CN105778440A - Environment-friendly pbt material and preparing method thereof - Google Patents
Environment-friendly pbt material and preparing method thereof Download PDFInfo
- Publication number
- CN105778440A CN105778440A CN201610231197.9A CN201610231197A CN105778440A CN 105778440 A CN105778440 A CN 105778440A CN 201610231197 A CN201610231197 A CN 201610231197A CN 105778440 A CN105778440 A CN 105778440A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- powder
- parts
- zinc oxide
- weight
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an environment-friendly pbt material.The environment-friendly pbt material is prepared from, by weight, 1-2 parts of lauroyl diethanolamide, 2-3 parts of ammonium metaborate, 2.7-4 parts of phytosterol, 70-80 parts of caprolactam, 10-13 parts of attapulgite, 1-1.4 parts of zinc acetate, 2-3 parts of gamma-aminopropyl triethoxy silicane, 18-20 parts of oxalic acid, 300-370 parts of poly butylene tertephehalate, 1-2 parts of hydroxyl ethidene diphosphonic acid, 6-8 parts of oxidized polyethlene wax, 4-7 parts of polyvinylpyrrolidone, 0.9-1 part of trioctylphosphine butyltin, 10-14 parts of dioctyl sebacate and 4-6 parts of hydrous zinc borate.The material is safe, environmentally friendly and free of toxicity and pollution.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of environmental protection pbt material and preparation method thereof.
Background technology
ZnO was widely studied in the last few years as a kind of photocatalyst-type anti-biotic agent, and it generates strong oxygen under photocatalysis
The active function groups of the property changed kills antibacterial.It has nontoxic, nonirritant, good stability, and difficult decomposition under high temperature, timeliness is long
For a long time, cheap, the advantage such as aboundresources, have broad application prospects；
The common carrier being presently used for loaded optic catalyst mainly has CNT (CNTs) and activated carbon, mesoporous material, Linesless charcoal
Black and zeolites etc. can obtain the nano-particle of size uniform by load, in turn ensure that functional nano-composites simultaneously
High stability.Nano-photocatalyst/porous mineral compound system, i.e. assembles Nano semiconductor photocatalyst or loads to mineral
In the hole of material or on surface, not only solve the agglomeration traits of nano-photocatalyst granule, reduce its consumption, also simultaneously
Utilize the high-specific surface area of porous mineral, strong characterization of adsorption to realize in water or the targeting enrichment of pollutants in air, urged by light
Agent is more effectively carried out light degradation；
Therefore nano-photocatalyst/porous mineral compound system can improve the disposal efficiency of catalysis material, reduces again
Its consumption and preparation cost, accomplished to have complementary advantages, and this support type composite had both remained the character of nano-particle itself,
Closed by the interface between nano-particle and matrix simultaneously, some new assembly effects can be produced again, make whole complex
System shows as distinctive synergistic enhancing effect, thus significantly improves the functional characteristic of material, but presently used carrier is the most all deposited
In the shortcoming such as expensive, surface activity point is low, therefore, research and develop a kind of novel carrier material and be the most increasingly subject to
The attention of scholars, find a kind of cheap, surface activity is high and the novel carriers of good stability seems the most necessary；
Polyamide due to its good mechanical property, barrier property, anti-wear performance, acid-proof alkaline and good processing characteristics,
Increasingly become indispensable material as engineering plastics and non-fibre material, its application relate to auto parts and components, cord fabric,
The fields such as tyre equatorial, electronic apparatus, household supplies, consumption becomes kinds most in polyamide product.But applying
Cheng Zhong, the polar group of polyamide 6 material makes it be prone to absorb moisture, causes dry state and low temperature impact strength is low, product
Easily there is the phenomenon such as plastic deformation, serious wear in product poor stability, friction, additionally, uses as mine engineering plastics, do not possess
Antistatic property, easily produces gas explosion etc., thus affects the stability of its product size, antiwear and friction reduction property and electrically
Can, which has limited its range of application；
Attapulgite, as a kind of natural nanometer fibrous clay mineral, has 2:1 type layer chain structure, in its crystal structure
There is a large amount of pore passage structure, and have that specific surface area is big, surface activity site is many, energy of adsorption
By force, excellent biocompatibility and the chemically and thermally feature such as stability, be a kind of economical and practical carrier material, giving birth to
The aspects such as thing, environment, new material have broad application prospects；Therefore it is an object of the invention to nano-photocatalyst with recessed
Convex rod stone is effectively combined, and is the most effectively distributed in polyamide, prepares a kind of novel composite.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of environmental protection pbt material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of environmental protection pbt material, it is made up of the raw material of following weight parts:
Lauric acid diethyl amide 1-2, ammonium metaborate 2-3, plant sterol 2.7-4, caprolactam 70-80, attapulgite 10-
13, zinc acetate 1-1.4, gamma-aminopropyl-triethoxy-silane 2-3, ethanedioic acid 18-20, polybutylene terephthalate (PBT) 300-
370,1-hydroxy ethylidene-1,1-diphosphonic acid 1-2, OPE 6-8, polyvinylpyrrolidone 4-7, three sad butyl tin 0.9-1, the last of the ten Heavenly stems
Adipate 10-14, hydration zinc borate 4-6.
