weight: 646.9
The molecular structural formula is as follows:
the preparation method comprises the following steps:
(1) selecting each chemical material
(2) In-situ modification preparation of nano silicon dioxide composite auxiliary antioxidant
Firstly, preparing solution
Measuring 51ml of absolute ethyl alcohol, and placing the absolute ethyl alcohol in a beaker for later use; measuring 29ml of ammonia water, and placing the ammonia water in a conical flask with a rubber plug for later use; measuring 5.0ml of tetraethoxysilane and 50ml of absolute ethyl alcohol, placing the tetraethoxysilane and the absolute ethyl alcohol in a beaker for mixing, and stirring the mixture by using a glass rod to uniformly mix the mixture for later use; weighing and dissolving the auxiliary antioxidant 168 in 150ml of acetone, uniformly stirring to prepare an acetone solution, wherein the mass-volume ratio of the auxiliary antioxidant 168 to the acetone is 1:6mg/ml, and placing the solution into a conical flask with a glass plug for later use after the auxiliary antioxidant 168 and the acetone are completely dissolved;
② process for preparing nano silicon dioxide composite auxiliary antioxidant by in-situ modification
Placing absolute ethyl alcohol and an ammonia water solution into a three-neck flask, then placing the three-neck flask into a magnetic stirring heating sleeve, starting a stirrer, starting heating, setting the rotating speed of the stirrer to be 200r/min, setting the heating temperature to be 65 ℃, and configuring a condensation reflux device; adding the tetraethoxysilane solution into a three-neck flask at the speed of 0.5ml/min when the temperature reaches 45 ℃ during the temperature rise; after the condensation reflux reaction is carried out for 2 hours, the acetone solution is dripped into the three-neck flask at the speed of 0.5 ml/min; condensing and refluxing for 5 h;
③ ultrasonic water bath dispersion reaction
After the reaction is finished, placing the three-neck flask in an ultrasonic water bath pool for continuous reaction, wherein the water bath temperature is 60 ℃, the ultrasonic frequency is 80KHz, the power is 90W, and the reaction time is 2 h;
fourthly, washing and suction filtration
Putting the product solution obtained in the step (III) into a beaker, adding 150ml of absolute ethyl alcohol, and stirring for 3min to obtain a washing solution; filtering the washing liquid to obtain a filter cake, placing the filter cake in 200ml of absolute ethyl alcohol, stirring to obtain washing liquid, and filtering; performing the above steps for 5 times to obtain a filter cake;
adding the filter cake into 200ml of deionized water, stirring and washing for 5min to obtain a washing liquid; filtering and washing until the filtrate is neutral to obtain a product filter cake;
drying, grinding and sieving
Putting the product filter cake into a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the vacuum degree is 0.1MPa, and the drying time is 2 h;
and grinding the dried powder by using an agate mortar and a pestle, and then sieving by using a 400-mesh sieve to obtain the nano silicon dioxide composite auxiliary antioxidant product.
2. The method for preparing the nano-silica composite antioxidant in situ through modification as claimed in claim 1, wherein the chemical material used in the preparation in the step (1) is selected, and the quality purity and the concentration are controlled as follows: the purity of the ethyl orthosilicate is 99.9 percent, and the purity of the absolute ethyl alcohol is 99.9 percent; the purity of the acetone is 99.9 percent; the purity of the auxiliary antioxidant 168 is 99.9 percent; the purity of the deionized water is 99.9%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810380191.7A CN108285551B (en) | 2018-04-25 | 2018-04-25 | Method for preparing nano-silica composite auxiliary antioxidant through in-situ modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810380191.7A CN108285551B (en) | 2018-04-25 | 2018-04-25 | Method for preparing nano-silica composite auxiliary antioxidant through in-situ modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108285551A CN108285551A (en) | 2018-07-17 |
| CN108285551B true CN108285551B (en) | 2021-01-15 |
Family
ID=62834749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810380191.7A Active CN108285551B (en) | 2018-04-25 | 2018-04-25 | Method for preparing nano-silica composite auxiliary antioxidant through in-situ modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108285551B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113444527A (en) * | 2021-06-29 | 2021-09-28 | 江苏品和石油科技有限公司 | Preparation method of antioxidant stabilizer for lithium ion diaphragm pore-forming oil |
| CN116606491B (en) * | 2023-05-16 | 2024-03-19 | 广东诚和信新材料有限公司 | Anti-aging PE material and synthesis process thereof |
| CN118459919B (en) * | 2024-07-09 | 2024-09-27 | 江苏冠联新材料科技股份有限公司 | Ageing-resistant high-strength HNBR (nitrile butadiene rubber) sizing material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100992875B1 (en) * | 2008-07-21 | 2010-11-08 | 경북대학교 산학협력단 | Antioxidant loaded sustained release porous silica matrix and preparing method thereof |
| CN104497360B (en) * | 2014-12-02 | 2017-06-20 | 华南理工大学 | Immobilized Hinered phenols antioxidant of nano silicon and its preparation method and application |
| CN104556072B (en) * | 2015-01-12 | 2016-06-08 | 太原理工大学 | A kind of in-situ modified method preparing monodisperse nano silicon dioxide |
| CN104817727A (en) * | 2015-04-17 | 2015-08-05 | 广州合成材料研究院有限公司 | Carried antioxygen and preparation method thereof |
| CN105199171A (en) * | 2015-10-15 | 2015-12-30 | 山东阳谷华泰化工股份有限公司 | Preparation method of white carbon black masterbatch, obtained product and application of product to high-wear-resistance white carbon black reinforcing material for rubber |
| CN107337809A (en) * | 2017-06-27 | 2017-11-10 | 华南理工大学 | It is a kind of that there is feature mesoporous silicon dioxide nano particle for preventing old effect and preparation method and application |
-
2018
- 2018-04-25 CN CN201810380191.7A patent/CN108285551B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108285551A (en) | 2018-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108285551B (en) | Method for preparing nano-silica composite auxiliary antioxidant through in-situ modification | |
| CN104556072B (en) | A kind of in-situ modified method preparing monodisperse nano silicon dioxide | |
| CN105199435A (en) | Preparation method of cobalt blue and clay mineral hybrid pigment | |
| CN110343259B (en) | Green fluorescent sandwich type zinc coordination polymer and preparation method and application thereof | |
| CN108530679B (en) | Method for preparing nano-silica composite antioxidant through in-situ modification | |
| CN108794972B (en) | A kind of antibacterial antistatic ABS composite material and preparation method thereof | |
| CN105665737A (en) | Biosynthesis method of nano Ag | |
| CN105061784A (en) | Polyethylene wax coated stable potassium ferrate and preparation method thereof | |
| CN102030359A (en) | Preparation method of nano zinc oxide powder | |
| CN107956000B (en) | A kind of synthetic method and products obtained therefrom of NiO multistage doughnut | |
| CN102827516A (en) | Environmentally friendly water-based paint capable of removing formaldehyde through reacting and preparation method thereof | |
| CN103143318B (en) | Preparation method for siliceous earth/FeOOH composite materials in micro-nano structure | |
| CN110655655B (en) | Cyan fluorescent zinc-organic coordination polymer and preparation method and application thereof | |
| CN106395908A (en) | Preparation method of bamboo joint structure Mn2O3 | |
| CN103308357B (en) | A kind of lead oil lacquer coat standard substance and preparation method | |
| CN100398441C (en) | Method of preparing nano-zinc borate | |
| CN103803639B (en) | Ionic liquid is utilized to prepare the method for nano-ITO powder | |
| CN104069818B (en) | The preparation method of the radial magnetic core-shell mesoporous silicon material of phenyl functionalization | |
| CN104277069B (en) | Synthesis and application of new nano hybrid | |
| CN104530711A (en) | Flame retarding room temperature vulcanized silicone rubber composite material and preparing method thereof | |
| CN108912276A (en) | A kind of heterogeneous ion-exchange membrane material of biocompatibility and preparation method thereof | |
| CN105254638A (en) | Method for controlling crystal form of nanometer oxotitanium phthalocyanine by using supergravity technology | |
| CN104650122B (en) | A kind of preparation method of organic-metallic thin film | |
| CN103803640B (en) | Method for preparing nanometer ITO (indium tin oxide) powder by virtue of coprecipitation method | |
| CN108485315A (en) | A method of preparing composite Nano silica using antioxidant is in-situ modified |
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 | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lian Dandan Inventor after: Zhang Ruiping Inventor after: Lu Jianjun Inventor after: Dai Jinming Inventor after: Niu Mei Inventor after: Han Menxin Inventor after: Ren Jingyi Inventor before: Lu Jianjun Inventor before: Lian Dandan Inventor before: Zhang Ruiping Inventor before: Dai Jinming Inventor before: Niu Mei Inventor before: Han Menxin Inventor before: Ren Jingyi |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221216 Address after: 201400 Zone 8, Building B, No. 528, Zhangwenmiao Road, Nanqiao Town, Fengxian District, Shanghai Patentee after: Shanghai Yichen New Materials Co.,Ltd. Address before: 030024 No. 79 West Main Street, Taiyuan, Shanxi, Yingze Patentee before: Taiyuan University of Technology |