CN107629323A - A kind of method that composite is prepared using freeze-drying - Google Patents
A kind of method that composite is prepared using freeze-drying Download PDFInfo
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- CN107629323A CN107629323A CN201711099124.XA CN201711099124A CN107629323A CN 107629323 A CN107629323 A CN 107629323A CN 201711099124 A CN201711099124 A CN 201711099124A CN 107629323 A CN107629323 A CN 107629323A
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Abstract
The invention discloses a kind of method that composite is prepared using freeze-drying, method is：Lignin or hydroxyethyl cellulose are configured to the aqueous solution, lignin aeroge or hydroxyethyl cellulose aeroge are obtained after freeze-dried, matrix resin is well mixed with the aeroge after obtained aeroge or carbonization, mixed and extruded with twin-screw, described composite is prepared, described matrix resin is polypropylene or polyethylene.After the present invention is dried lignin or hydroxyethyl cellulose using simple freeze-drying method, obtain the auxiliary agent raw material of loose laminated structure, it is mixed with matrix resin again to obtain polymer composite, this method effectively increases the mixed effect between lignin or hydroxyethyl cellulose and matrix resin, solubility property of the added material in matrix resin is improved, so as to improve the performance of the composite of preparation.
Description
Technical field
The invention belongs to field of composite material preparation, and in particular to a kind of side that composite is prepared using freeze-drying
Method.
Background technology
Lignin is a kind of rich reserves, reproducible valuable source, and preparing, degradable, reproducible macromolecule is compound
There is important development prospect in terms of material.But many non-polar high polymers such as polypropylene, polyethylene, due to lignin
Between compatibility it is very poor, in composite material is prepared, lignin is difficult to be well mixed with matrix material, thus can not be compared with
Good performance composite effect, the improvement to material property are limited.
Existing raising addition auxiliary agent method dispersed in matrix material has changes particle diameter by modes such as grindings, or changes
Become polarity of addition auxiliary agent etc., but these method effects are limited, it is inefficient, and method of modifying is complicated.Received using preparation
The method of rice material can also improve the compatibility of addition auxiliary agent and matrix material, but preparation method of nano material is complicated, cost
It is of a relatively high.Patent of invention such as Publication No. CN102604307A discloses a kind of polypropylene composite materials, the invention
Esterification occurs by using hydroxyl in esterifying agent containing double bond and lignin, and further by modified lignin resin and substituted olefine list
Body is grafted, and so as to reduce oh group in lignin, increases modified lignin and polyacrylic compatibility, although this method can
To improve dispersiveness of the lignin in polypropylene matrix, but modification method is numerous and diverse.
The content of the invention
For deficiencies of the prior art, freeze-drying is utilized to prepare it is an object of the invention to provide one kind compound
The method of material, solves the problems, such as the matrix resin poor compatibility such as lignin and polypropylene, polyethylene.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of method that composite is prepared using freeze-drying, method are：Lignin or hydroxyethyl cellulose are configured to water
Solution, lignin aeroge or hydroxyethyl cellulose aeroge are obtained after freeze-dried, by obtained aeroge and matrix tree
Fat is well mixed, and is mixed and extruded with twin-screw, that is, described composite is prepared, and described matrix resin is polypropylene or gathered
Ethene.
The aeroge of above-mentioned preparation can first be placed in tube furnace and be carbonized in argon gas atmosphere before being mixed with matrix resin,
It is well mixed again with matrix resin, is mixed and extruded with twin-screw, prepares the polymer composite of carbon material.
Preferably, the concentration of aqueous solution is 10 ~ 100mg/L.Concentration is smaller, is got over the mixed effect of matrix resin
It is good.But concentration is too small, the preparation cost of the aeroges such as lignin can be increased.
Preferably, the mass fraction of the aeroge is the 0.5 ~ 12% of aeroge and matrix resin gross mass.
Preferably, the lignin is alkali lignin.
Preferably, the carburizing temperature is 600 ~ 1000 DEG C, carbonization time is 1 ~ 2h.
The lignin aqueous solution of the present invention can freeze in liquid nitrogen, can also be freezed in refrigerator.It is fast using liquid nitrogen frozen speed,
The growth time of ice cube is short, and lignin is dispersed in smaller in ice cube, is advantageous to improve dried lignin aeroge
Intensity.
Compared with prior art, the present invention has the advantages that：
1st, after the present invention is dried lignin or hydroxyethyl cellulose using simple freeze-drying method, loose nanometer is obtained
The aeroge raw material of the laminated structure of level thickness, then it is mixed with matrix resin to obtain polymer composite, the party
Method effectively increases the mixed effect between lignin or hydroxyethyl cellulose and matrix resin, improves added material in matrix
Solubility property in resin, so as to improve the performance of the composite of preparation.
2nd, the present invention improves the physical pattern of additive material by Freeze Drying Technique, and by controlling freeze-drying
The concentration of solution, the thickness of aeroge is adjusted, and then regulate and control aeroge to be distributed in the composite, further improve composite wood
Expect to obtain physical property, the inventive method processing step is simple, it is efficient to prepare.
Brief description of the drawings
Fig. 1 is the shape appearance figure of PP composite material section section prepared by embodiment 9 and embodiment 11.
Scanning electron microscope (SEM) photograph after the lignin aqueous solution freeze-drying that Fig. 2 is 100mg/mL.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
The lignin used in the embodiment of the present invention is alkali lignin, and the method for preparing alkali lignin solution is routine side
Method.
Embodiment 1
Lignin raw material is mixed with polypropylene, wherein lignin and polyacrylic mass fraction are respectively 2% and 98%, with double spiral shells
Bar extruder is extruded at 185 DEG C, and institute's extruded material is prepared into corresponding dumbbell shape structure batten carries out sample test, stretching speed
When rate is 50 mm/min, its elongation at break reaches 35%, less than the 54% of virgin pp, Young's modulus 625MPa.
Embodiment 2
By lignin dissolution in water, prepare the lignin aqueous solution of 100 mg/L concentration, by lignin liquor in liquid nitrogen it is fast
After quickly cooling is frozen, and be freeze-dried, be prepared into lignin aeroge, then mixed with polypropylene, wherein lignin with it is polyacrylic
Mass fraction is respectively 2% and 98%, is extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into corresponding dumbbell
Type structure batten carries out sample test, and when rate of extension is 50 mm/min, its elongation at break reaches 58%, and Young's modulus is
637MPa。
Embodiment 3
By lignin dissolution in water, prepare the lignin aqueous solution of 50 mg/L concentration, by lignin liquor in liquid nitrogen it is quick
After freezing, and it is freeze-dried, is prepared into lignin aeroge, is then mixed with polypropylene, wherein lignin and polyacrylic matter
Amount fraction is respectively 2% and 98%, is extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into corresponding dumbbell shape
Structure batten carries out sample test, and when rate of extension is 50 mm/min, its elongation at break reaches 96%, and Young's modulus is
644MPa。
Embodiment 4
By lignin dissolution in water, prepare the lignin aqueous solution of 10 mg/L concentration, by lignin liquor in liquid nitrogen it is quick
After freezing, and it is freeze-dried, is prepared into lignin aeroge, is then mixed with polypropylene, wherein lignin and polyacrylic matter
Amount fraction is respectively 4% and 96%, is extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into corresponding dumbbell shape
Structure batten carries out sample test, and when rate of extension is 50 mm/min, its elongation at break reaches 120%, and Young's modulus is
658MPa。
Embodiment 5
By lignin dissolution in water, prepare the lignin aqueous solution of 50 mg/L concentration, by lignin liquor in liquid nitrogen it is quick
After freezing, and it is freeze-dried, is prepared into lignin aeroge, is then mixed with polypropylene, wherein lignin and polyacrylic matter
Amount fraction is respectively 5% and 95%, is extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into corresponding dumbbell shape
Structure batten carries out sample test, and when rate of extension is 50 mm/min, its elongation at break reaches 55%, and Young's modulus is
660MPa。
Embodiment 6
By lignin dissolution in water, prepare the lignin aqueous solution of 50 mg/L concentration, by lignin liquor in liquid nitrogen it is quick
After freezing, and it is freeze-dried, is prepared into lignin aeroge, is then mixed with polypropylene, wherein lignin and polyacrylic matter
Amount fraction is respectively 10% and 90%, is extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into corresponding dumbbell shape
Structure batten carries out sample test, and when rate of extension is 50 mm/min, its elongation at break reaches 50%, and Young's modulus is
720MPa。
Embodiment 7
Hydroxyethyl cellulose is dissolved in the water, prepare 50 mg/L concentration the aqueous solution, by solution in liquid nitrogen snap frozen
Afterwards, and it is freeze-dried, is prepared into aeroge, is then mixed with polypropylene, wherein hydroxyethyl cellulose and polyacrylic quality point
Number is respectively 2% and 98%, is extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into corresponding dumbbell shape structure
Batten carries out sample test, and when rate of extension is 50 mm/min, its elongation at break reaches 65%, Young's modulus 625MPa.
Embodiment 8
By lignin dissolution in water, prepare the lignin aqueous solution of 100 mg/L concentration, by lignin liquor in liquid nitrogen it is fast
After quickly cooling is frozen, and it is freeze-dried, is prepared into lignin aeroge.Lignin aeroge is placed in tube furnace, in argon gas atmosphere
And be heat-treated 1 hour under the conditions of 600 DEG C, the carbon aerogels of sheet are prepared after cooling, after then it is mixed with polypropylene, wherein
Both mass fractions are respectively 2% and 98%, are extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into accordingly
Dumbbell shape structure batten carry out sample test, when rate of extension is 50 mm/min, its Young's modulus is 660MPa, pure PP's
Young's modulus in tension is 610 MPa, elongation at break 57%.
Embodiment 9
By lignin dissolution in water, prepare the lignin aqueous solution of 100 mg/L concentration, by lignin liquor in liquid nitrogen it is fast
After quickly cooling is frozen, and it is freeze-dried, is prepared into lignin aeroge.Lignin aeroge is placed in tube furnace, in argon gas atmosphere
And be heat-treated 1 hour under the conditions of 900 DEG C, the carbon aerogels of sheet are prepared after cooling, after then it is mixed with polypropylene, wherein
Both mass fractions are respectively 2% and 98%, are extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into accordingly
Dumbbell shape structure batten carry out sample test, when rate of extension is 50 mm/min, its Young's modulus is 700MPa, pure PP's
Young's modulus in tension is 610 MPa, elongation at break 48%.
Embodiment 10
Hydroxyethyl cellulose is dissolved in the water, the hydroxyethyl cellulose solution of 100 mg/L concentration is prepared, by hydroxy ethyl fiber
Plain solution is freeze-dried in liquid nitrogen after snap frozen.Prepared aeroge is placed in tube furnace, in argon gas atmosphere and
Both it is heat-treated 1 hour under the conditions of 900 DEG C, the carbon aerogels of sheet is prepared after cooling, then mix it with polypropylene, wherein
Mass fraction be respectively 2% and 98%, with double screw extruder in 185 DEG C of extrusions, institute's extruded material is prepared into corresponding mute
Bell type structure batten carries out sample test, and when rate of extension is 50 mm/min, its Young's modulus is 640Mpa, elongation at break
For 56%.
Embodiment 11
Lignin raw material is placed in tube furnace, is heat-treated 1 hour under the conditions of argon gas atmosphere and 900 DEG C, piece is prepared after cooling
The carbon material of shape, then it is mixed with polypropylene, wherein both mass fractions are respectively 2% and 98%, use twin-screw extrusion
Machine is extruded at 185 DEG C, and institute's extruded material is prepared into corresponding dumbbell shape structure batten carries out sample test, rate of extension 50
During mm/min, its elongation at break reaches 40%, less than the 54% of virgin pp, Young's modulus 630MPa.
Embodiment 12
By lignin dissolution in water, prepare the lignin aqueous solution of 10 mg/L concentration, by lignin liquor in liquid nitrogen it is quick
After freezing, and it is freeze-dried, is prepared into lignin aeroge, is then mixed with polypropylene, wherein lignin and polyacrylic matter
Amount fraction is respectively 5% and 95%, is extruded with double screw extruder at 185 DEG C, institute's extruded material is prepared into corresponding dumbbell shape
Structure batten carries out sample test, and when rate of extension is 50 mm/min, its elongation at break reaches 88%, and Young's modulus is
660MPa。
Embodiment 13
Hydroxyethyl cellulose is dissolved in the water, the hydroxyethyl cellulose solution of 50 mg/L concentration is prepared, by hydroxyethyl cellulose
Solution is freeze-dried in liquid nitrogen after snap frozen, is prepared into aeroge, is then mixed it with polyethylene, wherein both
Mass fraction be respectively 4% and 96%, with double screw extruder in 185 DEG C of extrusions, institute's extruded material is prepared into corresponding mute
Bell type structure batten carries out sample test, and when rate of extension is 50 mm/min, its Young's modulus is 650Mpa, elongation at break
For 78%.
By above example as can be seen that fracture of composite materials elongation prepared by the present invention can reach 120%,
Apparently higher than the elongation at break of virgin pp（54%）.
Fig. 1 is the shape appearance figure of PP composite material section section prepared by embodiment 9 and embodiment 11, wherein in figure（1）、
（2）Embodiment 11, embodiment 9 are corresponded to respectively, as seen from the figure, are directly prepared by lignin carbon material after carbonization compound
The particle of uneven distribution is contained in material, its section of face, and by being freeze-dried the carbon material composite for being carbonized prepare again, its
Section face is uniform, and does not see the presence of particle, it can thus be seen that the inventive method effectively improves polypropylene and lignin
Mixed effect, the interaction of lignin and macromolecule matrix is promoted, further improve the mechanics and each side of composite
Performance.
Scanning electron microscope (SEM) photograph after the lignin aqueous solution freeze-drying that Fig. 2 is 100mg/mL, as can be seen from Figure, after freezing
Lignin is in the loose laminated structure of nanometer grade thickness, and this structure is advantageous to improve mixed between lignin and matrix resin
Close effect.
The above embodiment of the present invention is only example to illustrate the invention, and is not the implementation to the present invention
The restriction of mode.For those of ordinary skill in the field, other can also be made not on the basis of the above description
With the change and variation of form.Here all embodiments can not be exhaustive.It is every to belong to technical scheme
Row of the obvious changes or variations amplified out still in protection scope of the present invention.
Claims (6)
- A kind of 1. method that composite is prepared using freeze-drying, it is characterised in that match somebody with somebody lignin or hydroxyethyl cellulose The aqueous solution is made, lignin aeroge or hydroxyethyl cellulose aeroge are obtained after freeze-dried, by obtained aeroge with Matrix resin is well mixed, and is mixed and extruded with twin-screw, that is, described composite is prepared, and described matrix resin is poly- third Alkene or polyethylene.
- 2. the method according to claim 1 that composite is prepared using freeze-drying, it is characterised in that the aeroge Before being mixed with matrix resin, first aeroge is placed in tube furnace in argon gas atmosphere and is carbonized.
- 3. the method according to claim 1 or 2 that composite is prepared using freeze-drying, it is characterised in that the water Solution concentration is 10 ~ 100mg/L.
- 4. the method according to claim 1 or 2 that composite is prepared using freeze-drying, it is characterised in that the gas The mass fraction of gel is the 0.5 ~ 12% of aeroge and matrix resin gross mass.
- 5. the method according to claim 1 or 2 that composite is prepared using freeze-drying, it is characterised in that the wood Quality is alkali lignin.
- 6. the method according to claim 2 that composite is prepared using freeze-drying, it is characterised in that the carbonization temperature Spend for 600 ~ 1000 DEG C, carbonization time is 1 ~ 2h.
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| CN201711099124.XA CN107629323A (en) | 2017-11-09 | 2017-11-09 | A kind of method that composite is prepared using freeze-drying |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229307A (en) * | 2019-06-28 | 2019-09-13 | 陕西科技大学 | A kind of poly- polyisocyanates shape memory aeroge of HEC/CNC/ and its preparation method and application |
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| US20070208124A1 (en) * | 2006-03-02 | 2007-09-06 | Case Western Reserve University | Clay aerogel-based polymer composites, materials and methods |
| CN103396597A (en) * | 2013-08-19 | 2013-11-20 | 南京林业大学 | Cellulose nano-fiber reinforced charcoal powder/ultra-high molecule weight polyethylene preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229307A (en) * | 2019-06-28 | 2019-09-13 | 陕西科技大学 | A kind of poly- polyisocyanates shape memory aeroge of HEC/CNC/ and its preparation method and application |
| CN110229307B (en) * | 2019-06-28 | 2021-02-26 | 陕西科技大学 | HEC/CNC/polyisocyanate shape memory aerogel and preparation method and application thereof |
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