The preparation method of a kind of described environmental protection pbt material, comprises the following steps:
(1) by attapulgite, ammonium metaborate mixing, calcine 1-2 hour at 300-350 DEG C, join the hydrochloric acid of 3-5mol/l
Middle acidifying 3-5 hour, souring temperature is 20-35 DEG C, precipitation is washed 3-4 time after filtration, is dried at 80-90 DEG C, wears into thin
Powder, obtains activation attapulgite powder；
(2) take the 16-20% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25-30 times, stir；
(3) above-mentioned zinc acetate is joined in its weight 70-80 times, 46-50% ethanol solution, add above-mentioned activation concavo-convex
Rod soil powder, ultrasonic 10-20 minute, drips the ethanol solution of above-mentioned ethanedioic acid, magnetic agitation 3-4 minute after dropping, sucking filtration,
Product after sucking filtration is dried 3-5 hour at 110-116 DEG C, sends in Muffle furnace, at 600-640 DEG C, calcine 1.7-2 little
Time, cooling, obtain pretreatment zinc oxide load powder；
(4) by above-mentioned lauric acid diethyl amide, hydration zinc borate mixing, the deionization of compound weight 30-43 times is joined
In water, adding above-mentioned pretreatment zinc oxide load powder, 100-200 rev/min is stirred 20-30 minute, filters, by pungent with three for precipitation
Acid butyl stannum mixes, normal temperature drying, obtains zinc oxide load powder；
(5) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60-70 times, add γ-aminopropyl three second
TMOS, rises high-temperature and is 80-90 DEG C, insulated and stirred 1.7-2 hour, and precipitation is washed 2-3 time, at 50-60 DEG C by sucking filtration
It is vacuum dried 20-30 minute, obtains amino modified zinc oxide load powder；
(6) above-mentioned OPE is joined in polyvinylpyrrolidone, add plant sterol under stirring condition, send into
In the water-bath of 90-100 DEG C, insulated and stirred 6-10 minute, discharging, pre-above-mentioned 1-hydroxy ethylidene-1,1-diphosphonic acid mixes, and stirring, to room temperature, obtains
Premixed liquid；
(7) take the 10-16% of above-mentioned caprolactam weight, the 20-30% of residue ethanedioic acid weight, load with amino modified zinc oxide
Powder mixes, and adds the distilled water of compound weight 8-10 times, is sent in reactor, rises high-temperature and is 190-200 DEG C, insulation
React 3-4 hour, slowly cool to room temperature, be filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtain pre-polymerization modified oxidized
Zinc load powder；
(8) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add compound weight 4-7 times
Distilled water, is sent in reactor, rises high-temperature and is 200-230 DEG C, adds remaining ethanedioic acid, insulation reaction 3-3.5 hour,
Adding above-mentioned premixed liquid, 100-200 rev/min is stirred 7-10 minute, and discharging cools down, and filters, and at being deposited in 50-60 DEG C, vacuum is done
Dry 1-2 hour, obtain polymeric modification zinc oxide load powder；
(9) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
The invention have the advantage that first attapulgite is calcined and acidification by the present invention, attapulgite can be increased
The silicone hydroxyl group on stone surface, gives attapulgite surface more negative charge, increases its absorbability to metal cation,
By the attapulgite in-situ precipitate of absorption Zn2+ ion is obtained presoma, obtain ZnO/ attapulgite composite wood by calcination
Material, with attapulgite as carrier, can improve the dispersibility of ZnO nanoparticle, it is thus achieved that have the composite of high antibacterial activity,
Attapulgite as layer chain silicate clay, the advantages such as tool specific surface area is big and lateral reactivity site is many, load nano-ZnO
After, considerably increasing the contact area of ZnO and microorganism, high adsorption activity based on attapulgite, antibacterial can be by antibacterial material
Material absorption is forming enrichment about so that ZnO nano granule is easier to directly contact with antibacterial, thus plays its antibacterial characteristics
Cause inactivation of bacteria, then this composite is participated in the pre-polymerization process of caprolactam, utilize caprolactam open-loop products
Aminocaproic acid reacts with the amino of composite material surface, makes composite material surface be grafted a certain amount of polyamide prepolymer aggressiveness, at it
Surface forms one layer of strong boundary layer；Participate in the polymerization process of polyamide the most again, due to the polyamides of composite material surface grafting
Amine performed polymer can participate in the ring-opening polymerisation of caprolactam, therefore, it is possible to form " micronetwork " structure with masterbatch as core, enters
And add intensity and the toughness of polyamide substrate material, and, beneficially composite is in the dispersion of polyamide substrate material；
The material safety feature of environmental protection of the present invention is good, nontoxic pollution-free.
