CN105733145B - The graphene oxide, halogen-free flame retardance of polyvinyl alcohol material and preparation method thereof that a kind of amion acetic acid is modified - Google Patents
The graphene oxide, halogen-free flame retardance of polyvinyl alcohol material and preparation method thereof that a kind of amion acetic acid is modified Download PDFInfo
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Abstract
The invention discloses the graphene oxide, halogen-free flame retardance of polyvinyl alcohol material and preparation method thereof that a kind of amion acetic acid is modified.The graphene oxide that amion acetic acid is modified, is prepared by the method comprised the following steps：1) graphite oxide is added to the water, ultrasonic disperse, graphene oxide dispersion is made；2) amion acetic acid solution reacts 8~12h with graphene oxide dispersion at 90~95 DEG C, is separated after reaction, dries, produces；The mass ratio of amion acetic acid and graphene oxide is 1~5:1.By the way that amion acetic acid molecule is grafted in graphene oxide layer, on the one hand, graphene sheet layer has certain air barrier and anti-flammability；On the other hand, elecrtonegativity carboxyl then can be used for targeted induction MgAl LDH lamellas, so as to realize that MgAl LDH's is dispersed, plays graphene and MgAl LDH cooperative flame retardant effect, improves the flame retardant effect of PVA matrixes.
Description
Technical field
The invention belongs to polyvinyl alcohol flame-retardant material technical field, and in particular to the graphite oxide that a kind of amion acetic acid is modified
Alkene, further relate to halogen-free flame retardance of polyvinyl alcohol material and its preparation side of a kind of graphene oxide being modified using above-mentioned amion acetic acid
Method.
Background technology
Polyvinyl alcohol (PVA) is a kind of nontoxic, non-stimulated high polymer, have excellent film forming, mechanical strength and thoroughly
Bright property, there is important application in industries such as packaging, medicine and food.But because polyvinyl alcohol is flammable strong, it significantly limit
Its application.It is significant that polyvinyl alcohol flame-retardant material is obtained using method of modifying.
Halogen containing flame-retardant has the characteristics of convenient addition, good flame retardation effect, but has not met China's fire retardant industry environmental protection
Change, low toxicityization, high efficiency, the development trend of functionalization.Many scientific workers have been working on halogen-free flame retardance of polyvinyl alcohol material
Exploitation.
Patent CN103265714A discloses a kind of preparation method of polyvinyl alcohol/graphene composite thin film, including
Following steps：Prepare graphene oxide soliquid；Prepare polyvinyl alcohol and graphene oxide dispersion soln；Coating die is simultaneously
Non-isothermal is dried, and is stripped and is produced.The laminated film has the characteristics of safe, the feature of environmental protection is good；And the laminated film is saturating
Oxygen Coefficients highest have dropped 95.8%, have superelevation oxygen-barrier property.But the fire retardancy of single graphene oxide is limited,
The requirement of fire proofing can not be met.
Li Fayan etc. (Anhui chemical industry, the 2nd phase of volume 2013.04,39) have studied polyvinyl alcohol/magnalium bimetal hydroxide
The synthesis of thing (LDH) composite and performance, it uses solution blended process to be prepared for composite, and result of the test shows, adds
LDH can significantly improve PVA decomposition temperature, and have the function that to suppress residual combustion so that PVA thermal stability and resistance
Combustion performance has more obvious improvement；But agglomeration easily occurs, influences composite with LDH addition in testing
Mechanical property and fire resistance.
The content of the invention
It is an object of the invention to provide the graphene oxide that a kind of amion acetic acid is modified, so as to applied to polyvinyl alcohol
In fire proofing, it is limited to solve to add single graphene oxide flame retardant effect in existing polyvinyl alcohol material, and LDH addition
It is easy to the technical problem reunited.
Second object of the present invention is to provide a kind of polyethylene for the graphene oxide being modified using above-mentioned amion acetic acid
Alcohol bittern-free flame-proof material, PVA bittern-free flame-proof materials are made to meet from fiery self-extinguishment, the low cigarette of low toxicity and environmental requirement.
