CN115636986B - Nanocellulose composite filler and preparation method and application thereof - Google Patents
Nanocellulose composite filler and preparation method and application thereof Download PDFInfo
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- CN115636986B CN115636986B CN202211406091.XA CN202211406091A CN115636986B CN 115636986 B CN115636986 B CN 115636986B CN 202211406091 A CN202211406091 A CN 202211406091A CN 115636986 B CN115636986 B CN 115636986B
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- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 59
- 239000000945 filler Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920002678 cellulose Polymers 0.000 claims abstract description 37
- 239000001913 cellulose Substances 0.000 claims abstract description 37
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 30
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- 239000002904 solvent Substances 0.000 claims abstract description 17
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- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 239000000725 suspension Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 91
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 87
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 50
- 239000004626 polylactic acid Substances 0.000 claims description 38
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 26
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- 238000006243 chemical reaction Methods 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
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- 239000011159 matrix material Substances 0.000 abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 125000005372 silanol group Chemical group 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 description 30
- 235000019441 ethanol Nutrition 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 239000007900 aqueous suspension Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 13
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- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
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- 229920013657 polymer matrix composite Polymers 0.000 description 2
- 239000011160 polymer matrix composite Substances 0.000 description 2
- -1 polytetramethylene Polymers 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910014571 C—O—Si Inorganic materials 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention belongs to the field of functional composite materials, and discloses a nano cellulose composite filler, a preparation method and application thereof. Comprises the following steps: performing grafting modification on the nano cellulose CNF by using a silane coupling agent R to obtain nano cellulose CNF-R with the surface grafted with the silane coupling agent; and then, respectively dispersing the CNF-R and the polyglycol in water to respectively obtain a CNF-R suspension and a polyglycol aqueous solution, mixing, evaporating the solvent and drying to obtain the nano-cellulose composite filler. According to the invention, the silanol groups of the silane coupling agent and the hydroxyl groups of the nanocellulose are dehydrated for polycondensation, so that the number of hydroxyl groups is reduced, the surface polarity of CNF is effectively regulated and controlled, the hydrophobicity and dispersibility of the CNF in a polymer are improved, and then the outer layer is coated with polypropylene glycol PPG with plasticizing and compatibilizing effects, so that CNF-PPG filler is uniformly dispersed in a polymer blending system, and meanwhile, the compatibility between two phases of a matrix is improved by means of the PPG of the outer layer.
Description
Technical Field
The invention belongs to the field of functional composite materials, and relates to a nano cellulose composite filler, a preparation method and application thereof.
Background
Polymer blending is a method of mixing two or more polymers of different structures under certain conditions, thereby achieving improved polymer properties. In practice, it is common to add certain specific reinforcing fillers to the blend system to produce polymer matrix composites. The composite material not only can reduce the cost, but also has certain special properties such as mechanical properties, thermal stability, acid and alkali resistance, oxidation resistance and the like. In polymer blend systems, interfacial compatibility is an important factor in determining the performance of the composite, including interfacial compatibility between different polymer systems and interfacial compatibility between the polymer and reinforcing filler.
Cellulose is mainly derived from plants and is a renewable material in nature. In recent years, with the continuous advocated development of recycling economy in China and society, researchers take cellulose, which is a low-cost, easily-prepared and degradable green resource, as an important point for research and development. Cellulose Nanofiber (CNF) is one of the products, and has the characteristics of high transparency, high crystallization, low density, good biodegradation, good compatibility and the like, so that the cellulose nanofiber is widely used as a nano filler in a blending system. However, CNF has a high polarity and a large specific surface area, and therefore is a hydrophilic filler, and the particles are often agglomerated due to hydrogen bond interactions, and cannot be uniformly dispersed in a polymer matrix.
The silane coupling agent is a chemical reagent for carrying out surface treatment on the filler, and has the main structure of R-SiX 3 R represents a group having affinity or reactivity with a polymer molecule, and is an organophilic polymer group; x represents a hydrolyzable alkoxy group and is an inorganically philic filler group. The polymer can be grafted on the surface of the filler through hydrolysis, so that the polarity of the surface of the filler is regulated, the hydrophobic property of the filler is enhanced, and the dispersibility of the filler in a polymer is improved. Zhu Yan [1-2] Et al ((1) Zhu Yan, zhang Jifeng, gu Shikui, zhao Zhongguo, chen Ligui, cao Le. Effect of surface modified CNF on humid heat aging behavior of PBS/PLA blends [ J)]Chinese plastic, 2019,33 (12) 16-22; (2) Zhu Yan, cao Le, gu Shikui, zhang Jifeng, zhao Zhongguo, chen Ligui. Influence of surface modified CNF on crystallization and mechanical Properties of PLA/TPU blends [ J]Plastics, 2021,50 (02): 23-28) after modifying CNF with KH550, the dispersibility and compatibility of the CNF-KH550 filler between the matrixes are enhanced, but the degree of phase separation between PLA and PBS and TPU polymers is still relatively obvious.
At present, most of researches on a blending system are focused on surface modification of a filler or modification of compatibility of a polymer matrix by simply adding a plasticizing and compatibilizer, but the method has the problems of uneven filler dispersion and poor compatibility among polymer matrixes. Therefore, a new method is needed to be found, and meanwhile, the filler has good dispersibility in the polymer matrix and can improve the compatibility between the matrixes, so that the polymer matrix composite material can be put into practical use.
Disclosure of Invention
The invention aims at providing a preparation method of a nano cellulose composite filler.
The invention also aims to provide the nanocellulose composite filler prepared by the method.
It is a further object of the present invention to provide the use of the nanocellulose composite filler described above.
According to the molecular design thought, the invention uses silanol groups after hydrolysis of a silane coupling agent to react with hydroxyl groups of Cellulose Nanofiber (CNF), improves the surface polarity of CNF, improves the dispersibility of CNF in a polymer matrix, and coats a layer of PPG with plasticizing and compatibilizing properties, thereby preparing CNF-PPG nanofiller capable of improving the compatibility of a polymer blending system, and relates to a modification method for combining grafting and adsorption on the surface of nanocellulose.
The invention aims at realizing the following technical scheme:
the preparation method of the nano cellulose composite filler comprises the following steps:
performing grafting modification on the nano cellulose CNF by using a silane coupling agent R to obtain nano cellulose CNF-R with the surface grafted with the silane coupling agent;
and then, respectively dispersing the CNF-R and the polyglycol in water to respectively obtain a CNF-R suspension and a polyglycol aqueous solution, and preparing the nano-cellulose composite filler by mixing, evaporating the solvent and drying.
Preferably, the silane coupling agent is one of gamma-aminopropyl trimethoxysilane KH540, 3-aminopropyl triethoxysilane KH550, 3-glycidoxypropyl trimethoxysilane KH560, 3-methacryloxypropyl trimethoxysilane KH570 and 3-mercaptopropyl triethoxysilane KH580.
Preferably, the polyglycol is one or more than two of polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
Preferably, the grafting modification step is specifically as follows:
dissolving a silane coupling agent in ethanol/water solution, heating to 70-75 ℃, stirring and hydrolyzing for 3-5 h to obtain a water-soluble amino hyperbranched polymer HBSiO-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the And adding the nanocellulose into an ethanol/water solution, performing ultrasonic dispersion, pouring the dispersed nanocellulose into the ethanol/water solution of the silane coupling agent, stirring for 24-48h, performing grafting reaction at 70-75 ℃, cooling to obtain a nanocellulose solution, and performing centrifugation, washing of a lower-layer product and drying to obtain the nanocellulose CNF-R of which the surface is grafted with the silane coupling agent.
Preferably, the mass ratio of the silane coupling agent to the nanocellulose is 1:2-2:1, and the mass ratio of the polyglycol to the nanocellulose is 1:1-5:1.
Preferably, the ethanol/water solution is a mixed solution with the volume ratio v/v of ethanol to water of 90%/10%.
Preferably, the mass volume g/mL ratio of the silane coupling agent to the ethanol/water solution is 1-5: 50.
the mass volume g/mL ratio of the nanocellulose to the ethanol/water solution is 1-2:20.
Preferably, the drying is vacuum drying at 70-80 ℃ for 12-24h, and the centrifugation is 8000-10000 rpm for 10-20min.
Preferably, the polyglycol is polypropylene glycol with molecular weight of 400-800, and the concentration of polyglycol water solution is 0.02-0.05 g/mL.
The nano cellulose composite filler is prepared by the method.
The application of the nano cellulose composite filler in the preparation of polymer materials.
The synthesis route and reaction process of CNF-R take gamma-aminopropyl trimethoxy silane (KH 540) as an example, as shown in figure 1, the preparation flow of CNF-PPG is shown in figure 2, and the preparation flow of PLA/PBAT/CNF-PPG composite film is shown in figure 3.
R is one of the following:
compared with the prior art, the invention has the following advantages:
(1) According to the invention, two modification modes of grafting and adsorption are combined successfully to modify Cellulose Nanofiber (CNF), a novel nanofiller CNF-PPG is prepared, after PPG coating, the aggregation degree of CNF is obviously reduced, the interfacial compatibility between PLA and PBAT is effectively improved, the adhesion between two interfaces is tighter, and the phase separation degree between two interfaces is greatly reduced.
(2) The modified CNF-PPG is added into a polylactic acid (PLA)/polybutylene adipate-terephthalate (PBAT) blend to prepare the composite film, the tensile strength of the film is improved by 12.1 percent compared with that of the PLA/PBAT film, and the elongation at break is improved from 18.21 percent to 39.97 percent.
(3) According to the invention, the CNF is grafted by the silane coupling agent KH540, and then the CNF is coated by PPG, and the silanol groups of the silane coupling agent and the hydroxyl groups of the nanocellulose are used for dehydration and polycondensation, so that the polarity of the CNF surface is effectively improved by reducing the number of the hydroxyl groups, the hydrophobicity and the dispersibility of the CNF are improved, the PPG is used as a compatibilizer, the compatibility between polymer matrixes can be improved, the phase separation degree is reduced, and a solution idea is provided for researching the problem of two-phase incompatibility and the problem of filler dispersibility in a blending system.
Drawings
FIG. 1 is a chemical reaction process of a silane coupling agent (KH 540) modified Cellulose Nanofiber (CNF);
FIG. 2 is a preparation flow of CNF-PPG;
FIG. 3 is a flow chart of the preparation of a PLA/PBAT/CNF-PPG composite film;
FIG. 4 is an infrared spectrogram of CNF and CNF-PPG;
FIG. 5 is an X-ray energy spectrum of CNF, CNF-PPG;
FIG. 6 is a scanning electron microscope picture of CNF, CNF-PPG, PLA/PBAT/CNF-PPG;
FIG. 7 is a graph showing stress-strain curves of CNF and CNF-PPG added to a PLA/PBAT blend;
FIG. 8 is a scanning electron microscope image of the composite film PLA/PBAT/CNF-PVA of comparative examples 1-3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
PLA: polylactic acid (model: 4032D), available from Dongguan Hei Jiu Plastic raw materials Co., ltd., guangdong;
PBAT: polybutylene adipate-terephthalate (model: C1200), available from Dongguan Hei Sinumber plastics Co., ltd;
CNF: nanocellulose, available from Gui Linji macrotech limited;
PPG: polypropylene glycol (mn=400), available from aladine biochemical technologies inc;
gamma-aminopropyl trimethoxysilane (KH 540), 3-aminopropyl triethoxysilane (KH 550), 3-glycidoxypropyl trimethoxysilane (KH 560), 3-methacryloxypropyl trimethoxysilane (KH 570), 3-mercaptopropyl triethoxysilane (KH 580), available from aladine biochemistry technologies, inc.
Example 1
A method for preparing a nanocellulose filler with improved compatibility of a polymer blend system, comprising the following steps:
(1) Graft modification of CNF by silane coupling agent: 1g of KH540 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker, and hydrolyzed for 3h. In addition, 1g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 24 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 20min at 8000rmp, pouring out the upper liquid, and taking out to obtain CNF-KH540. And (3) washing for multiple times by using absolute ethyl alcohol to remove unreacted silane coupling agent on the surface, and finally placing the plain nanofiber in a vacuum oven and drying at 70 ℃ for 24 hours to obtain 1.2g of CNF-KH540 nanofiller.
(2) Coating treatment of CNF-KH540 by polypropylene glycol: 1g of CNF-KH540 was dissolved in 20mL of deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 5g of polypropylene glycol was weighed and 100mL of deionized water was added to dissolve completely to obtain a polypropylene glycol solution. Adding the cellulose nanofiber aqueous suspension into polypropylene glycol solution, magnetically stirring for 2 hours to uniformly disperse CNF-KH540 in PPG, evaporating aqueous solvent under the water bath condition of 90 ℃, drying the majority of solvent in a vacuum drying oven of 70 ℃ after evaporating, and finally obtaining 2.4g of CNF-PPG composite filler.
Example 2
A method for preparing a nanocellulose filler with improved compatibility of a polymer blend system, comprising the following steps:
(1) Graft modification of CNF by silane coupling agent: 2g of KH550 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker, and hydrolyzed for 4h. In addition, 2g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 48 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 20min at 8000rmp, pouring out the upper liquid, and taking out to obtain the CNF-KH550. Washing with absolute ethyl alcohol for multiple times to remove unreacted KH550 on the surface, and finally placing the plain nanofiber in a vacuum oven and drying at 70 ℃ for 48 hours to obtain 1.1g of CNF-KH550 nanofiller.
(2) Coating treatment of CNF-KH550 by polypropylene glycol: 1g of CNF-KH550 was dissolved in 20mL of deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 4g of polypropylene glycol was weighed and 100mL of deionized water was added to dissolve completely to obtain a polypropylene glycol solution. Adding the cellulose nanofiber aqueous suspension into polypropylene glycol solution, magnetically stirring for 4 hours to uniformly disperse CNF-KH550 in PPG, evaporating aqueous solvent under the water bath condition of 90 ℃, drying the majority of solvent in a vacuum drying oven of 70 ℃ after evaporating, and finally obtaining 2.2g of CNF-PPG composite filler.
Example 3
A method for preparing a nanocellulose filler with improved compatibility of a polymer blend system, comprising the following steps:
(1) Graft modification of CNF by silane coupling agent: 1g of KH560 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker, and hydrolyzed for 5h. In addition, 2g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 48 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 20min at 8000rmp, pouring out the upper liquid, and taking out to obtain CNF-KH560. Washing with absolute ethyl alcohol for multiple times to remove unreacted KH560 on the surface, and finally placing the plain nanofiber in a vacuum oven and drying at 70 ℃ for 48 hours to obtain 1.2g of CNF-KH560 nanofiller.
(2) Coating treatment of CNF-KH560 by polypropylene glycol: 2g of CNF-KH560 was dissolved in 20mL of deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 5g of polypropylene glycol was weighed and 100mL of deionized water was added to dissolve completely to obtain a polypropylene glycol solution. Adding the cellulose nanofiber aqueous suspension into polypropylene glycol solution, magnetically stirring for 2 hours to uniformly disperse CNF-KH560 in PPG, evaporating aqueous solvent under the water bath condition of 90 ℃, drying the majority of solvent in a vacuum drying oven of 70 ℃ after evaporating, and finally obtaining 2.2g of CNF-PPG composite filler.
Example 4
A method for preparing a nanocellulose filler with improved compatibility of a polymer blend system, comprising the following steps:
(1) Graft modification of CNF by silane coupling agent: 2g of KH570 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker and hydrolyzed for 5h. In addition, 1g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 24 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 20min at 8000rmp, pouring out the upper liquid, and taking out to obtain CNF-KH570. Washing with absolute ethyl alcohol for multiple times to remove unreacted KH570 on the surface, and finally placing the plain nanofiber in a vacuum oven and drying at 70 ℃ for 24 hours to obtain 1.2g of CNF-KH570 nanofiller.
(2) Coating treatment of CNF-KH570 by polypropylene glycol: 1g of CNF-KH570 was dissolved in 20mL of deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 5g of polypropylene glycol was weighed and 100mL of deionized water was added to dissolve completely to obtain a polypropylene glycol solution. Adding the cellulose nanofiber aqueous suspension into polypropylene glycol solution, magnetically stirring for 2 hours to uniformly disperse CNF-KH570 in PPG, evaporating aqueous solvent under the water bath condition of 90 ℃, drying the majority of solvent in a vacuum drying oven of 70 ℃ after evaporating, and finally obtaining 2.5g of CNF-PPG composite filler.
Example 5
A method for preparing a nanocellulose filler with improved compatibility of a polymer blend system, comprising the following steps:
(1) Graft modification of CNF by silane coupling agent: 1g of KH580 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker, and hydrolyzed for 5h. In addition, 2g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 24 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 30min at 8000rmp, pouring out the upper liquid, and taking out to obtain the CNF-KH580. Washing with absolute ethyl alcohol for multiple times to remove unreacted KH580 on the surface, and finally placing the plain nanofiber in a vacuum oven and drying at 70 ℃ for 12 hours to obtain 1.1g of CNF-KH580 nanofiller.
(2) Coating treatment of CNF-KH580 by polypropylene glycol: 2g of CNF-KH580 was dissolved in 20mL of deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 4g of polypropylene glycol was weighed and 100mL of deionized water was added to dissolve completely to obtain a polypropylene glycol solution. Adding the cellulose nanofiber aqueous suspension into polypropylene glycol solution, magnetically stirring for 2 hours to uniformly disperse CNF-KH580 in PPG, evaporating aqueous solvent under the water bath condition of 90 ℃, drying the majority of solvent in a vacuum drying oven of 70 ℃ after evaporating, and finally obtaining 1.9g of CNF-PPG composite filler.
As shown in FIG. 4, the infrared spectra of CNF, CNF-KH540 and CNF-PPG are 1514cm -1 、1148cm -1 And 800cm -1 Three newly added peaks are shown, corresponding to the stretching vibration peaks of N-H, si-O-C and Si-O-Si respectively, wherein the amino group represented by N-H is a functional group special for KH540, the Si-O-Si bond is obtained by self-polymerization of a silane coupling agent during hydrolysis, and the Si-O-C bond is obtained by dehydration of hydroxyl groups on the CNF surface and hydroxyl groups in silanol during heating. The above newly added characteristic peaks indicate that the reaction proceeds smoothly and KH540 was successfully grafted to the CNF surface.
The X-ray spectra of CNF, CNF-KH540, CNF-PPG are shown in FIG. 5, from which it can be seen that characteristic signal peaks representing N and Si appear at 401.70eV and 102.28eV, which are elements unique to silane coupling agents. FIGS. 5 e-f are 2p orbital spectra of Si from which it is seen that two peaks occur at binding energies at 102.18eV and 102.68eV, representing Si-O-Si and-SiO 3 bonds, respectively. In addition, as can be seen from Table 1, the content of C-O and O-C-O bonds is reduced, which indicates that the hydroxyl groups on CNF react with silanol groups formed by hydrolysis of the silane coupling agent, and macromolecular structures formed by hydrolysis of the coupling agent are grafted on the CNF surface. Furthermore, the C-C bond content increased from 62.28% in CNF to 80.98% in CNF-PPG, indicating that CNF was successfully coated by PPG. This is because the main chain of PPG is- (CH) 2 ) 3 After the CNF surface is coated with PPG, the content of C-C bonds is increased.
TABLE 1 relative carbon group content in CNF, CNF-KH540, CNF-PPG obtained by XPS analysis
Example 6
The preparation method of the PLA/PBAT/CNF comprises the following steps:
2.7g of PLA and 0.3g of PBAT were added to 30mL of methylene chloride solution, and dissolved by continuous stirring at room temperature, followed by adding 0.3g of CNF nanofiller to the blend solution and stirring for 12 hours. Finally, pouring the prepared solution into a glass culture dish, and putting the glass culture dish into a constant temperature and humidity drying box with the temperature of 25 ℃ and the relative humidity of 50 percent to dry for 48 hours to obtain the PLA/PBAT/CNF (90/10/10) composite film.
Example 7
The preparation method of the PLA/PBAT/CNF-PPG comprises the following steps:
2.7g of PLA and 0.3g of PBAT were added to 30mL of methylene chloride solution, and dissolved by continuous stirring at room temperature, followed by adding 0.06g of CNF-PPG nanofiller of example 1 to the blend solution and stirring continuously for 12 hours. Finally, pouring the prepared solution into a glass culture dish, and putting the glass culture dish into a constant temperature and humidity drying box with the temperature of 25 ℃ and the relative humidity of 50 percent to dry for 48 hours to obtain the PLA/PBAT/CNF-PPG (90/10/2) composite film.
Example 8
The preparation method of the PLA/PBAT/CNF-PPG comprises the following steps:
2.7g of PLA and 0.3g of PBAT were added to 30mL of methylene chloride solution, and dissolved by continuous stirring at room temperature, followed by adding 0.15g of CNF-PPG nanofiller of example 1 to the blend solution and stirring for 12 hours. Finally, pouring the prepared solution into a glass culture dish, and putting the glass culture dish into a constant temperature and humidity drying box with the temperature of 25 ℃ and the relative humidity of 50 percent to dry for 48 hours to obtain the PLA/PBAT/CNF-PPG (90/10/5) composite film.
Example 9
The preparation method of the PLA/PBAT/CNF-PPG comprises the following steps:
2.7g of PLA and 0.3g of PBAT were added to 30mL of methylene chloride solution, and dissolved by continuous stirring at room temperature, followed by adding 0.3g of CNF-PPG nanofiller of example 1 to the blend solution and stirring for 12 hours. Finally, pouring the prepared solution into a glass culture dish, and putting the glass culture dish into a constant temperature and humidity drying box with the temperature of 25 ℃ and the relative humidity of 50 percent to dry for 48 hours to obtain the PLA/PBAT/CNF-PPG (90/10/10) composite film.
The microscopic morphologies of CNF, CNF-PPG, PLA/PBAT/CNF and PLA/PBAT/CNF-PPG are observed by a scanning electron microscope, the result is shown in figure 6, the surface of CNF before grafting is smoother, and after KH540 modification, the product formed by hydrolysis of the coupling agent is grafted on the surface of CNF. The modified CNF is coated by PPG, and the product grafted on the surface of CNF plays a role of a bridge, so that the CNF and the PPG are closely combined. The CNF without any treatment is obviously gathered in the PLA/PBAT matrix, the gathering degree of the CNF is obviously reduced after PPG coating, the compatibility of PLA and PBAT is obviously improved, and the phase separation degree between the PLA and the PBAT is greatly reduced, which is caused by the compatibilization effect of the PPG.
And (3) respectively adding the CNF before modification and the CNF-PPG after modification into a polylactic acid (PLA)/polybutylene adipate-terephthalate (PBAT) blend to prepare a composite film spline, wherein the mechanical properties of the film are measured by referring to national standard GB/T13022-91 tensile property test method of plastic film. As shown in FIG. 7, the tensile strength of the PLA/PBAT film added with CNF is improved by 8.23% compared with that of the film without CNF, but CNF is easy to aggregate in the PLA/PBAT matrix due to the action of self hydrogen bond and cannot be uniformly dispersed, and the elongation at break is reduced compared with that of the PLA/PBAT film without CNF. And the tensile strength of the PLA/PBAT film added with CNF-PPG is improved by 12.1 percent compared with that of the PLA/PBAT film. The elongation at break is improved from 18.21% to 39.97%, which is mainly beneficial to the fact that CNF-PPG is used as a filler, plays a role of capacity-increasing in the film, and PPG is used as a compatibilizer to effectively improve the interfacial compatibility between PLA and PBAT, so that the adhesion between two interfaces is tighter, the elongation at break of the film is greatly improved, CNF is used as a reinforcing material and uniformly dispersed in a PLA/PBAT matrix under the coating of PPG, and the tensile strength of the film is effectively improved.
Comparative example 1
The preparation process of nanometer composite cellulose stuffing includes the following steps;
(1) Graft modification of CNF by silane coupling agent: 1g of KH540 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker, and hydrolyzed for 5h. In addition, 2g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 24 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 30min at 8000rmp, pouring out the upper liquid, and taking out to obtain the CNF. Washing with absolute ethanol for multiple times to remove unreacted KH540 on the surface, and finally placing the plain nanofiber in a vacuum oven, and drying at 70 ℃ for 12 hours to obtain 1.2g of CNF-KH540.
(2) Coating treatment of polyvinyl alcohol on CNF-KH 540: 1g of CNF-KH540 was dissolved in deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 4g of polyvinyl alcohol is weighed, deionized water is added, and then the mixture is heated to 70 ℃ until the mixture is completely dissolved, so that a polyvinyl alcohol solution is obtained. Adding the cellulose nanofiber aqueous suspension into a polyvinyl alcohol solution, magnetically stirring for 2 hours to uniformly disperse CNF-KH540 in PVA, evaporating the solvent under the water bath condition of 90 ℃, and drying the solvent overnight in a vacuum drying oven of 70 ℃ after most of the solvent is evaporated to dryness to finally obtain the CNF-PVA composite filler.
(3) 2.7g of PLA and 0.3g of PBAT were added to 30mL of methylene chloride solution, and dissolved by continuous stirring at room temperature, followed by adding 0.3g of CNF-PVA nanofiller to the blend solution, and stirring for 12 hours. Finally, pouring the prepared solution into a glass culture dish, and putting the glass culture dish into a constant temperature and humidity drying box with the temperature of 25 ℃ and the relative humidity of 50 percent to dry for 48 hours to obtain the PLA/PBAT/CNF-PVA (90/10/10) composite film.
Comparative example 2
The preparation process of nanometer composite cellulose stuffing includes the following steps;
(1) Graft modification of CNF by silane coupling agent: 1g of KH540 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker, and hydrolyzed for 5h. In addition, 2g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 24 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 30min at 8000rmp, pouring out the upper liquid, and taking out to obtain the CNF. Washing with absolute ethanol for multiple times to remove unreacted KH540 on the surface, and finally placing the plain nanofiber in a vacuum oven, and drying at 70 ℃ for 12 hours to obtain 1.2g of CNF-KH540.
(2) Coating treatment of polyvinyl alcohol on CNF-KH 540: 1g of CNF-KH540 was dissolved in deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 4g of polyvinyl alcohol is weighed, deionized water is added, and then the mixture is heated to 70 ℃ until the mixture is completely dissolved, so that a polyvinyl alcohol solution is obtained. Adding the cellulose nanofiber aqueous suspension into a polyvinyl alcohol solution, magnetically stirring for 2 hours to uniformly disperse CNF-KH540 in PVA, evaporating the solvent under the water bath condition of 90 ℃, and drying the solvent overnight in a vacuum drying oven of 70 ℃ after most of the solvent is evaporated to dryness to finally obtain the CNF-PVA composite filler.
(3) 2.4g of PLA and 0.6g of PBAT were added to 30mL of methylene chloride solution, and dissolved by continuous stirring at room temperature, followed by adding 0.3g of CNF-PVA nanofiller to the blend solution, and stirring for 12 hours. Finally, pouring the prepared solution into a glass culture dish, and putting the glass culture dish into a constant temperature and humidity drying box with the temperature of 25 ℃ and the relative humidity of 50 percent to dry for 48 hours to obtain the PLA/PBAT/CNF-PVA (80/20/10) composite film.
Comparative example 3
The preparation process of nanometer composite cellulose stuffing includes the following steps;
(1) Graft modification of CNF by silane coupling agent: 1g of KH540 was dissolved in 50mL of ethanol/water (90%/10%) solution, warmed to 75deg.C, magnetically stirred in a beaker, and hydrolyzed for 5h. In addition, 2g of cellulose nanofibers were dispersed in 20mL of ethanol/water (90%/10%) solution, followed by ultrasonic dispersion, and then poured into the above solution, and the mixed solution was stirred at 75 ℃ for 24 hours, and then cooled to room temperature, to obtain a nanocellulose solution. And (3) putting the nanocellulose solution into a centrifuge, centrifuging for 30min at 8000rmp, pouring out the upper liquid, and taking out to obtain the CNF. Washing with absolute ethanol for multiple times to remove unreacted KH540 on the surface, and finally placing the plain nanofiber in a vacuum oven, and drying at 70 ℃ for 12 hours to obtain 1.2g of CNF-KH540.
(2) Coating treatment of polyvinyl alcohol on CNF-KH 540: 1g of CNF-KH540 was dissolved in deionized water and dispersed in an ultrasonic water bath for 30min to give an aqueous suspension of cellulose nanofibers. 4g of polyvinyl alcohol is weighed, deionized water is added, and then the mixture is heated to 70 ℃ until the mixture is completely dissolved, so that a polyvinyl alcohol solution is obtained. Adding the cellulose nanofiber aqueous suspension into a polyvinyl alcohol solution, magnetically stirring for 2 hours to uniformly disperse CNF-KH540 in PVA, evaporating the solvent under the water bath condition of 90 ℃, and drying the solvent overnight in a vacuum drying oven of 70 ℃ after most of the solvent is evaporated to dryness to finally obtain the CNF-PVA composite filler.
(3) 2.1g of PLA and 0.9g of PBAT were added to 30mL of methylene chloride solution, and dissolved by continuous stirring at room temperature, followed by adding 0.3g of CNF-PVA nanofiller to the blend solution, and stirring for 12 hours. Finally, pouring the prepared solution into a glass culture dish, and putting the glass culture dish into a constant temperature and humidity drying box with the temperature of 25 ℃ and the relative humidity of 50 percent to dry for 48 hours to obtain the PLA/PBAT/CNF-PVA (70/30/10) composite film.
The polymer selected in the comparative example was polyvinyl alcohol PVA, which is a hydrophilic polymer that is used in many applications for adhesives, liquid dispersants, and the like. When the CNF-PVA composite filler is added into a matrix, the filler is easy to aggregate due to poor compatibility with a hydrophobic polymer matrix, and the matrix is subjected to phase separation. As can be seen from fig. 8, after CNF-PVA is added, there is a significant void between PLA and PBAT interface in the matrix, which will have an impact on the performance of the PLA/PBAT/CNF-PVA composite film.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. A method for preparing a nanocellulose composite filler for polylactic acid/polybutylene adipate-terephthalate, which is characterized by comprising the following steps:
performing grafting modification on the nano cellulose CNF by using a silane coupling agent R to obtain nano cellulose CNF-R with the surface grafted with the silane coupling agent;
then, respectively dispersing CNF-R and polyglycol in water to respectively obtain a CNF-R suspension and polyglycol aqueous solution, mixing, evaporating solvent and drying to prepare the nano-cellulose composite filler;
the silane coupling agent isγ-aminopropyl trimethoxysilane;
the polyglycol is polypropylene glycol, the molecular weight is 400-800, and the concentration of the polyglycol aqueous solution is 0.02-0.05 g/mL;
the mass ratio of the silane coupling agent R to the nanocellulose is 1:2-2:1, and the mass ratio of the polyglycol to the nanocellulose is 1:1-5:1.
2. The method for preparing a nanocellulose composite filler for polylactic acid/polybutylene adipate-terephthalate as claimed in claim 1, wherein the grafting modification step specifically comprises the following steps:
dissolving a silane coupling agent in an ethanol/water solution, heating to 70-75 ℃, and stirring and hydrolyzing for 3-5 h; and adding the nanocellulose into an ethanol/water solution, performing ultrasonic dispersion, pouring the dispersed nanocellulose into the ethanol/water solution of the silane coupling agent, stirring for 24-48h, performing grafting reaction at 70-75 ℃, cooling to obtain a nanocellulose solution, and performing centrifugation, washing of a lower-layer product and drying to obtain the nanocellulose CNF-R of which the surface is grafted with the silane coupling agent.
3. The method for preparing the nanocellulose composite filler for polylactic acid/polybutylene adipate-terephthalate as claimed in claim 2, wherein the ethanol/water solution is a mixed solution with the volume ratio v/v of ethanol to water of 90%/10%.
4. The method for preparing the nanocellulose composite filler for polylactic acid/polybutylene adipate-terephthalate according to claim 2, wherein the drying is performed at 70-80 ℃ for 12-24 hours in vacuum, and the centrifugation is performed at 8000-10000 rpm for 10-20 minutes.
5. A nanocellulose composite filler for polylactic acid/polybutylene adipate-terephthalate, characterized in that it is prepared by the method of any one of claims 1-4.
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