CN106432802B - A kind of preparation method of caged molecular modification graphene oxide fire retardant - Google Patents
A kind of preparation method of caged molecular modification graphene oxide fire retardant Download PDFInfo
- Publication number
- CN106432802B CN106432802B CN201610846413.0A CN201610846413A CN106432802B CN 106432802 B CN106432802 B CN 106432802B CN 201610846413 A CN201610846413 A CN 201610846413A CN 106432802 B CN106432802 B CN 106432802B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- pepa
- acyl chlorides
- fire retardant
- molecular modification
- 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
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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Fireproofing Substances (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of preparation method of caged molecular modification graphene oxide fire retardant is related to a kind of preparation method of fire retardant, and the synthesis of young laying ducks in cage first activates PEPA with purifying and acyl chlorides;The covalent bond of acyl chlorides PEPA and graphene oxide again:Weigh 50-100g graphene oxides, it is dispersed in 100-400ml dioxane solvents, ultrasound 2-5h under 20-40Khz frequencies, and it is poured into the activation PEPA midbody solutions of the acyl chlorides obtained by step 2, under 80-220r/min rotating speeds, caged molecular modification graphene oxide fire retardant is made in 50-80 DEG C of the reaction was continued 5-8h.Caged molecular modification graphene oxide fire retardant is made.Prepared fire retardant is halogen-free, high-efficiency low-toxicity, environmental-friendly, is a kind of environment friendly flame retardant.Product of the present invention can be widely applied to the fire protection flame retarding of the high molecular materials such as coating, plastics, rubber in daily production and living.
Description
Technical field
The present invention relates to a kind of preparation methods of fire retardant, and in particular to a kind of caged molecular modification graphene oxide is fire-retardant
The preparation method of agent.
Background technology
The extensive use of high molecular material brings while we facilitate and also brings on a disaster, and high molecular flammable properties are more next
It is more concerned by people, the generation of fire preventing, protects the life of the people and property safety to become the most important thing, fire retardant is answered
It transports and gives birth to, have become a kind of important pluronic polymer now.Fire retardant type is various, and most preferably halogen system is fire-retardant for effect
Agent, although halogenated flame retardant can improve the flame retardant property of material well, can discharge in use it is toxic, have corrosion
Property gas, secondary injury caused to the mankind, and pollute environment.Enhance with the safety and environmental consciousness of people, fire retardant is positive
Low toxicity, low cigarette, environmentally friendly direction are developed, halogen-free flameproof becomes research hotspot, and phosphorus flame retardant has efficient, low
The advantages that cigarette, low toxicity, Halogen, is acknowledged as the fire proofing additive of a kind of environment-friendly type, it is fire-retardant to be widely used in high molecular material
In, it is the next-generation fire retardant being most hopeful instead of halogen flame.Wherein, PEPA is a representative of phosphorus flame retardant,
It has stable hexa-atomic bicyclo cage shaped structure, and thermal stability and chemical stability are excellent, and phosphorus content is widely used up to 17.2%,
Flame retarding efficiency is high, has both the fire-retardant double action of gas phase, condensed phase, can form coke protective layer in polymer combustion, inhibit
Burning has excellent flame retarding efficiency, thermal stability and hydrolytic resistance.
Graphene is also good fire proofing, and since the advent of the world just obtains enough concerns, unique nanostructure
There are important researching value, a series of researchs about graphene all to actively develop with performance.With nanocomposite
Research is goed deep into, and the anti-flammability of polymer/graphene nano composite material causes the extensive concern of domestic and foreign scholars.It is hindered with tradition
Combustible material is compared, and a small amount of graphene can improve the thermal stability of polymeric matrix, and this novel flame redundant material has
There are the characteristics of environmental protection, low toxicity, excellent combination property, but the fire-retardant rank relatively low then limit value scope of application of Graphene fire retardant,
Then scientific research personnel starts the research of Compositional type modified graphene fire retardant, grows up since this Compositional type graphene.