Detailed description of the invention
A kind of environmental protection pbt material, it is made up of the raw material of following weight parts:
Lauric acid diethyl amide 1, ammonium metaborate 2, plant sterol 2.7, caprolactam 70, attapulgite 10, zinc acetate 1, γ
Aminopropyl triethoxysilane 2, ethanedioic acid 18, polybutylene terephthalate (PBT) 300,1-hydroxy ethylidene-1,1-diphosphonic acid 1, aoxidize poly-second
Alkene wax 6, polyvinylpyrrolidone 4, three octanoic acid butyl tin 0.9, di-n-octyl sebacate 10, hydration zinc borate 4.
The preparation method of a kind of described environmental protection pbt material, comprises the following steps:
(1) by attapulgite, ammonium metaborate mixing, calcine 1 hour at 300 DEG C, join acidifying 3 in the hydrochloric acid of 3mol/l little
Time, souring temperature is 20 DEG C, precipitation is washed 3 times after filtration, is dried, wears into fine powder, obtain activation attapulgite powder at 80 DEG C；
(2) take the 16% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25 times, stir；
(3) above-mentioned zinc acetate is joined in its weight 70 times, the ethanol solution of 46%, adds above-mentioned activation attapulgite powder,
Ultrasonic 10 minutes, dripping the ethanol solution of above-mentioned ethanedioic acid, magnetic agitation 3 minutes after dropping, sucking filtration, by the product after sucking filtration
Thing is dried 3 hours at 110 DEG C, sends in Muffle furnace, calcines 1.7 hours at 600 DEG C, and cooling obtains pretreatment zinc oxide and bears
Carry powder；
(4) by above-mentioned lauric acid diethyl amide, hydration zinc borate mixing, the deionized water of compound weight 30 times is joined
In, add above-mentioned pretreatment zinc oxide load powder, 100 revs/min are stirred 20 minutes, filter, will precipitation and three octanoic acid butyl tin
Mixing, normal temperature drying, obtain zinc oxide load powder；
(5) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60 times, add γ aminopropyl-triethoxy
Silane, rising high-temperature is 80 DEG C, insulated and stirred 1.7 hours, and precipitation is washed 2 times by sucking filtration, is vacuum dried 20 points at 50 DEG C
Clock, obtains amino modified zinc oxide load powder；
(6) above-mentioned OPE is joined in polyvinylpyrrolidone, add plant sterol under stirring condition, send into 90
DEG C water-bath in, insulated and stirred 6 minutes, discharging, pre-above-mentioned 1-hydroxy ethylidene-1,1-diphosphonic acid mix, stirring to room temperature, obtain premixed liquid；
(7) take the 10% of above-mentioned caprolactam weight, the 20% of residue ethanedioic acid weight, mix with amino modified zinc oxide load powder
Closing, add the distilled water of compound weight 8 times, be sent in reactor, rising high-temperature is 190 DEG C, and insulation reaction 3 hours is slow
Slow cool down, to room temperature, is filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtains pre-polymerization modified zinc oxide load powder；
(8) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add the steaming of compound weight 4 times
Distilled water, is sent in reactor, and rising high-temperature is 200 DEG C, adds remaining ethanedioic acid, insulation reaction 3 hours, adds above-mentioned pre-
Mixed liquid, 100 revs/min are stirred 7 minutes, and discharging cools down, and filter, and will be deposited at 50 DEG C vacuum drying 1 hour, and obtain polymeric modification oxygen
Change zinc load powder；
(9) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
Performance test:
Hot strength is 96MPa；
Notch impact strength (KJ/m2) 10.12；
Vertical combustion (1.6mm) FV-O；
The zinc oxide load powder wherein prepared is O.lg/L to colibacillary minimum inhibitory concentration.
