CN108752769A - A method of preparing regeneration nano-cellulose/poly styrene composite material using Pickering lotions - Google Patents
A method of preparing regeneration nano-cellulose/poly styrene composite material using Pickering lotions Download PDFInfo
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- CN108752769A CN108752769A CN201810332356.3A CN201810332356A CN108752769A CN 108752769 A CN108752769 A CN 108752769A CN 201810332356 A CN201810332356 A CN 201810332356A CN 108752769 A CN108752769 A CN 108752769A
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- cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
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Abstract
The present invention relates to a kind of methods preparing regeneration nano-cellulose/poly styrene composite material using Pickering lotions, including：Prepared by Pickering lotions, prepared by regeneration nano-cellulose/poly styrene composite material.The present invention prepares Pickering lotions using regeneration nano-cellulose, and stability of emulsion is high, and stable styrene polymerization may be implemented；Regeneration nano-cellulose/the poly styrene composite material being prepared, regenerate nano-cellulose good dispersion in polystyrene, with the good transparency, thermodynamic stability, biodegradability and biocompatibility, it can be used for the fields such as transparent material, environmentally-friendly plastic, biological medicine material.
Description
Technical field
The invention belongs to the field of composite material preparation of biomass nano material and organic high molecular compound, more particularly to
A method of preparing regeneration nano-cellulose/poly styrene composite material using Pickering lotions.
Background technology
In recent years, it is had been to be concerned by more and more people using biomass nano material preparation composite material.Biology in 2009
The world market of matter nano material is worth about 254,000,000,000 dollars, this number is estimated to reach 3 trillion dollars in the year two thousand twenty.Biomass
Nanocomposite have been widely used for the fields such as chemistry, physics, catalysis, material science, biological medicine (Trache D,
Hussin M H,Haafiz M K M,et al.Recent progress in cellulose nanocrystals:
sources and production[J].Nanoscale,2017,9(5):1763-1786).In various biological materials,
Cellulose is because raw material sources are extensive, it is considered to be a kind of inexhaustible material, it meets people to green and biofacies
Hold growing demand (Klemm D, Kramer F, Moritz S, the et al.Nanocelluloses of product:a new
family of nature-based materials[J].Angewandte Chemie International Edition,
2011,50(24):5438-5466).Nano-cellulose refers to the cellulose macromolecule collection that nano-scale is on a certain scale
Aggressiveness.The advantages that nanofiber procatarxis its bigger serface, high reaction activity, biodegradable and recyclability, become
New research hotspot.It is difficult hydrophobic that prepare the greatest problem that nano-cellulose composite material faces, which be hydrophilic nano-cellulose,
Polymer in good dispersion.This is because there are very strong hydrogen bond action, polar nano-cellulose in nano-cellulose surface
It is easy to assemble in apolar polymer matrices.In order to solve this problem, most common method is carried out to nano-cellulose
The surface hydrophobicities such as esterification, silanization, surface grafting are modified.But surface, which is modified, can destroy interfibrous Hyarogen-bonding, reduce multiple
Performance (Khalil H P S A, Bhat A H, the Yusra A F I.Green composites from of condensation material
sustainable cellulose nanofibrils:A review[J].Carbohydrate Polymers,2012,87
(2):963-979；Zhang Y,Wu J,Wang B,et al.Cellulose nanofibril-reinforced
biodegradable polymer composites obtained via a Pickering emulsion approach
[J].Cellulose,2017,24(8):3313-3322)。
Traditional emulsion polymerization is to stablize hydrophobic oil phase monomer using the surfactant of small molecule.Use solids
Stablize monomer (Pickering lotions) instead of traditional surface-active and carries out in-situ polymerization, it cannot be solving nano-cellulose
In polymer the problem of fine dispersion on have a good application prospect.Compared with the lotion for traditionally using surfactant,
Pickering has many advantages, such as that dosage is small, stable, environmentally safe.Jia Xuejuan etc. is prepared for using dissolving regeneration method
The regeneration nano-cellulose that yield is high, suspension stability is good, finds simultaneously, and regeneration nano-cellulose can be used for stablizing
Pickering lotions have in composite material and are widely applied very much foreground (Jia X, Xu R, Shen W, et
al.Stabilizing oil-in-water emulsion with amorphous cellulose[J].Food
Hydrocolloids,2015,43:275-282)。
Invention content
Technical problem to be solved by the invention is to provide a kind of regeneration nanofiber is prepared using Pickering lotions
The method of element/poly styrene composite material, this method prepare Pickering lotions, emulsion-stabilizing using regeneration nano-cellulose
Property it is high, stable styrene polymerization may be implemented, the regeneration nano-cellulose/poly styrene composite material being prepared, regeneration
Nano-cellulose fine dispersion in polystyrene has the good transparency, thermodynamic stability, biodegradability and life
Object compatibility can be used for the fields such as transparent material, environmentally-friendly plastic, biological medicine material.
A kind of side preparing regeneration nano-cellulose/poly styrene composite material using Pickering lotions of the present invention
Method, the specific steps are：
(1) will regeneration nano-cellulose suspension be used as water phase, styrene of the addition containing initiator be oil phase, homogeneous,
Obtain Pickering lotions, wherein the mass fraction that regeneration nano-cellulose accounts for styrene is 0.2%-20%, and initiator accounts for
The mass fraction of styrene is 0.1%-5%；
(2) by Pickering emulsion polymerizations in step (1), then through hot pressing, regeneration nano-cellulose/polystyrene is obtained
Composite material.
Regeneration nano-cellulose suspension is to dissolve regenerated nano-cellulose using phosphoric acid to suspend in the step (1)
Liquid.
Initiator is AIBN in the step (1)；The mass fraction of oil phase is 1%-50% in Pickering lotions.
Homogeneous rotating speed is 5000rpm-20000rpm, homogenizing time 1-30min in the step (1), and homogeneous environments are
Ice bath.
Polymerization temperature is 60 DEG C -90 DEG C in the step (2), polymerization time 3-10h.
Hot pressing temperature is 150 DEG C -250 DEG C, hot pressing pressure 10MPa-2000Mpa in the step (2), and hot pressing time is
2-5min。
The present invention is added styrene monomer as oil phase, prepares to regenerate nano-cellulose solid particle as stabilizer
Pickering lotions carry out emulsion polymerization by Pickering lotions, and hot pressing prepares regeneration nano-cellulose/polystyrene
Composite material.Composite material obtained can be widely applied to other high-tech such as transparent material, environmentally-friendly plastic, biological medicine material
Field.
Advantageous effect
(1) present invention prepares Pickering lotions using regeneration nano-cellulose, and stability of emulsion is high, may be implemented steady
Fixed styrene polymerization.
(2) regeneration nano-cellulose/poly styrene composite material prepared by the present invention, regeneration nano-cellulose is in polyphenyl second
Good dispersion in alkene has the good transparency, thermodynamic stability, biodegradability and biocompatibility, Ke Yiyong
In fields such as transparent material, environmentally-friendly plastic, biological medicine materials.
Description of the drawings
Fig. 1 is Pickering lotion figures prepared by embodiment 1；
Fig. 2 is Pickering lotion microscope figures prepared by embodiment 1；
Fig. 3 is the SEM figures of regeneration nano-cellulose/poly styrene composite material prepared by embodiment 1；
Fig. 4 is the transparency figure of regeneration nano-cellulose/poly styrene composite material prepared by embodiment 1；
Fig. 5 is the UV-vis test charts of regeneration nano-cellulose/poly styrene composite material prepared by embodiment 1；
Fig. 6 is the TG phenograms of regeneration nano-cellulose/poly styrene composite material prepared by embodiment 1；
Fig. 7 is the high temperature rheology phenogram of regeneration nano-cellulose/poly styrene composite material prepared by embodiment 1.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) it takes 7mL to regenerate nano-cellulose suspension (dissolving regenerated nano-cellulose suspension using phosphoric acid), is added
The styrene (mass fraction that AIBN accounts for styrene is 0.5%) that 3mL contains AIBN, regeneration nano-cellulose quality is respectively benzene
The 0.2% of Ethylene mass, 0.5%, 0.8%, 1.1%, 2%.Ice bath is with the rotating speed homogenous disperse of 10000rpm in homogenizer
10min is to get to stable styrene Pickering lotions.
(2) styrene Pickering lotions in step (1) are kept the temperature into 9h for 75 DEG C under nitrogen protection, prepares regenerated fiber
The polystyrene microsphere of element package, then at 180 DEG C, under the conditions of 500MPa, hot pressing 3min obtains regeneration nano-cellulose/poly-
Benzene composite material.
(3) regeneration nano-cellulose/poly styrene composite material in 5mg steps (2) is taken to carry out TG tests, temperature 60-600
DEG C, test result shows to regenerate nano-cellulose/poly styrene composite material incipient degradation temperature and most degradation (see Fig. 6)
Temperature increases, and thermodynamic property increases.
(4) regeneration nano-cellulose/poly styrene composite material of 1mm thickness is taken to be placed on the tablet of 50mm, heating 220
DEG C, control shape becomes 1%, shear velocity 0.1Hz-10Hz.Test result shows to regenerate nano-cellulose and gather (see Fig. 7)
Styrene recombination energy forms network structure, increases with the increase storage modulus of regenerated fiber content.
Fig. 2 shows：Difference regeneration nanofiber cellulose content can prepare the Pickering lotions of styrene monomer.
Fig. 3 shows：The difference regeneration polymerizable styrene monomer of nanofiber cellulose content, prepares polystyrene regenerated fiber
Plain composite material.
Fig. 4 shows：The polystyrene of difference regeneration nanofiber cellulose content has the good transparency, can be used for transparent
Material.
Fig. 5 shows：Regeneration nano-cellulose/poly styrene composite material can keep very high light transmittance, can be used for transparent
Material.
Embodiment 2
(1) it takes 7mL to regenerate nano-cellulose suspension (dissolving regenerated nano-cellulose suspension using phosphoric acid), is added
The styrene (mass fraction that AIBN accounts for styrene is 0.5%) that 3mL contains AIBN, the quality for regenerating nano-cellulose is benzene second
The 0.5% of alkene quality.In homogenizer ice bath with the rotating speed homogenous disperse 10min of 10000rpm to get to stable styrene
Pickering lotions.
(2) styrene Pickering lotions in step (1) are kept the temperature 3,5,7,9,11h for 75 DEG C respectively under nitrogen protection,
The polystyrene microsphere for preparing regenerated cellulose package, then at 180 DEG C, under the conditions of 500MPa, hot pressing 3min prepares regeneration and receives
Rice cellulose/poly styrene composite material.The yield of polystyrene, is shown in Table 1 under different polymerization times, the results showed that when polymerization
Between it is longer, the yield of polystyrene is higher.
Table 1
| Time (h) | Yield/% |
| 3 | 52 |
| 5 | 76 |
| 7 | 93.8 |
| 9 | 95.6 |
| 11 | 97.3 |
Embodiment 3
(1) it takes 7mL to regenerate nano-cellulose suspension (dissolving regenerated nano-cellulose suspension using phosphoric acid), is added
The different styrene of 3mL AIBN contents, the mass fraction that AIBN accounts for styrene are respectively 0.25%, 0.5%, 0.75%, 1%,
1.25%.Regenerate 0.5% that nano-cellulose quality is styrene quality.Ice bath is equal with the rotating speed of 10000rpm in homogenizer
Matter disperses 10min to get to stable styrene Pickering lotions.
(2) styrene Pickering lotions in step (1) are kept the temperature into 9h for 75 DEG C under nitrogen protection, prepares regenerated fiber
The polystyrene microsphere of element package, then at 180 DEG C, under the conditions of 500MPa, hot pressing 3min, preparation regeneration nano-cellulose/poly-
Benzene composite material.The yield of polystyrene, is shown in Table 2 when the initiator of different content is added, the results showed that, the initiation of addition
Agent content is more, and the yield of polystyrene is higher.
Table 2
| AIBN mass fractions/% | Yield/% |
| 0.25 | 68 |
| 0.5 | 87 |
| 0.75 | 90.4 |
| 1 | 93.8 |
| 1.25 | 95 |
Claims (6)
1. a kind of method preparing regeneration nano-cellulose/poly styrene composite material using Pickering lotions, specific steps
For：
(1) nano-cellulose suspension will be regenerated as water phase, styrene of the addition containing initiator is oil phase, and homogeneous obtains
Pickering lotions, wherein the mass fraction that regeneration nano-cellulose accounts for styrene is 0.2%-20%, and initiator accounts for benzene second
The mass fraction of alkene is 0.1%-5%；
(2) by Pickering emulsion polymerizations, hot pressing in step (1), regeneration nano-cellulose/poly styrene composite material is obtained.
2. described in accordance with the claim 1 a kind of compound using Pickering lotions preparation regeneration nano-cellulose/polystyrene
The method of material, which is characterized in that regeneration nano-cellulose suspension is to dissolve regenerated receive using phosphoric acid in the step (1)
Rice cellulose suspension.
3. described in accordance with the claim 1 a kind of compound using Pickering lotions preparation regeneration nano-cellulose/polystyrene
The method of material, which is characterized in that initiator is AIBN in the step (1)；The mass fraction of oil phase in Pickering lotions
For 1%-50%.
4. described in accordance with the claim 1 a kind of compound using Pickering lotions preparation regeneration nano-cellulose/polystyrene
The method of material, which is characterized in that homogeneous rotating speed is 5000rpm-20000rpm, homogenizing time 1- in the step (1)
30min, homogeneous environments are ice bath.
5. described in accordance with the claim 1 a kind of compound using Pickering lotions preparation regeneration nano-cellulose/polystyrene
The method of material, which is characterized in that polymerization temperature is 60 DEG C -90 DEG C in the step (2), polymerization time 3-11h.
6. described in accordance with the claim 1 a kind of compound using Pickering lotions preparation regeneration nano-cellulose/polystyrene
The method of material, which is characterized in that hot pressing temperature is 150 DEG C -250 DEG C in the step (2), hot pressing pressure 10MPa-
2000MPa, hot pressing time 2-5min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368838A (en) * | 2021-06-15 | 2021-09-10 | 青岛科技大学 | Biomass nano-cellulose porous material with surface loaded with nano-transition metal oxide and preparation method thereof |
| CN115678162A (en) * | 2022-11-01 | 2023-02-03 | 吉林大学 | Preparation method of cellulose nanofiber/polypropylene composite material |
-
2018
- 2018-04-13 CN CN201810332356.3A patent/CN108752769A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368838A (en) * | 2021-06-15 | 2021-09-10 | 青岛科技大学 | Biomass nano-cellulose porous material with surface loaded with nano-transition metal oxide and preparation method thereof |
| CN115678162A (en) * | 2022-11-01 | 2023-02-03 | 吉林大学 | Preparation method of cellulose nanofiber/polypropylene composite material |
| CN115678162B (en) * | 2022-11-01 | 2023-09-26 | 吉林大学 | Preparation method of cellulose nanofiber/polypropylene composite material |
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