Invention content
The present invention provides a kind of preparation method of caged molecular modification graphene oxide fire retardant, and this method prepares a kind of high
Effect, environmental protection, less toxic, excellent combination property modified graphene oxide fire retardant.
The technical scheme adopted by the invention to solve the technical problem is that:
A kind of preparation method of caged molecular modification graphene oxide fire retardant, this approach includes the following steps:
The synthesis and purifying of step 1. young laying ducks in cage
In 500ml three-necked flasks, 0.2-1mol pentaerythrites and 0.2-1mol phosphorus oxychloride is added, then pour into 150-
300ml dioxane reacts 1-3h, with subsequent in 80-90 DEG C of water-bath as solvent under the mixing speed of 80-220r/min
Continuous to be warming up to 90-100 DEG C, back flow reaction 2-4h, end temperature is fixed on 95 DEG C, and solvent is slowly steamed when being stirred to react, and obtains
To white solid.Above-mentioned white solid is taken to be dissolved in 200-400ml absolute ethyl alcohols, the 80-180r/ in 70-85 DEG C of water-bath
It is stirred under the mixing speed of min to being completely dissolved, is filtered at 15-30 DEG C, is cooling, recrystallize, being dried in vacuo 10- at 60-120 DEG C
For 24 hours, spare.
Step 2. acyl chlorides activates PEPA
It takes the dioxane that 100-300ml newly steams in three-necked flask, weighs 0.2-1mol diacid chlorides, pour into and fill solvent
Flask in, under nitrogen protection, under 80-220r/min rotating speeds, electromagnetic agitation 3-15min weighs the PEPA of 0.2-1mol, PEPA
Divide 5-30 times and be added in there-necked flask, be slowly added into reaction bulb per the speed of minor tick 3-30min, and acid binding agent adjusting is added
Solution pH value is 7-10, reacts 4-6h at 50-80 DEG C, and acyl chlorides is made and activates PEPA intermediates.
The covalent bond of step 3. acyl chlorides PEPA and graphene oxide
50-100g graphene oxides are weighed, are dispersed in 100-400ml dioxane solvents, are surpassed under 20-40Khz frequencies
Sound 2-5h, and be poured into the activation PEPA midbody solutions of the acyl chlorides obtained by step 2, under 80-220r/min rotating speeds, 50-
Caged molecular modification graphene oxide fire retardant is made in 80 DEG C of the reaction was continued 5-8h.
A kind of preparation method of the caged molecular modification graphene oxide fire retardant, it is characterised in that:Described two
Acyl chlorides is the one such or several combination of Adipoyl Chloride, ethanedioly chloride, glutaryl chlorine, sebacoyl chloride.
A kind of preparation method of the caged molecular modification graphene oxide fire retardant, it is characterised in that:Described
PEPA and diacid chloride mole ratio are 1:1.
A kind of preparation method of the caged molecular modification graphene oxide fire retardant, it is characterised in that:Described applies
Sour agent is one or more combinations in triethylamine, pyridine, n,N-diisopropylethylamine.
Beneficial effects of the present invention are embodied in following several aspects:
A kind of preparation method of caged molecular modification graphene oxide fire retardant of the present invention, preparation method letter
Single, easy to operate, raw material is easy purchase.In fire retardant P element can synergistic graphene, effectively improve the flame retardant grade of graphene oxide
Not, the modified graphene oxide fire retardant of low toxicity, low cigarette, Halogen is prepared.
Description of the drawings
Fig. 1 caged molecular modification graphene oxide reaction mechanism figures.
Specific implementation mode
With reference to the particular specific embodiment embodiment that present invention be described in more detail.