Third object of the present invention is to provide the preparation method of above-mentioned halogen-free flame retardance of polyvinyl alcohol material.
In order to realize the above object the technical solution adopted in the present invention is：The graphite oxide that a kind of amion acetic acid is modified
Alkene, it is prepared by following steps：
1) graphite oxide is added to the water, ultrasonic disperse, graphene oxide dispersion is made；
2) amion acetic acid solution is added in graphene oxide dispersion obtained by step 1), is warming up to 90~95 DEG C of reactions
8~12h, separated after reaction, dry, produce；The mass ratio of amion acetic acid and graphene oxide is 1~5:1.
Graphene is a kind of typical two-dimentional carbon nanomaterial, has good electrical and thermal conductivity and physical barrier, because
And it may be used as fire proofing.As its oxidation product, graphene oxide (GO) has a variety of oxygen-containing functional groups, is on graphene
The product that is substituted by hydroxyl, carboxyl and epoxy radicals of partial double bond, it has flakiness ratio big, is readily dispersed in water and other are molten
The characteristics of in agent.
From ageing and security consideration, graphene oxide is preferably made by Hummers methods.In its product structure, side
Edge has derivative carboxylic acid group, is mainly phenolic hydroxyl group and epoxy radicals in plane.Graphite oxide is stirred vigorously through ultrasound or high shear, in water
It is middle to form stable graphene oxide suspension.Because GO activity group contents increase, partial reduction processing can be carried out, is made
Redox graphene (RGO), so as to need to be modified it according to different.The present invention utilizes amion acetic acid (Glycine)
It is modified, its reaction mechanism is the epoxy reaction of the amino and graphene oxide by amion acetic acid, so as to by ammonia
Guanidine-acetic acid is grafted on graphene sheet layer, and the carboxyl of amion acetic acid is not involved in reaction and remained, and its reaction mechanism is as follows：
In step 1), the mass ratio of graphite oxide and water is：1:100~600.
In step 2), described be separated into is separated by suction method or centrifugal process.Consider from separative efficiency, suction method enters
One step is filtered preferably by the filter membrane that aperture is 0.22 μm；The further preferred centrifugal condition of centrifugal process is under 8000rpm
30min is centrifuged.Gained filter cake will be filtered or centrifuge obtained slurry, further drying, produce amion acetic acid modification
Graphene oxide.
The graphene oxide that amion acetic acid provided by the invention is modified, by the way that amion acetic acid molecule is grafted into graphite oxide
On alkene lamella, on the one hand, graphene sheet layer has certain air barrier and anti-flammability；On the other hand, elecrtonegativity carboxyl is then
Available for positively charged other types fire retardant (such as LDH classes) is stablized, other types fire retardant is realized in polymer P VA
It is dispersed, acted on so as at utmost play the cooperative flame retardant of graphene and other fire retardants, significantly improve PVA bases
The flame retardant effect of body.
The halogen-free flame retardance of polyvinyl alcohol material of the graphene oxide provided by the invention being modified using above-mentioned amion acetic acid, by
The graphene oxide and magnalium type layered double-hydroxide that polyvinyl alcohol, amion acetic acid are modified form, and the mass ratio of three is
100:(0.1~5)：(1~6).
Magnalium type layered double-hydroxide (MgAl-LDH) is passed through by positively charged main layer board and interlayer anion
The compound that the interaction assembling of non-covalent bond forms, its structure are similar to shepardite Mg (OH)2, by MgO6Octahedron shares
Prismatic is into elementary layer, the Mg on layer2+Can be within the specific limits by Al3+Same order elements so that laminate is positively charged, interlayer
There is tradable anion to be balanced with the positive charge on laminate.MgAl-LDH can be prepared using a variety of prior arts, such as low
Saturation coprecipitation, high supersaturated coprecipitation, hydrothermal synthesis method, nucleation/crystallization isolation method, ion-exchange etc., also can be straight
Connect and use commercially available prod, such as the synthetic hydrotalcite (production code member 652288, CAS 11097-59-9) of Aldrich.
MgAl-LDH fire retardant mechanism is, when heated, its constitution water laminated sheet hydroxyl and interlayer ion are with water and CO2's
Form is deviate from, and playing reduces burning gases concentration and barrier O2Fire retardation；MgAl-LDH constitution water, laminate hydroxyl and
Interlayer ion departs from laminate in different temperature, can discharge fire retardant matter in (200~800 DEG C) in lower temperature；Hindering
During combustion, caloric receptivity is big, advantageously reduces high temperature caused by burning, and the product after being thermally decomposed is a kind of porous material
Material, specific surface area is larger, adsorbable pernicious gas, has fire-retardant and suppression cigarette double effects.
The preparation method of above-mentioned halogen-free flame retardance of polyvinyl alcohol material, comprises the following steps：
1) graphene oxide that amion acetic acid is modified is added to the water, ultrasonic disperse, obtains the oxygen of amion acetic acid modification
Graphite alkene dispersion liquid；
2) graphene oxide dispersion that amion acetic acid obtained by step 1) is modified is added in poly-vinyl alcohol solution, stirred
Uniformly, magnalium type layered double-hydroxide dispersion liquid is added, is stirred, dries, produces.
In step 1), graphene oxide and the mass ratio of water that amion acetic acid is modified are (0.2~1)：100.In this quality
Than scope configure the graphene oxide dispersion of amion acetic acid modification, be advantageous to improve ultrasonic efficiency and dispersion stable.
In the poly-vinyl alcohol solution, the mass ratio of polyvinyl alcohol and water is 1:(5~20).
The mechanical property of stability and composite from solution considers, the preferred cold soluble type PVA of polyvinyl alcohol.Enter one
Walk the polyvinyl alcohol that the preferred trade mark is 2488,2088 or 1788.
Step 2) the magnalium type layered double-hydroxide dispersion liquid is that magnalium type layered double-hydroxide is added into water
In, ultrasonic disperse 20min, produce.From subsequent reactions efficiency and the stability of dispersion liquid, magnalium type layered double-hydroxide
Mass ratio with water is preferably 1：(5~10).
In step 2), after the completion of the graphene oxide solution addition that amion acetic acid is modified, the time of stirring is 1~4h；Magnesium
After the completion of aluminium profiles layered double-hydroxide dispersion liquid adds, the time of stirring is 1~4h.By being sufficiently stirred, can make each anti-
Answer thing to be well mixed, promote stable reaction effectively to carry out.
The preparation method of halogen-free flame retardance of polyvinyl alcohol material provided by the invention, the graphene oxide table that amion acetic acid is modified
Face carboxyl stretches out and is in elecrtonegativity, and MgAl-LDH lamellas are in electropositive, in aqueous, graphene oxide layer targeting
MgAl-LDH lamellas are induced, so as to realize that MgAl-LDH's is dispersed, effectively avoid MgAl-LDH reunion.In poly- second
In enol bittern-free flame-proof material, amion acetic acid serves the effect of graphene oxide and MgAl-LDH lamella complexing agents, amino with
Connected by chemical bond power between graphene oxide, be connected with MgAl-LDH by electrostatic force, can be at utmost
Realize that graphene and MgAl-LDH are acted on PVA cooperative flame retardant；This method operating procedure is simple, the PVA Halogens resistance of preparation
Combustible material, good flame retardation effect, meet environmental requirement, have a good application prospect.
Brief description of the drawings
Fig. 1 is the graphene oxide (Glycine- that the graphene oxide of the embodiment of the present invention 1 (GO) is modified with amion acetic acid
RGO infrared spectrogram).
