CN105837785A - Preparation method of attapulgite/fluorinated polyurethane nanocomposite - Google Patents
Preparation method of attapulgite/fluorinated polyurethane nanocomposite Download PDFInfo
- Publication number
- CN105837785A CN105837785A CN201610428822.9A CN201610428822A CN105837785A CN 105837785 A CN105837785 A CN 105837785A CN 201610428822 A CN201610428822 A CN 201610428822A CN 105837785 A CN105837785 A CN 105837785A
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- modified
- reaction
- preparation
- carrying
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- 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
- C08K3/346—Clay
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention relates to a preparation method of an attapulgite/ fluorinated polyurethane nanocomposite. The method comprises the steps of firstly, carrying out pretreatment on attapulgite, specifically, dispersing the attapulgite into deionized water, adding a dispersing agent-sodium hexametaphosphate into the deionized water, stirring and then centrifuging, drying and then grinding, acidizing the purified attapulgite, and then carrying out centrifugal drying and sieving; secondly, carrying out organic modification on the attapulgite, specifically, firstly hydrolyzing a silane coupling agent KH550, then adding alcohol and the pretreated attapulgite, carrying out a reflux reaction and then filtering, drying the obtained filter cake, grinding and sieving to obtain modified attapulgite; finally, evenly mixing fluorinated polyether polyol and the modified attapulgite in a nitrogen atmosphere condition, then adding isocyanate into the mixture, heating, carrying out a reaction and then vacuumizing, removing bubbles, adding a chain extender-triethanolamine, stirring and then molding by vacuum solidification. The preparation method is mild in conditions, simple and convenient in operation, easy in control of conditions and low in cost.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of polymer based nanocomposites, a kind of concavo-convex
The preparation method of rod soil/fluorochemical urethane nano composite material.
Background technology
Fluorochemical urethane is reported at first from nineteen forty-seven Bayer, rises so far to first patent of 1958, experienced by 50
The development course in remaining year.In PU structure, introduce fluorine-containing groups, not only remain the height determined due to polyurethane (PU) structure
Intensity, high resiliency, high-wearing feature, excellent cryogenic property and adhesive property, be also provided with high heat-resisting because of the existence of C-F key
Property, weatherability, chemical resistance, water and oil repellant, lubricity, anti-stain characteristic, good biocompatibility etc..Thus, FPU
In national defence, military project, the field such as civilian, there is vast application prospect and development space.
In recent years, utilize phyllosilicate that polymer is modified, be the one of polymer based nanocomposites research
Individual important directions.Owing to phyllosilicate itself has natural nano effect, add the performance that just can make composite on a small quantity
Increased substantially very much, such as heat stability, mechanical property etc..This has promoted polyurethane-base nano composite material research the most in succession
The development that deepens continuously.Compared with the montmorillonite in conventional layer silicate mineral, attapulgite is one dimension fibre club shaped structure,
Being more easy to dissociate and disperse, owing to specific surface area is big, surface activity is high, easily reunites, and the hydroxyl that surface is containing polarized, Jing Guoyou
Machine modification, its surface from total hydrophilic become appropriateness lipophile, there is inorganic and organic double properties, improve itself and
Interface compatibility between high polymer.Attapulgite is a kind of silicate mineral rich in magnalium, has 2:1 type layer structure,
I.e. two-layer tetrahedral si-o film one layer of magnesia of folder or alumina octahedral, due to the restriction of crystal structure, attapulgite grows into
For nanoclub-like crystal form.The essential structure unit of its crystal structure is parallel to the silicon-oxy tetrahedron double-strand composition of C axle, respectively
Individual interchain is connected by oxygen atom, every four one of the sensing (i.e. the top, angle of silicon-oxy tetrahedron) of the free oxygen atom of silicon-oxy tetrahedron
Group, arrangement mode makes tetrahedral sheet be continuously connected at interchain alternately up and down, thus constitutes chain phyllosilicate.But four sides
It is discontinuous that the discordance that the free oxygen atom of body points to determines octahedral sheet, forms a lot of duct, and this is also concavo-convex
Rod soil is different from the place of other phyllosilicates such as montmorillonite.Due to the layer chain fiber club shaped structure of attapulgite, big
The activated silica hydroxyl etc. that specific surface area and rich surface contain, it is possible to reach good dispersion in polymer network structure so that it is become
Supporting material for one preferable clay polymer nanocomposites (CPN).In recent years, many documents are had to report with concavo-convex
Rod soil is polymer-modified, can the good nano composite material of processability.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of attapulgite/fluorochemical urethane nanometer
The preparation method of composite, the preparation method of described this attapulgite/fluorochemical urethane nano composite material to solve
Its heat stability of fluorochemical urethane simple in prior art and the best technical problem of mechanical property.