Embodiment 1
The synthesis and purifying of step 1. young laying ducks in cage
In 500ml three-necked flasks, 1mol pentaerythrites and 1mol phosphorus oxychloride is added and to pour into 300ml dioxane molten
Agent reacts 3h in 85 DEG C of water-baths under the mixing speed of 180r/min, then raises temperature to 93 DEG C, back flow reaction 3h, last temperature
Degree is fixed on 95 DEG C, and solvent is slowly steamed when being stirred to react, obtains white solid.Take above-mentioned white solid dissolving 300ml without
It in water-ethanol, stirs to being completely dissolved, is filtered at 25 DEG C, cooling is tied again under the mixing speed of 120r/min in 80 DEG C of water-baths
It is brilliant, be dried in vacuo for 24 hours at 120 DEG C, it is spare.
Step 2. acyl chlorides activates PEPA
It takes the dioxane that 150ml newly steams in three-necked flask, weighs 0.2mol diacid chlorides, pour into the flask for filling solvent
In, under nitrogen protection, under 120r/min rotating speeds, electromagnetic agitation 8min, and be added triethylamine adjust solution pH value be 8, weigh with
The PEPA of diacid chloride equimolar amounts, point 18 additions, until adding, react 5h at 80 DEG C per minor tick 10min, acyl chlorides are made
Activate PEPA midbody solutions.
The covalent bond of step 3. acyl chlorides PEPA and graphene oxide
Graphene oxide water solution is made by improved Hummers methods, the dry 48h in vacuum freeze drier,
Obtain graphene oxide powder.The above-mentioned graphene oxide powders of 100g are weighed, are dispersed in 250ml dioxane solvents, ultrasonic 5h,
And be poured into the activation PEPA midbody solutions of the acyl chlorides obtained by step 2, caged molecular modification is made in the reaction was continued 8h
Graphene oxide fire retardant.It is dried in vacuo for 24 hours, for use.
Step 4. aqueous epoxy resins and the dispersion of modified graphene oxide fire retardant are ground
Caged molecule made from 10 parts of aqueous epoxy resins, 5 parts of deionized waters and 2 parts of steps 3 is weighed by mass fraction
Fire retardant, water are poured into water-base epoxy tree in grinding pot and are mixed, is placed on ball milling in ball mill by modified graphene oxide fire retardant
40min is uniformly mixed, and 10 parts of curing agent is added after taking-up, it is mixed to obtain coating by magnetic agitation 1h under the rotating speed of 150r/min
Close liquid.
It is prepared by step 5. fire resistant coating
During curing, surface sand-blasting process is carried out to steel disc with sand-blasting machine, then cleans surface with acetone soak, placed
Wait for spray-on coating.The coating mixed liquor that step 4 obtains is poured into spray gun, carries out the spraying work of steel disc via spray gun respectively
Make, coating is equably sprayed on steel disc.After spraying, steel disc is placed on shady and cool dry local 72h, dryness finalization.
Embodiment 2
The synthesis and purifying of step 1. young laying ducks in cage
In 500ml three-necked flasks, 1mol pentaerythrites and 1mol phosphorus oxychloride is added and to pour into 350ml dioxane molten
Agent reacts 3h in 85 DEG C of water-baths under the mixing speed of 180r/min, then raises temperature to 93 DEG C, back flow reaction 3h, last temperature
Degree is fixed on 95 DEG C, and solvent is slowly steamed when being stirred to react, obtains white solid.Take above-mentioned white solid dissolving 300ml without
It in water-ethanol, stirs to being completely dissolved, is filtered at 25 DEG C, cooling is tied again under the mixing speed of 120r/min in 80 DEG C of water-baths
It is brilliant, be dried in vacuo for 24 hours at 120 DEG C, it is spare.
Step 2. acyl chlorides activates PEPA
It takes the dioxane that 150ml newly steams in three-necked flask, weighs 0.1mol diacid chlorides, pour into the flask for filling solvent
In, under nitrogen protection, under 150r/min rotating speeds, electromagnetic agitation 8min, and be added triethylamine adjust solution pH value be 8, weigh with
The PEPA of diacid chloride equimolar amounts, point 9 additions, until adding, react 5h at 80 DEG C per minor tick 8min, acyl chlorides are made and lives
Change PEPA midbody solutions.