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The graphene oxide that the amion acetic acid that the present embodiment provides is modified, is prepared by following steps：
1) graphite oxide that 0.5gHummers methods obtain is added in 300mL water, ultrasonic disperse 30min, oxidation is made
Graphene dispersing solution；1.5g amion acetic acids are dissolved in 200mL water, amion acetic acid solution is made；
2) amion acetic acid solution obtained by step 1) is added drop-wise in graphene oxide dispersion obtained by step 1), stirred in magnetic force
Mix down, be warming up to 90 DEG C of reaction 8h, obtain amion acetic acid modified graphene oxide dispersion liquid；The use of aperture is 0.22 μm of cellulose
Filter membrane is filtered, and is removed unreacted amion acetic acid, the amion acetic acid modified graphite filter cake of isolated purifying, is dried, i.e.,
.
The infrared spectrogram such as Fig. 1 for the graphene oxide (Glycine-RGO) that amion acetic acid manufactured in the present embodiment is modified
Shown, GO is the infrared spectrum of graphene oxide, and as seen from the figure, GO is in 1730cm-1There is carbonylic stretching vibration peak in place, but
In Glycine-RGO, this peak disappears, and represents that GO is reduced to RGO；In addition, the 1300cm in Glycine-RGO-1Occur
One new C-N stretching vibration peak, shows that amion acetic acid is successfully grafted on the lamella of graphene oxide.
The halogen-free flame retardance of polyvinyl alcohol material for the graphene oxide that the above-mentioned amion acetic acid that the present embodiment provides is modified, by gathering
The graphene oxide and magnalium type layered double-hydroxide composition that vinyl alcohol, amion acetic acid are modified, the mass ratio of three is 100:
0.1:1。
The preparation method for the above-mentioned halogen-free flame retardance of polyvinyl alcohol material that the present embodiment provides, comprises the following steps：
1) graphene oxide that 0.1g amion acetic acids are modified is added in 50mL water, ultrasonic disperse 30min, obtains amino
The graphene oxide dispersion that acetic acid is modified；100g cold cuts polyvinyl alcohol (2488 type) is dissolved in 500mL water, obtains polyethylene
Alcoholic solution；
2) graphene oxide dispersion that amion acetic acid obtained by step 1) is modified is added in poly-vinyl alcohol solution, stirred
MgAl-LDH dispersion liquids (the double hydroxides of magnalium type stratiform of the layered double-hydroxide of magnalium type containing 1g are added dropwise to being uniformly dispersed in 2h
The mass ratio of thing and water is 1:5, ultrasonic disperse 20min, produce), continue to stir 4h, be put into baking oven and dry, produce.
Embodiment 2
The graphene oxide that the amion acetic acid that the present embodiment provides is modified, is prepared by following steps：
1) graphite oxide that 2gHummers methods obtain is added in 500mL water, ultrasonic disperse 30min, oxidation stone is made
Black alkene dispersion liquid；10g amion acetic acids are dissolved in 500mL water, amion acetic acid solution is made；
2) amion acetic acid solution obtained by step 1) is added drop-wise in graphene oxide dispersion obtained by step 1), stirred in magnetic force
Mix down, be warming up to 95 DEG C of reaction 10h, obtain amion acetic acid modified graphene oxide dispersion liquid；Existed using supercentrifuge
30min is centrifuged under 8000rpm, unreacted amion acetic acid is removed, isolated slurry, drying, produces.
The halogen-free flame retardance of polyvinyl alcohol material for the graphene oxide that the above-mentioned amion acetic acid that the present embodiment provides is modified, by gathering
The graphene oxide and magnalium type layered double-hydroxide composition that vinyl alcohol, amion acetic acid are modified, the mass ratio of three is 100:
5:5。
The preparation method for the above-mentioned halogen-free flame retardance of polyvinyl alcohol material that the present embodiment provides, comprises the following steps：
1) graphene oxide that 5g amion acetic acids are modified is added in 500mL water, ultrasonic disperse 30min, obtains amino
The graphene oxide dispersion that acetic acid is modified；100g cold cuts polyvinyl alcohol (2088 type) is dissolved in 500mL water, obtains polyethylene
Alcoholic solution；
2) graphene oxide dispersion that amion acetic acid obtained by step 1) is modified is added in poly-vinyl alcohol solution, stirred
MgAl-LDH dispersion liquids (the double hydroxides of magnalium type stratiform of the layered double-hydroxide of magnalium type containing 5g are added dropwise to being uniformly dispersed in 2h
The mass ratio of thing and water is 1:10, ultrasonic disperse 20min, produce), continue to stir 4h, be put into baking oven and dry, produce.
Embodiment 3
The graphene oxide that the amion acetic acid that the present embodiment provides is modified, is prepared by following steps：
1) graphite oxide that 2gHummers methods obtain is added in 500mL water, ultrasonic disperse 30min, oxidation stone is made
Black alkene dispersion liquid；10g amion acetic acids are dissolved in 500mL water, amion acetic acid solution is made；
2) amion acetic acid solution obtained by step 1) is added drop-wise in graphene oxide dispersion obtained by step 1), stirred in magnetic force
Mix down, be warming up to 95 DEG C of reaction 10h, obtain amion acetic acid modified graphene oxide dispersion liquid；The use of aperture is 0.22 μm of fiber
Plain filter membrane is filtered, and is removed unreacted amion acetic acid, the amion acetic acid modified graphite filter cake of isolated purifying, is dried,
Produce.
The halogen-free flame retardance of polyvinyl alcohol material for the graphene oxide that the above-mentioned amion acetic acid that the present embodiment provides is modified, by gathering
The graphene oxide and magnalium type layered double-hydroxide composition that vinyl alcohol, amion acetic acid are modified, the mass ratio of three is 100:
3:6。
The preparation method for the above-mentioned halogen-free flame retardance of polyvinyl alcohol material that the present embodiment provides, comprises the following steps：
1) graphene oxide that 3g amion acetic acids are modified is added in 500mL water, ultrasonic disperse 30min, obtains amino
The graphene oxide dispersion that acetic acid is modified；100g cold cuts polyvinyl alcohol (1788 type) is dissolved in 500mL water, obtains polyethylene
Alcoholic solution；
2) graphene oxide dispersion that amion acetic acid obtained by step 1) is modified is added in poly-vinyl alcohol solution, stirred
MgAl-LDH dispersion liquids (the double hydroxides of magnalium type stratiform of the layered double-hydroxide of magnalium type containing 6g are added dropwise to being uniformly dispersed in 2h
The mass ratio of thing and water is 1:5, ultrasonic disperse 20min, produce), continue to stir 4h, be put into baking oven and dry, produce.
Embodiment 4
The graphene oxide that the amion acetic acid that the present embodiment provides is modified, is prepared by following steps：
1) graphite oxide that 2gHummers methods obtain is added in 500mL water, ultrasonic disperse 30min, oxidation stone is made
Black alkene dispersion liquid；2g amion acetic acids are dissolved in 200mL water, amion acetic acid solution is made；
2) amion acetic acid solution obtained by step 1) is added drop-wise in graphene oxide dispersion obtained by step 1), stirred in magnetic force
Mix down, be warming up to 93 DEG C of reaction 12h, obtain amion acetic acid modified graphene oxide dispersion liquid；The use of aperture is 0.22 μm of fiber
Plain filter membrane is filtered, and is removed unreacted amion acetic acid, the amion acetic acid modified graphite filter cake of isolated purifying, is dried,
Produce.