Claims (2)
1. an environmental protection pbt material, it is characterised in that it is made up of the raw material of following weight parts:
Lauric acid diethyl amide 1-2, ammonium metaborate 2-3, plant sterol 2.7-4, caprolactam 70-80, attapulgite 10-
13, zinc acetate 1-1.4, gamma-aminopropyl-triethoxy-silane 2-3, ethanedioic acid 18-20, polybutylene terephthalate (PBT) 300-
370,1-hydroxy ethylidene-1,1-diphosphonic acid 1-2, OPE 6-8, polyvinylpyrrolidone 4-7, three sad butyl tin 0.9-1, the last of the ten Heavenly stems
Adipate 10-14, hydration zinc borate 4-6.
2. the preparation method of an environmental protection pbt material as claimed in claim 1, it is characterised in that comprise the following steps:
(1) by attapulgite, ammonium metaborate mixing, calcine 1-2 hour at 300-350 DEG C, join the hydrochloric acid of 3-5mol/l
Middle acidifying 3-5 hour, souring temperature is 20-35 DEG C, precipitation is washed 3-4 time after filtration, is dried at 80-90 DEG C, wears into thin
Powder, obtains activation attapulgite powder；
(2) take the 16-20% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25-30 times, stir；
(3) above-mentioned zinc acetate is joined in its weight 70-80 times, 46-50% ethanol solution, add above-mentioned activation concavo-convex
Rod soil powder, ultrasonic 10-20 minute, drips the ethanol solution of above-mentioned ethanedioic acid, magnetic agitation 3-4 minute after dropping, sucking filtration,
Product after sucking filtration is dried 3-5 hour at 110-116 DEG C, sends in Muffle furnace, at 600-640 DEG C, calcine 1.7-2 little
Time, cooling, obtain pretreatment zinc oxide load powder；
(4) by above-mentioned lauric acid diethyl amide, hydration zinc borate mixing, the deionization of compound weight 30-43 times is joined
In water, adding above-mentioned pretreatment zinc oxide load powder, 100-200 rev/min is stirred 20-30 minute, filters, by pungent with three for precipitation
Acid butyl stannum mixes, normal temperature drying, obtains zinc oxide load powder；
(5) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60-70 times, add γ-aminopropyl three second
TMOS, rises high-temperature and is 80-90 DEG C, insulated and stirred 1.7-2 hour, and precipitation is washed 2-3 time, at 50-60 DEG C by sucking filtration
It is vacuum dried 20-30 minute, obtains amino modified zinc oxide load powder；
(6) above-mentioned OPE is joined in polyvinylpyrrolidone, add plant sterol under stirring condition, send into
In the water-bath of 90-100 DEG C, insulated and stirred 6-10 minute, discharging, pre-above-mentioned 1-hydroxy ethylidene-1,1-diphosphonic acid mixes, and stirring, to room temperature, obtains
Premixed liquid；
(7) take the 10-16% of above-mentioned caprolactam weight, the 20-30% of residue ethanedioic acid weight, load with amino modified zinc oxide
Powder mixes, and adds the distilled water of compound weight 8-10 times, is sent in reactor, rises high-temperature and is 190-200 DEG C, insulation
React 3-4 hour, slowly cool to room temperature, be filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtain pre-polymerization modified oxidized
Zinc load powder；
(8) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add compound weight 4-7 times
Distilled water, is sent in reactor, rises high-temperature and is 200-230 DEG C, adds remaining ethanedioic acid, insulation reaction 3-3.5 hour,
Adding above-mentioned premixed liquid, 100-200 rev/min is stirred 7-10 minute, and discharging cools down, and filters, and at being deposited in 50-60 DEG C, vacuum is done
Dry 1-2 hour, obtain polymeric modification zinc oxide load powder；
(9) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610231197.9A CN105778440A (en) | 2016-04-14 | 2016-04-14 | Environment-friendly pbt material and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610231197.9A CN105778440A (en) | 2016-04-14 | 2016-04-14 | Environment-friendly pbt material and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105778440A true CN105778440A (en) | 2016-07-20 |
Family
ID=56396591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610231197.9A Pending CN105778440A (en) | 2016-04-14 | 2016-04-14 | Environment-friendly pbt material and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105778440A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380984A (en) * | 2016-09-30 | 2017-02-08 | 芜湖市鸿坤汽车零部件有限公司 | Decorative antibacterial leather coating and preparation method thereof |
| CN106433045A (en) * | 2016-09-22 | 2017-02-22 | 苏州佰思科节能环保科技有限公司 | Light wear-resistant PBT composite environment-friendly material and preparation method thereof |
| CN107603165A (en) * | 2017-09-06 | 2018-01-19 | 绵阳旺通科技有限公司 | A kind of " micronetwork " pollution-free environment-friendly type pbt materials and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN102952327A (en) * | 2011-08-25 | 2013-03-06 | 上海杰事杰新材料(集团)股份有限公司 | Resin composite material and its preparation method and use |
| CN104448299A (en) * | 2013-09-24 | 2015-03-25 | 骏马化纤股份有限公司 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
-
2016
- 2016-04-14 CN CN201610231197.9A patent/CN105778440A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN102952327A (en) * | 2011-08-25 | 2013-03-06 | 上海杰事杰新材料(集团)股份有限公司 | Resin composite material and its preparation method and use |
| CN104448299A (en) * | 2013-09-24 | 2015-03-25 | 骏马化纤股份有限公司 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433045A (en) * | 2016-09-22 | 2017-02-22 | 苏州佰思科节能环保科技有限公司 | Light wear-resistant PBT composite environment-friendly material and preparation method thereof |
| CN106380984A (en) * | 2016-09-30 | 2017-02-08 | 芜湖市鸿坤汽车零部件有限公司 | Decorative antibacterial leather coating and preparation method thereof |
| CN107603165A (en) * | 2017-09-06 | 2018-01-19 | 绵阳旺通科技有限公司 | A kind of " micronetwork " pollution-free environment-friendly type pbt materials and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Multi-component design and in-situ synthesis of visible-light-driven SnO2/g-C3N4/diatomite composite for high-efficient photoreduction of Cr (VI) with the aid of citric acid | |
| CN108855011B (en) | Composite material with adsorption-visible light catalytic degradation synergistic effect and application thereof | |
| CN105860452A (en) | Antimicrobial pbt material and preparation method thereof | |
| CN108704611B (en) | Magnetic ferromanganese oxide loaded mesoporous cellulose biochar composite material and preparation method and application thereof | |
| Ye et al. | Interfacial engineering of vacancy-rich nitrogen-doped FexOy@ MoS2 Co-catalytic carbonaceous beads mediated non-radicals for fast catalytic oxidation | |
| Ma et al. | Study of cyano and hydroxyl groups modification on the properties of porous carbon nitride synthesized by using a salt assistant method | |
| CN105778440A (en) | Environment-friendly pbt material and preparing method thereof | |
| El Messaoudi et al. | A comparative review of the adsorption and photocatalytic degradation of tetracycline in aquatic environment by g-C3N4-based materials | |
| CN112675805B (en) | Preparation method of hydroxyapatite nanowire composite molybdenum disulfide adsorbent | |
| CN105107477A (en) | Hyperbranched polymer/clay mineral hybrid material and preparation method thereof | |
| CN103087553A (en) | Maleic anhydride grafted modified halloysite nanotube and preparation method thereof | |
| CN107098429A (en) | A kind of BiVO4/BiPO4Composite and its preparation method and application | |
| Bo et al. | Interior engineering of seaweed-derived N-doped versatile carbonaceous beads with Co x O y for universal organic pollutant degradation | |
| CN105838043A (en) | Attapulgite-modified pbt material and preparation method thereof | |
| CN105778441A (en) | Heat-preservation pbt material and preparing method thereof | |
| CN105860454A (en) | Anti-oxidant pbt material and preparation method thereof | |
| CN105778437A (en) | Composite silicon modified pbt material and preparing method thereof | |
| CN105860448A (en) | Pbt material for automobile exterior part and preparing method thereof | |
| CN107902660B (en) | Preparation of SiO from yellow phosphorus slag2Method for preparing ATO-based conductive powder material | |
| CN105802148A (en) | Pbt material and preparation method thereof | |
| CN105802150A (en) | Hydrophobic anti-leakage pbt material and preparation method thereof | |
| CN107603165A (en) | A kind of " micronetwork " pollution-free environment-friendly type pbt materials and preparation method thereof | |
| CN105860450A (en) | Zinc oxide loaded pbt material and preparation method thereof | |
| CN105778438A (en) | Stable type pbt material and preparation method thereof | |
| CN105860451A (en) | Antistatic pbt material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160720 |