The covalent bond of step 3. acyl chlorides PEPA and graphene oxide
Graphene oxide water solution is made by improved Hummers methods, the dry 48h in vacuum freeze drier,
Obtain graphene oxide powder.The above-mentioned graphene oxide powders of 70g are weighed, are dispersed in 200ml dioxane solvents, ultrasonic 5h,
And be poured into the activation PEPA midbody solutions of the acyl chlorides obtained by step 2, caged molecular modification is made in the reaction was continued 8h
Graphene oxide fire retardant.It is dried in vacuo for 24 hours, for use.
Step 4. aqueous epoxy resins and the dispersion of modified graphene oxide fire retardant are ground
Caged molecule made from 10 parts of aqueous epoxy resins, 5 parts of deionized waters and 2 parts of steps 3 is weighed by mass fraction
Fire retardant, water are poured into water-base epoxy tree in grinding pot and are mixed, is placed on ball milling in ball mill by modified graphene oxide fire retardant
40min is uniformly mixed, and 10 parts of curing agent is added after taking-up, it is mixed to obtain coating by magnetic agitation 1h under the rotating speed of 150r/min
Close liquid.
It is prepared by step 5. fire resistant coating
During curing, surface sand-blasting process is carried out to steel disc with sand-blasting machine, then cleans surface with acetone soak, placed
Wait for spray-on coating.The coating mixed liquor that step 4 obtains is poured into spray gun, carries out the spraying work of steel disc via spray gun respectively
Make, coating is equably sprayed on steel disc.After spraying, steel disc is placed on shady and cool dry local 72h, dryness finalization.
Comparative example 1
By mass fraction weigh 10 parts aqueous epoxy resins, 5 parts of deionized waters.Water and water-base epoxy tree are poured into grinding
It is mixed in tank, is placed on ball milling 40min in ball mill, be uniformly mixed, 10 parts of curing agent is added after taking-up, in turning for 150r/min
The lower magnetic agitation 1h of speed obtains coating mixed liquor.Fire resistant coating is prepared by step 5.
The formula and the performance table of comparisons of embodiment 1-2 and ratio 1
From the performance of upper table embodiment 1-2 and comparative example 1 relatively in as can be seen that the addition of fire retardant to epoxy resin
Surface drying time influences very little;The addition of fire retardant makes the adhesive force of coating be slightly decreased, but is not influenced on the application of coating;Resistance
The addition of combustion agent improves the fire endurance time of epoxy coating, and compared with pure epoxy coating, fire resistance period is improved more than 30%;
The addition of fire retardant influences epoxy coating water resistance and salt spray resistance 480h tests all very small.
Claims (2)
1. a kind of preparation method of caged molecular modification graphene oxide fire retardant, which is characterized in that the method preparation process
It is as follows:
The synthesis and purifying of step 1. young laying ducks in cage
In 500ml three-necked flask, 1mol pentaerythrites and 1mol phosphorus oxychloride is added and pours into 300ml dioxane solvents,
3h is reacted under the mixing speed of 180r/min in 85 DEG C of water-baths, then raises temperature to 93 DEG C, back flow reaction 3h, end temperature is solid
95 DEG C are scheduled on, solvent is slowly steamed when being stirred to react, obtains white solid, takes the above-mentioned white solid dissolving anhydrous second of 300ml
In alcohol, stirred under the mixing speed of 120r/min in 80 DEG C of water-baths to being completely dissolved, filtered at 25 DEG C, cooling recrystallization,
It is dried in vacuo at 120 DEG C for 24 hours, it is spare;
Step 2. acyl chlorides activates PEPA
It takes the dioxane that 150ml newly steams in three-necked flask, weighs 0.2mol diacid chlorides, pour into the flask for filling solvent,
Under nitrogen protection, under 120r/min rotating speeds, electromagnetic agitation 8min, and it is 8 that triethylamine, which is added, to adjust solution pH value, is weighed and two
The PEPA of acyl chlorides equimolar amounts, point 18 additions, until adding, react 5h at 80 DEG C per minor tick 10min, acyl chlorides are made and lives
Change PEPA midbody solutions;
The covalent bond of step 3. acyl chlorides PEPA and graphene oxide
Graphene oxide water solution is made by improved Hummers methods, dry 48h, obtains oxygen in vacuum freeze drier
Graphite alkene powder weighs the above-mentioned graphene oxide powders of 100g, is dispersed in 250ml dioxane solvents, ultrasonic 5h, and will
It is poured into the activation PEPA midbody solutions of the acyl chlorides obtained by step 2, the reaction was continued 8h, obtained caged molecular modification oxidation
Graphene fire retardant;Vacuum drying is for 24 hours.