The halogen-free flame retardance of polyvinyl alcohol material for the graphene oxide that the above-mentioned amion acetic acid that the present embodiment provides is modified, by gathering
The graphene oxide and magnalium type layered double-hydroxide composition that vinyl alcohol, amion acetic acid are modified, the mass ratio of three is 100:
1:4。
The preparation method for the above-mentioned halogen-free flame retardance of polyvinyl alcohol material that the present embodiment provides, comprises the following steps：
1) graphene oxide that 1g amion acetic acids are modified is added in 150mL water, ultrasonic disperse 30min, obtains amino
The graphene oxide dispersion that acetic acid is modified；100g cold cuts polyvinyl alcohol (1788 type) is dissolved in 500mL water, obtains polyethylene
Alcoholic solution；
2) graphene oxide dispersion that amion acetic acid obtained by step 1) is modified is added in poly-vinyl alcohol solution, stirred
MgAl-LDH dispersion liquids (the double hydroxides of magnalium type stratiform of the layered double-hydroxide of magnalium type containing 4g are added dropwise to being uniformly dispersed in 2h
The mass ratio of thing and water is 1:8, ultrasonic disperse 20min, produce), continue to stir 4h, be put into baking oven and dry, produce.
Test example
The halogen-free flame retardance of polyvinyl alcohol material of embodiment 1~4, which is respectively placed in, to be suppressed in vulcanizing press.Compression molding
Machine is arranged to 170 DEG C of plate temperature, 170 DEG C of lower plate temperatures, hot pressing pressure 10MPa, hot pressing 1h, cold pressing 30min, then will be pressed
The model of system is tailored as 120 × 6.5 × 3mm battens, tests its oxygen index (OI).
Limited oxygen index evaluation of measuring material is ignited or started one of index of complexity of burning, and characterizes material
Expect the important parameter of combustibility.Its principle is at the specified experimental conditions, it is proper in oxygen-nitrogen mixture body to be tested sample
Minimum oxygen percentage during stable flame combustion can be maintained well.Oxygen index (OI) numerical value is higher to represent that material is more nonflammable, fire prevention
Security is better, and the fire resistance of polymeric material is better.The resistance of the halogen-free flame retardance of polyvinyl alcohol material of embodiment 1~4
It is as shown in table 1 to fire result of the test.
The fire retardancy test result of the halogen-free flame retardance of polyvinyl alcohol material of the embodiment 1~4 of table 1
| Sequence number | Limited oxygen index, % |
| Pure PVA | 22.1 |
| Embodiment 1 | 26.7 |
| Embodiment 2 | 35.7 |
| Embodiment 3 | 34.3 |
| Embodiment 4 | 30.3 |
From the fire retardancy test result of table 1, the limited oxygen index highest of halogen-free flame retardance of polyvinyl alcohol material of the invention
Reach 35.7%, there is good flame retardant effect.
Claims (4)
- A kind of 1. halogen-free flame retardance of polyvinyl alcohol material, it is characterised in that the graphene oxide being modified by polyvinyl alcohol, amion acetic acid Formed with magnalium type layered double-hydroxide, the mass ratio of three is 100:(0.1~5)：(1~6)；The graphene oxide that the amion acetic acid is modified, is prepared by the method comprised the following steps：1) graphite oxide is added to the water, ultrasonic disperse, graphene oxide dispersion is made；2) amion acetic acid solution is added in graphene oxide dispersion obtained by step 1), be warming up to 90~95 DEG C of reactions 8~ 12h, separated after reaction, dry, produce；Wherein, the mass ratio of amion acetic acid and graphene oxide is 1~5:1.
- 2. halogen-free flame retardance of polyvinyl alcohol material as claimed in claim 1, it is characterised in that the step 1) graphite oxide is The graphite oxide that Hummers methods obtain.
- 3. halogen-free flame retardance of polyvinyl alcohol material as claimed in claim 1, it is characterised in that in step 2), it is described be separated into it is logical Cross suction method or centrifugal process is separated.
- 4. the preparation method of halogen-free flame retardance of polyvinyl alcohol material as claimed in claim 1, it is characterised in that including following step Suddenly：1) graphene oxide that amion acetic acid is modified is added to the water, ultrasonic disperse, obtains the oxidation stone of amion acetic acid modification Black alkene dispersion liquid；2) graphene oxide dispersion that amion acetic acid obtained by step 1) is modified is added in poly-vinyl alcohol solution, stirring is equal It is even, magnalium type layered double-hydroxide dispersion liquid is added, is stirred, dries, produces.
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