The invention provides the preparation method of a kind of attapulgite/fluorochemical urethane nano composite material, including walking as follows
Rapid:
(1) step that attapulgite carries out pretreatment, disperses attapulgite in deionized water, adds dispersant
Sodium hexameta phosphate, described attapulgite and the mass ratio of dispersant are 10:0.1 ~ 1, after stirring 2 ~ 4h the most at normal temperatures, the end
Layer residue discards, and upper strata suspension is centrifuged, is ground after drying, then attapulgite clay after purifying soil is dispersed in hydrochloric acid molten
In liquid, then sieve with centrifugal drying after acetone and deionized water alternately washing to neutrality grinding；
(2) one carry out organically-modified step to attapulgite, are first hydrolyzed Silane coupling agent KH550, solution system
For H2O and ethanol, described ethanol, the volume ratio of H2O and KH550 are 72:8:20, after stirring 1-3h, regulate solution under room temperature
PH value is to 4-5, the silane coupler solution after being hydrolyzed, and then adding volume ratio in a reaction vessel is the second of 1:1
Attapulgite after the process of alcohol and water, step (1), adds the KH550 solution hydrolyzed, and described attapulgite, KH550 are molten
In liquid and reaction vessel, the mass volume ratio of the mixed solution of second alcohol and water is 5-10g:100ml:150 ~ 500ml, and this system exists
Under the conditions of 60-70 DEG C, back flow reaction is after 1 ~ 4 hour, filters system, and gained filter cake carries out drying grinding and sieving, and obtains
The attapulgite modified of Amino End Group is contained on surface；
(3) by fluorine-containing polyether glycol and modified attapulgite first mix and blend 30-60min, it is subsequently adding diphenyl
Methylene diisocyanate, this system is gradually heating to 80 DEG C from 40 DEG C, after system temperature reaches 80 DEG C, is further continued for reacting 2-
3h, whole course of reaction is carried out the most under nitrogen atmosphere, and reaction terminates to add chain extender triethanolamine, and described fluorochemical polyether is many
Unit's alcohol, MDI, the mol ratio of triethanolamine are 1:3:1.33, described attapulgite mass fraction
For described fluorine-containing polyether glycol, MDI and the 0.5-2% of triethanolamine quality sum, stirring
After 1-2min, product is poured in politef template, vacuum solidification molding under the conditions of 30 DEG C.
Further, the concentration of the hydrochloric acid solution described in step (1) is 1mol/L, and the acid treatment time is 1 ~ 5h, so
Its crystal structure also will not be destroyed in the surface being possible not only to activate ATT owing to acid concentration is the highest.
Further, in step (2), attapulgite has carried out the method for modifying of surface grafting, and its modified surface is newly grafted
Amino End Group, impart the double properties of attapulgite inorganic-organic, it is possible to and fluorochemical urethane intermolecular generation chemical reaction
Combining with the form of chemical bond, the compatibility is greatly improved.
Further, fluorine-containing polyether glycol in step (3), is to utilize boron trifluoride diethyl etherate and ethylene glycol as primosome
System, uses the soft segment lateral chain fluorine-containing polyether glycol that the method synthetic molecular weight of activity controllable cationic polymerization is controlled.
The present invention mainly utilizes the method that the organically-modified means of chemistry and organic synthesis combine, and rich surface is contained work
Property the inorganic attapulgite of Si-OH group, by it is carried out surface graft modification i.e.: utilize Silane coupling agent KH550 hydrolysis after
The stable chemical bond of the Si-OH formed and the Si-OH generation chemical reaction formation Si-O-Si of attapulgite's surface, and its end group
Functional group is amino (-NH3), thus realize organic surface graft modification of attapulgite.This modified attapulgite can
With the isocyano generation chemical reaction with fluorochemical urethane performed polymer such that it is able to by the attapulgite effect by chemical bond
And be connected on fluorochemical urethane molecule.Utilize Silane coupling agent KH550 that attapulgite is modified, can be at inorganic substances
And between organic substance, erect one " molecular bridge ", inorganic attapulgite mineral are passed through with organic fluorochemical urethane molecule
Chemical bond is connected, and has the most both achieved the chemical bonds of organic and inorganic, and on the other hand attapulgite is as a kind of novel
Nano filling is filled in fluorochemical urethane system, not only improves the heat stability of fluorochemical urethane, mechanical performance etc., and makes
It plays outstanding weather-proof, acid and alkali-resistance, the excellent antiseptic property such as ageing-resistant in sapecial coating field, it is achieved fluorine-containing poly-ammonia
The target of ester low fluorine high performance.
The present invention uses the method for silane coupler surface grafting, carries out organically-modified to attapulgite, and synthetic surface contains
There is the silane coupler modified attapulgite ATT-KH of Amino End Group；And by the method for controllable cationic polymerization by fluorochemical polyether
Polyhydric alcohol (FPO) and MDI (MDI) are synthesized fluorine-containing poly-ammonia under 80 DEG C of nitrogen protective conditions
Ester performed polymer, is subsequently adding attapulgite and chain extender curing molding under the conditions of uniform temperature of modification, it is thus achieved that attapulgite
The fluorochemical urethane nano composite material of soil functionalization.
The present invention compares with prior art, and its technological progress is significant.The present invention uses the inorganic nano attapulgite to be
Modified filler, selects silane coupler that attapulgite carries out surface grafting, thus realize attapulgite and fluorochemical urethane it
Between chemical bonding, fluorochemical urethane is modified, it is thus achieved that a kind of novel nano combined material of attapulgite/fluorochemical urethane
Material.The present invention contrasts simple fluorochemical urethane, and not only heat stability is the most relative with mechanical property improves, and its acid and alkali-resistance,
Corrosion-resistant, ageing-resistant performance also improves a lot.Process of the present invention reaction condition is gentle, it is not necessary to use any additive, concavo-convex
Rod soil itself is cheap, and therefore, this synthetic method has the feature of economy, inexpensive.The synthesis technique of the present invention is simple,
Experiment condition is gentle, and whole preparation system easily builds, and easy and simple to handle, condition is easily-controllable, and product process facilitates simple and direct.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of embodiment 1 gained KH550 rear ATT, ATT-KH550 before modified.
Fig. 2 is the infrared spectrum of embodiment 1 gained KH550 rear FPU-0, FPU-2%ATT-KH550 before modified.
Fig. 3 is that embodiment 1, embodiment 2 and embodiment 3 gained mass fraction are respectively the ATT-KH550 with 2%, 1% and 0
XRD for the FPU of filler characterizes.
Fig. 4 is the SEM figure of embodiment 1 gained KH550 ATT before modified (Fig. 4 A) and modified ATT-KH550 (Fig. 4 B).
Detailed description of the invention
Below by embodiment and combine accompanying drawing and further illustrate the present invention, but protection scope of the present invention is not limited to
These embodiments.
Various raw materials used in various embodiments of the present invention are commercially available if no special instructions.
Embodiment 1
The preparation method of a kind of attapulgite/fluorochemical urethane composite, comprises the steps:
(1) pretreatment of attapulgite
Purify and acidification: 10g attapulgite is disperseed in deionized water, adds 0.5g sodium hexametaphosphate dispersant,
After mixed system stirs 4h at normal temperatures, bottom residue discards, and after being centrifuged upper strata suspension, is dried and grinds.It
Afterwards attapulgite clay after purifying soil is carried out acidification, 5g attapulgite is dispersed in the HCl solution of 50mL1mol/L, room temperature
After lower mixed system stirs one hour, it is centrifuged mixed liquor being dried and grinding sieving.
(2) attapulgite is organically-modified
Silane coupling agent KH550 is modified: being first hydrolyzed silane coupler, solution system is ethanol, H2O, KH550 (body
Long-pending ratio is 72:8:20), after system stirring 2h, regulation solution ph to 4-5.50ml ethanol and 50ml is added in three hole flasks
Water, 5g purify the attapulgite after acidifying, then pour KH550 solution (ethanol/water/KH550=72/8/ that 100ml has hydrolyzed into
20), system after back flow reaction 24h, is filtered under the conditions of 70 DEG C by this system, and gained filter cake carries out drying grinding mistake
300 mesh sieves, obtain surface and contain the attapulgite modified of Amino End Group.
(3) preparation of attapulgite/fluorochemical urethane nano composite material
Fluorine-containing polyether glycol (molecular weight 1500), MDI, the mol ratio of triethanolamine are 1:3:
1.3, in attapulgite/fluorochemical urethane nanocomposite system that design synthesis obtains, modified attapulgite quality is divided
Number is 2%.First fluorine-containing polyether glycol 3.0g and modified attapulgite 0.097g stirs mixing under the conditions of nitrogen atmosphere
Uniformly, adding 1.46gMDI after 30min, this system is gradually heating to 80 DEG C from 40 DEG C, after system temperature reaches 80 DEG C, is further continued for
Reaction 3h, whole course of reaction is carried out the most under nitrogen atmosphere.Reaction adds 0.3875gTEA after terminating, and stirs rapidly 2min
After, product is poured in politef template, vacuum solidification molding under the conditions of 30 DEG C.
Use Perkin Elmer Spectrum 100 FTIR spectrophotometer, to above-mentioned gained
The modified attapulgite of KH550 and attapulgite/fluorochemical urethane nano composite material are characterized, the infrared spectrum of gained
Scheme the most as shown in Figure 1, 2, low frequency range (1200-800cm-1) the asymmetric strong absorption of secondary of predominantly attapulgite, and Si-
The bending vibration district of O, and high frequency region (3700-2800cm-1) it is mainly hydroxyl and the stretching vibration of water of crystallization and zeolite water etc..Recessed
Convex rod soil is modified through KH550, at 2926cm-1Occurring in that faint C-H absworption peak, 1554cm-1 occurs in that the feature of-NH3 is inhaled
Receive, illustrate that KH550 has been grafted to ATT surface.Fluorochemical urethane C-F absworption peak near 800cm-1 is substantially strengthened, this
It is likely due to ATT absorption of vibrations of Si-O-Si near 800cm-1 cause.
Use Germany's BrukerD8 ADVANCE X-ray diffractometer, material nano combined to attapulgite/fluorochemical urethane
Material has done crystal structure analysis, and 2=20oFor the peculiar peak of FPU, and attapulgite/fluorochemical urethane nano composite material is come
Say, 2=8.56oNear occur in that the characteristic peak of (110) crystal face of small and weak ATT, can be concluded that attapulgite success
Enter in FPU system.
The Quanta FEG Flied emission environmental scanning electron microscope using FEI Co. observes the table of ATT after before modified
Face morphology change, the attapulgite rod crystalline substance bundle after contrast before modified is it is found that the brilliant Shu Changdu of its single rod is the most several at several microns
Ten microns, diameter about tens nanometer (Fig. 4 A).Attapulgite after silane coupler processes, its surface topography becomes
Changing, there is projection in attapulgite rod crystalline substance surface, diameter is thicker, with the presence of still have bonding with the brilliant bundle of rod and rod crystalline substance, process is described
Modified attapulgite rod crystalline substance surface grafting KH550 and major part rod is brilliant or (Fig. 4 B) that exist with aggregation.
Embodiment 2
The preparation method of a kind of attapulgite/fluorochemical urethane nano composite material, comprises the steps:
(1) pretreatment of attapulgite
Purify and acidification: 10g attapulgite is disperseed in deionized water, adds 0.5g sodium hexametaphosphate dispersant,
After mixed system stirs 4h at normal temperatures, bottom residue discards, and after being centrifuged upper strata suspension, is dried and grinds.It
Afterwards attapulgite clay after purifying soil is carried out acidification, 5g attapulgite is dispersed in the HCl solution of 50mL1mol/L, room temperature
After lower mixed system stirs one hour, it is centrifuged being dried to mixed liquor to neutrality with acetone and deionized water alternately washing
And grind sieve.
(2) attapulgite is organically-modified
Silane coupling agent KH550 is modified: being first hydrolyzed silane coupler, solution system is ethanol, H2O, KH550 (72/
8/20), after system stirs one hour, regulation solution ph to 4-5.50ml ethanol and 50ml water, 5g is added in three hole flasks
Purify the attapulgite after acidifying, then pour the KH550 solution (ethanol/water/KH550=72/8/20) that 100ml has hydrolyzed, this body into
Under the conditions of tying up to 70 DEG C after back flow reaction 24h, filtering system, gained filter cake carries out drying grinding and crossing 300 mesh sieves,
The attapulgite modified of Amino End Group is contained to surface.
(3) preparation of attapulgite/fluorochemical urethane nano composite material
Fluorine-containing polyether glycol (molecular weight 1500), MDI, triethanolamine mol ratio are 1:3:
1.33, in fluorochemical urethane/nanocomposite system that design synthesis obtains, modified attapulgite mass fraction is 1%.
First fluorine-containing polyether glycol 3.0g and modified attapulgite 0.048g is uniformly mixed under the conditions of nitrogen atmosphere,
Adding 1.46gMDI after 30min, this system is gradually heating to 80 DEG C from 40 DEG C, after system temperature reaches 80 DEG C, is further continued for reaction
3h, whole course of reaction is carried out the most under nitrogen atmosphere.Reaction adds 0.3875gTEA after terminating, rapidly after stirring, and will reaction
Product is poured in politef template, vacuum solidification molding under the conditions of 30 DEG C.
Embodiment 3
The preparation method of a kind of novel attapulgite soil/fluorochemical urethane nano composite material, comprises the steps:
(1) pretreatment of attapulgite
Purify and acidification: 10g attapulgite is disperseed in deionized water, adds 0.5g sodium hexametaphosphate dispersant,
After mixed system stirs 4h at normal temperatures, bottom residue discards, and after being centrifuged upper strata suspension, is dried and grinds.It
Afterwards attapulgite clay after purifying soil is carried out acidification, 5g attapulgite is dispersed in the HCl solution of 50mL1mol/L, room temperature
After lower mixed system stirs one hour, it is centrifuged being dried to mixed liquor to neutrality with acetone and deionized water alternately washing
And grind sieve.
(2) attapulgite is organically-modified
Silane coupling agent KH550 is modified: being first hydrolyzed silane coupler, solution system is ethanol, H2O, KH550
(72/8/20), after system stirs one hour, regulation solution ph to 4-5.In three hole flasks add 50ml ethanol and
50mlH2O, 5g purify the attapulgite after acidifying, add KH550 solution (ethanol/water/KH550=that 100ml has hydrolyzed
72/8/20), system after back flow reaction 24h, is filtered under the conditions of 70 DEG C by this system, and gained filter cake grinds also after drying
Cross 300 mesh sieves, obtain surface and contain the attapulgite modified of Amino End Group.
(3) preparation of attapulgite/fluorochemical urethane nano composite material
Fluorine-containing polyether glycol (molecular weight 1500), MDI, triethanolamine mol ratio are 1:3:
1.33, in fluorochemical urethane/nanocomposite system that design synthesis obtains, modified attapulgite mass fraction is 1.5
%.First, after fluorine-containing polyether glycol 3.0g and 1.46gMDI mixing, this system is gradually heating to 80 DEG C from 40 DEG C, system temperature
After reaching 80 DEG C, being further continued for reacting 3h, whole course of reaction is carried out the most under nitrogen atmosphere.0.3875gTEA is added after 3h, fast
After speed stirring, product is poured in politef template, vacuum solidification molding under the conditions of 30 DEG C.
Claims (2)
1. the preparation method of attapulgite/fluorochemical urethane nano composite material, it is characterised in that comprise the steps:
(1) step that attapulgite carries out pretreatment, disperses attapulgite in deionized water, adds dispersant
Sodium hexameta phosphate, described attapulgite and the mass ratio of dispersant are 10:0.1 ~ 1, after stirring 2 ~ 4h the most at normal temperatures, the end
Layer residue discards, and upper strata suspension is centrifuged, is ground after drying, then attapulgite clay after purifying soil is dispersed in hydrochloric acid molten
In liquid, then sieve with centrifugal drying after acetone and deionized water alternately washing to neutrality grinding；
(2) one carry out organically-modified step to attapulgite, are first hydrolyzed Silane coupling agent KH550, solution system
For H2O and ethanol, described ethanol, the volume ratio of H2O and KH550 are 72:8:20, after stirring 1-3h, regulate solution under room temperature
PH value is to 4-5, the silane coupler solution after being hydrolyzed, and then adding volume ratio in a reaction vessel is the second of 1:1
Attapulgite after the process of alcohol and water, step (1), adds the KH550 solution hydrolyzed, and described attapulgite, KH550 are molten
In liquid and reaction vessel, the mass volume ratio of the mixed solution of second alcohol and water is 5-10g:100ml:150 ~ 500ml, and this system exists
Under the conditions of 60-70 DEG C, back flow reaction is after 1 ~ 4 hour, filters system, and gained filter cake carries out drying grinding and sieving, and obtains
The attapulgite modified of Amino End Group is contained on surface；
(3) by fluorine-containing polyether glycol and modified attapulgite first mix and blend 30-60min, it is subsequently adding diphenyl
Methylene diisocyanate, this system is gradually heating to 80 DEG C from 40 DEG C, after system temperature reaches 80 DEG C, is further continued for reacting 2-
3h, whole course of reaction is carried out the most under nitrogen atmosphere, and reaction terminates to add chain extender triethanolamine, and described fluorochemical polyether is many
Unit's alcohol, MDI, the mol ratio of triethanolamine are 1:3:1.33, described attapulgite mass fraction
For described fluorine-containing polyether glycol, MDI and the 0.5-2% of triethanolamine quality sum, stirring
After 1-2min, product is poured in politef template, vacuum solidification molding under the conditions of 30 DEG C.
The preparation method of a kind of attapulgite/fluorochemical urethane nano composite material the most as claimed in claim 1, its feature exists
In: the concentration of the hydrochloric acid solution described in step (1) is 1mol/L, within the acid treatment time is 5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610428822.9A CN105837785B (en) | 2016-06-16 | 2016-06-16 | A kind of preparation method of attapulgite/fluorochemical urethane nanocomposite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610428822.9A CN105837785B (en) | 2016-06-16 | 2016-06-16 | A kind of preparation method of attapulgite/fluorochemical urethane nanocomposite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105837785A true CN105837785A (en) | 2016-08-10 |
| CN105837785B CN105837785B (en) | 2018-10-12 |
Family
ID=56576204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610428822.9A Expired - Fee Related CN105837785B (en) | 2016-06-16 | 2016-06-16 | A kind of preparation method of attapulgite/fluorochemical urethane nanocomposite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105837785B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109501401A (en) * | 2018-11-27 | 2019-03-22 | 广州迦淇之卉服装有限公司 | A kind of high-strength abrasion-proof TPU composite material and preparation method thereof |
| CN109824941A (en) * | 2019-03-07 | 2019-05-31 | 中国人民解放军海军工程大学 | A kind of preparation method of the modification hollow glass microbead of surface grafting fluorine resin |
| CN110564052A (en) * | 2019-08-13 | 2019-12-13 | 宜兴西工维新科技有限公司 | Fruit and vegetable packaging material with regulation function and ethylene adsorption function and preparation method thereof |
| CN110655635A (en) * | 2019-09-09 | 2020-01-07 | 浙江凯色丽科技发展有限公司 | Polyurethane composite emulsion containing mica-based conductive material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443129A (en) * | 2011-10-24 | 2012-05-09 | 常州奥特纳新材料科技有限公司 | Method for preparing attapulgite/polyurethane composite material |
| CN103319725A (en) * | 2013-06-26 | 2013-09-25 | 兰州理工大学 | Unsaturated polyester nano attapulgite material and preparation method thereof |
| CN104004158A (en) * | 2014-06-13 | 2014-08-27 | 上海理工大学 | Method for preparing soft-segment side-chain fluorinated polyurethane with low fluorine content and high surface performance |
-
2016
- 2016-06-16 CN CN201610428822.9A patent/CN105837785B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443129A (en) * | 2011-10-24 | 2012-05-09 | 常州奥特纳新材料科技有限公司 | Method for preparing attapulgite/polyurethane composite material |
| CN103319725A (en) * | 2013-06-26 | 2013-09-25 | 兰州理工大学 | Unsaturated polyester nano attapulgite material and preparation method thereof |
| CN104004158A (en) * | 2014-06-13 | 2014-08-27 | 上海理工大学 | Method for preparing soft-segment side-chain fluorinated polyurethane with low fluorine content and high surface performance |
Non-Patent Citations (3)
| Title |
|---|
| 孙玉智: ""有机凹凸棒土/聚氨酯弹性体纳米复合材料的研究"", 《太原理工大学硕士学位论文》 * |
| 童婷: ""凹凸棒土矿物相组成、改性及脱色性能的研究"", 《北京化工大学硕士研究生学位论文》 * |
| 葛震等: ""含氟聚氨酯的合成及其应用研究进展"", 《化工新型材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109501401A (en) * | 2018-11-27 | 2019-03-22 | 广州迦淇之卉服装有限公司 | A kind of high-strength abrasion-proof TPU composite material and preparation method thereof |
| CN109501401B (en) * | 2018-11-27 | 2020-04-21 | 上海沙驰服饰有限公司 | High-strength wear-resistant TPU composite fabric and preparation method thereof |
| CN109824941A (en) * | 2019-03-07 | 2019-05-31 | 中国人民解放军海军工程大学 | A kind of preparation method of the modification hollow glass microbead of surface grafting fluorine resin |
| CN110564052A (en) * | 2019-08-13 | 2019-12-13 | 宜兴西工维新科技有限公司 | Fruit and vegetable packaging material with regulation function and ethylene adsorption function and preparation method thereof |
| CN110655635A (en) * | 2019-09-09 | 2020-01-07 | 浙江凯色丽科技发展有限公司 | Polyurethane composite emulsion containing mica-based conductive material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105837785B (en) | 2018-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105837785A (en) | Preparation method of attapulgite/fluorinated polyurethane nanocomposite | |
| CN109593464A (en) | A kind of organic silicon rubber coating of room curing and high temperature resistant, preparation method and application | |
| CN106751741B (en) | A kind of preparation method of polyurethane nano composite material | |
| CN106752119B (en) | A kind of preparation method of carbon black nano material | |
| CN101979443B (en) | Method for producing modified white carbon black | |
| CN106745010A (en) | A kind of lignin-base biological carbon/silica multi-dimension nano hybrid material and its preparation method and application | |
| CN100497171C (en) | Low water absorption silicon-dioxide | |
| CN110204244A (en) | Preparation method and application of graphene oxide-TEOS/silane composite nanomaterial | |
| CN105860435A (en) | Halloysite nanotube / epoxy nanocomposite | |
| EP2982660B1 (en) | Method for producing moulded hydrophobic heat insulation forms | |
| CN101613112A (en) | A kind of preparation of attapulgite modified by silane coupling agent | |
| CN103665939A (en) | Method for integrally preparing high-dispersity ultrafine magnesium hydroxide flame retardant | |
| CN1248224A (en) | Method for making hydrophobic silica gels under neutral conditions | |
| CN108911599B (en) | Method for simultaneously preparing iron oxide and silicon dioxide aerogel pad from iron tailings | |
| CN108623833A (en) | A kind of preparation method of multi-functional aerogel composite | |
| CN103772990A (en) | Preparation method of room temperature sulfurated silicon rubber material co-enhanced by lignin and white black carbon | |
| DE69921450T2 (en) | PROCESS FOR PREPARING TREATED SILICA | |
| CN1654566A (en) | Calcium silicate hydrate nano coating and its production method | |
| KR102316793B1 (en) | Preparation method of needle type metal -silica aerogel composite particle and needle type metal-silica aerogel composite particle prepared by the same | |
| CN109880180A (en) | Nano-cellulose/cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof | |
| CN103204992A (en) | Method for preparing low-viscosity high-boiling silicone oil from raw material of chlorosilane high boiling residue | |
| KR100533734B1 (en) | Process for preparing polymer-layered compound nanocomposite | |
| CN110539536B (en) | Lightweight silica aerogel composite thermal insulation fabric and preparation method thereof | |
| CN104891504B (en) | A kind of method for extracting white carbon from cinder | |
| CN106629742A (en) | Hydrophobic fumed silica preparation method |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181012 Termination date: 20210616 |