2. a kind of preparation method of caged molecular modification graphene oxide fire retardant, which is characterized in that the method preparation process
It is as follows:
The synthesis and purifying of step 1. young laying ducks in cage
In 500ml three-necked flask, 1mol pentaerythrites and 1mol phosphorus oxychloride is added and pours into 350ml dioxane solvents,
3h is reacted under the mixing speed of 180r/min in 85 DEG C of water-baths, then raises temperature to 93 DEG C, back flow reaction 3h, end temperature is solid
95 DEG C are scheduled on, solvent is slowly steamed when being stirred to react, obtains white solid;Take the above-mentioned white solid dissolving anhydrous second of 300ml
In alcohol, stirred under the mixing speed of 120r/min in 80 DEG C of water-baths to being completely dissolved, filtered at 25 DEG C, cooling recrystallization,
It is dried in vacuo at 120 DEG C for 24 hours, it is spare;
Step 2. acyl chlorides activates PEPA
It takes the dioxane that 150ml newly steams in three-necked flask, weighs 0.1mol diacid chlorides, pour into the flask for filling solvent,
Under nitrogen protection, under 150r/min rotating speeds, electromagnetic agitation 8min, and it is 8 that triethylamine, which is added, to adjust solution pH value, is weighed and two
The PEPA of acyl chlorides equimolar amounts, point 9 additions, until adding, react 5h at 80 DEG C per minor tick 8min, acyl chlorides activation are made
PEPA midbody solutions;
The covalent bond of step 3. acyl chlorides PEPA and graphene oxide
Graphene oxide water solution is made by improved Hummers methods, dry 48h, obtains oxygen in vacuum freeze drier
Graphite alkene powder;
The above-mentioned graphene oxide powders of 70g are weighed, are dispersed in 200ml dioxane solvents, ultrasonic 5h, and it is poured into step
In acyl chlorides activation PEPA midbody solutions obtained by two, it is fire-retardant that caged molecular modification graphene oxide is made in the reaction was continued 8h
Agent;Vacuum drying is for 24 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610846413.0A CN106432802B (en) | 2016-09-23 | 2016-09-23 | A kind of preparation method of caged molecular modification graphene oxide fire retardant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610846413.0A CN106432802B (en) | 2016-09-23 | 2016-09-23 | A kind of preparation method of caged molecular modification graphene oxide fire retardant |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106432802A CN106432802A (en) | 2017-02-22 |
CN106432802B true CN106432802B (en) | 2018-10-26 |
Family
ID=58166458
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610846413.0A Active CN106432802B (en) | 2016-09-23 | 2016-09-23 | A kind of preparation method of caged molecular modification graphene oxide fire retardant |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106432802B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111420634B (en) * | 2020-03-20 | 2022-09-13 | 广东工业大学 | Bifunctional group magnetic graphene oxide adsorption material, preparation method and application |
CN112011262A (en) * | 2020-08-21 | 2020-12-01 | 嵊州市汇业新材料科技有限公司 | High-flame-retardancy polycarbonate modified polyurethane coating and preparation method thereof |
CN117343679B (en) * | 2023-12-04 | 2024-02-06 | 烟台隆达树脂有限公司 | Preparation method of high-heat-conductivity epoxy electronic adhesive |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105199159B (en) * | 2015-10-27 | 2017-08-08 | 沈阳化工大学 | A kind of graft grapheme flame retardant rubber and preparation method |
CN105802015A (en) * | 2016-04-29 | 2016-07-27 | 宁波宏协承汽车部件有限公司 | Flame retardant PP automotive front windshield lower clipping strip material and preparation method thereof |
-
2016
- 2016-09-23 CN CN201610846413.0A patent/CN106432802B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN106432802A (en) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Haeri et al. | Recent progress on the metal-organic frameworks decorated graphene oxide (MOFs-GO) nano-building application for epoxy coating mechanical-thermal/flame-retardant and anti-corrosion features improvement | |
CN106432802B (en) | A kind of preparation method of caged molecular modification graphene oxide fire retardant | |
WO2020182111A1 (en) | Molybdenum disulfide hybrid flame retardant coated with phosphorus-nitrogen-zinc two-dimensional supramolecule and application thereof | |
CN105344327A (en) | Preparation method of MOFs graphene composite material | |
CN106916336B (en) | The method of ion liquid modified hollow glass micropearl and using it as the flame retardant thermoplastic polyurethane elastomer of fire retardant | |
CN105561864B (en) | A kind of imidazoline amophoteric surface active agent and preparation method | |
CN108190963B (en) | Multistage hollow CoFe2O4Material, CoFe2O4Preparation method and application of/C composite material | |
CN107312455A (en) | A kind of photocuring environment-friendly type weatherability PVD finish paints and its preparation method and application | |
WO2013182023A1 (en) | Carbon fiber surface modifier, modified carbon fiber, composite material and preparation methods therefor | |
CN103013322B (en) | Preparation method of epoxy non-isocyanate polyurethane heavy anti-corrosion coating | |
CN109486348A (en) | A kind of fire-proof corrosive-resistant paint preparation method | |
WO2022188597A1 (en) | Low-hygroscopicity pa10t and synthesis method therefor | |
CN101003544A (en) | Method for preparing finished products of salt mixture of organic cobalt class of giving priority to cobalt boroacidate | |
CN104650726A (en) | Thermal insulation high-elasticity waterproof paint and preparation method thereof | |
CN102690545B (en) | Electric equipment moisture resistance, corrosion resistance and insulation protection agent and preparation method thereof | |
CN106751469B (en) | A kind of fluorine titanium Hybrid fire retardant and the preparation method and application thereof | |
CN102965050A (en) | Nano-kieselguhr modified adhesive for packaging | |
CN101967275A (en) | Nano magnesium carbonate modified fire protection engineering plastic and preparation method thereof | |
KR101367558B1 (en) | Polymer membranes for fuel cells, based on interpolyelectrolyte complexes of polyaniline and nafion or it's analogues | |
CN107163519A (en) | A kind of graphene/PET composite boards of the resistance to molten drop of high intensity and preparation method thereof | |
CN107090100B (en) | A kind of environmental protection phosphorus-nitrogen one-component expansion type flame retardant and preparation method thereof | |
CN106519318B (en) | A kind of integrated natural rubber of fire-retardant enhancing and preparation method thereof | |
CN108192290A (en) | A kind of environment protecting thermal insulating material used for building exterior wall and preparation method thereof | |
CN105837631B (en) | A kind of preparation method of phosphorous modified epoxy plasticizer and obtained plasticizer | |
CN105949509B (en) | A kind of six methylenephosphonic acid magnesium fire retardant of hybrid inorganic-organic 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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |