CN110591308B - Poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and preparation method thereof - Google Patents

Poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and preparation method thereof Download PDF

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CN110591308B
CN110591308B CN201910793303.6A CN201910793303A CN110591308B CN 110591308 B CN110591308 B CN 110591308B CN 201910793303 A CN201910793303 A CN 201910793303A CN 110591308 B CN110591308 B CN 110591308B
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陈建香
唐创
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Jiangsu University of Technology
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    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
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    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

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Abstract

The invention relates to a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and a preparation method thereof, wherein the surface of CNC is respectively modified and grafted with hexadecanoyl chloride or caprolactone through acylation and esterification reaction on the surface of CNC, and the surface of the CNC is modified to make the surface of the modified CNC hydrophobic, thereby being beneficial to improving the compatibility of the CNC and PHBV and enhancing the interface bonding force between the modified CNC and the PHBV; meanwhile, the modified CNC has the effect of promoting the crystallization process of the PHBV, can improve the crystallization temperature of the PHBV, and can obviously improve the tensile property of the PHBV.

Description

Poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and a preparation method thereof.
Background
Poly (beta-hydroxybutyrate valerate), referred to as PHBV for short, PHBV not only has many mechanical properties similar to petroleum-based polymers, but also has good biodegradability, biocompatibility and optical activity. However, the thermal degradation temperature of PHBV is close to the melting point, so that its thermal stability is not good enough, which causes instability in the melt processing process. And the PHBV also has the defects of overlarge spherulite, high crystallinity, brittle quality and the like, and the defects have adverse effects on the forming and processing process of the PHBV product, so that the production cost is higher, the industrialization is difficult to realize, and the application of the PHBV is limited. In order to widen the application field of the PHBV, the PHBV is often blended with other bio-based degradable materials at present to optimize the processing performance of the PHBV.
Nanocrystalline Cellulose (CNC) is a highly crystalline nanomaterial extracted from cellulose microfibrils. Compared with other substances used for modifying PHBV, the CNC has the advantages of light weight, biodegradability, good biocompatibility, renewability and the like, and has important application value in the fields of reinforced composite materials, photoelectric materials, drug release and the like. Therefore, by blending the CNC and the PHBV, the performance of the PHBV can be improved, and the degradability of the blended material is ensured. Studies have shown that CNC can act as a heterogeneous nucleating agent to accelerate the crystallization process of PHBV. However, the interface compatibility between CNC and PHBV is poor, and the mechanical properties of the PHBV matrix cannot be improved basically by CNC.
Disclosure of Invention
In order to solve the technical problem of poor compatibility of PHBV and CNC, a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and a preparation method thereof are provided.
The invention is realized by the following technical scheme:
a preparation method of a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material comprises the following steps: placing the modified nano-crystalline cellulose and the poly (beta-hydroxybutyrate valerate) in a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and 60r/min of rotation speed to obtain the poly (beta-hydroxybutyrate valerate)/modified nano-crystalline cellulose composite material; the modified nanocrystalline cellulose is nanocrystalline cellulose with a surface modified and grafted with hexadecanoyl chloride or caprolactone.
Further, the modified nanocrystalline cellulose accounts for 0.5-2 wt% of the composite material; preferably, the modified nanocrystalline cellulose accounts for 0.5-1 wt% of the composite material; preferably, the modified nanocrystalline cellulose is nanocrystalline cellulose with a surface that has been modified and grafted with caprolactone.
Further, the preparation method of the surface modified and grafted hexadecanoyl chloride nano-crystalline cellulose comprises the following steps: dispersing the nanocrystalline cellulose in dimethyl sulfoxide, adding 1 wt% of sodium hydroxide aqueous solution, performing ultrasonic treatment, then performing magnetic stirring for 1h, dropwise adding hexadecanoyl chloride, performing magnetic stirring for 44 h at 60 ℃, after the reaction is finished, washing, dialyzing and freeze-drying the product, and finally obtaining the nanocrystalline cellulose with the surface modified and grafted hexadecanoyl chloride.
Furthermore, the mass volume ratio of the nanocrystalline cellulose to the dimethyl sulfoxide is 1g:100mL, the volume ratio of the dimethyl sulfoxide to the sodium hydroxide aqueous solution is 100:1, and the molar ratio of the nanocrystalline cellulose to the hexadecanoyl chloride is 1: 2.
Further, the preparation method of the nanocrystalline cellulose with the surface modified and grafted caprolactone comprises the following steps:
(1) under the protection of nitrogen, mechanically stirring N-methylimidazole and 1-allyl chloride under the heating condition of 45-60 ℃, condensing and refluxing, reacting for 10-15h, and removing unreacted raw materials and impurities to prepare 1-allyl-3-methylimidazole chloride ionic liquid;
(2) dispersing nanocrystalline cellulose in the ionic liquid, stirring at 70-90 ℃ to obtain a uniform transparent solution, adding acetic anhydride, continuously reacting for 2-4h at 70-90 ℃, transferring the reaction liquid to a polymerization tube of a Schlenk operating system to perform gas inflation and deflation for 1-3 times, then adding caprolactone and catalyst amount of dimethylaminopyridine, reacting for 5-7h in an oil bath at 70-90 ℃ in the polymerization tube under the protection of nitrogen under magnetic stirring, washing a product after the reaction is finished, and drying to constant weight to obtain the nanocrystalline cellulose with the modified surface and the grafted caprolactone.
Further, the volume ratio of the N-methylimidazole to the 1-allyl chloride in the step (1) is 10: (10-15).
Furthermore, the mass ratio of the nanocrystalline cellulose, the ionic liquid and the acetic anhydride in the step (2) is 1 (20-25) to (2.3-2.8); the molar ratio of the nanocrystalline cellulose to the caprolactone is 1: 3.
The invention also aims to provide the poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material prepared by the preparation method.
The beneficial technical effects are as follows: the CNC surface has a large amount of hydroxyl groups, the hydrophilicity is extremely strong, the hydroxyl groups on the CNC surface can provide a large amount of active reaction sites, the CNC surface hydroxyl groups are acylated and grafted with hexadecanoyl chloride, or the CNC surface hydroxyl groups are acetylated firstly and then esterified and grafted with caprolactone, the CNC surface is modified and grafted with hexadecanoyl chloride or caprolactone respectively, the CNC surface is modified, the modified CNC surface is hydrophobic, the compatibility of the CNC and the PHBV is improved, and the interface bonding force between the modified CNC and the PHBV is enhanced; meanwhile, the modified CNC has the effect of promoting the crystallization process of the PHBV, can improve the crystallization temperature of the PHBV, and can obviously improve the tensile property of the PHBV.
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FIG. 1 is a scanning electron micrograph of sample 1-CNC, sample 2-CNC-g-C16, and sample 3-CNC-g-CL in example 1, wherein the scale for sample 1 is 500nm, the scale for sample 2 is 200nm, and the scale for sample 2 is 200 nm.
FIG. 2 is an infrared spectrum of sample 1-CNC, sample 2-CNC-g-C16, sample 3-CNC-g-CL in example 1.
FIG. 3 is a DSC curve of the composite materials of examples 2-6 at a temperature increase/decrease rate of 7K/min.
FIG. 4 is a DSC curve of the materials of example 3, example 6, comparative example 1, comparative example 2 at a cooling rate of 7K/min.
Fig. 5 is a plot of the relative crystallinity of the materials of example 3, example 6, comparative example 1, comparative example 2.
Fig. 6 is a plot of the spherulitic growth rate for the materials of example 3, example 6, comparative example 1, comparative example 2.
Detailed Description
The invention is further described below with reference to the figures and specific examples, without limiting the scope of the invention.
Example 1
Sample 1: the CNC was vacuum dried for 6 hours and recorded as sample 1.
Sample 2: dispersing 1g of CNC (computerized numerical control) into 100mL of dimethyl sulfoxide, adding 1mL of sodium hydroxide aqueous solution with the concentration of 1 wt%, performing ultrasonic treatment, and performing magnetic stirring at room temperature for 1 hour; hexadecanoyl chloride (molar ratio of CNC to hexadecanoyl chloride is 1:2) was then added dropwise, magnetically stirred at 60 ℃ for 44 hours, the resulting product was centrifuged with water and acetone several times, dialyzed for 5-7 days, and freeze-dried to give CNC with surface modification and grafting of hexadecanoyl chloride, abbreviated as CNC-g-C16, which was designated as sample 2.
Sample 3: (1) adding 10.3g N-methylimidazole and 12.4g 1-allyl chloride into a dry three-neck flask under the protection of nitrogen, mechanically stirring, condensing and refluxing, wherein the reaction temperature is 55 ℃, the reaction time is 13 hours, and after the reaction is finished, removing unreacted chemical reagents and impurities through a separating funnel and a rotary evaporator to obtain 1-allyl-3-methylimidazole chloride ionic liquid, which is abbreviated as-AMIM Cl;
(2) dispersing 1.0g of CNC in 22.7g of ionic liquid [ AMIM ] Cl, stirring for 1h at 80 ℃ to obtain a uniform and transparent solution, then adding 2.52g of acetic anhydride, continuously reacting for 3h at 80 ℃, transferring the solution to a polymerization tube of a Schlenk operating system for three times of inflation and deflation after the reaction is finished, then adding 2.26g of caprolactone and catalytic amount of p-Dimethylaminopyridine (DMAP), reacting the polymerization tube in an oil bath at 80 ℃ under the protection of nitrogen and under magnetic stirring for 6h, adding a large amount of deionized water to stop the reaction after the ring-opening polymerization reaction is finished, washing for multiple times to remove the ionic liquid and unreacted raw materials, and finally drying to constant weight to obtain the CNC with modified surface and grafted caprolactone, which is abbreviated as CNC-g-CL and is marked as sample 3.
The samples 1, 2 and 3 were observed by a scanning electron microscope, and the surface topography of the particles is shown in FIG. 1. As can be seen from FIG. 1, the CNC is a rod-like structure, and the average lengths and diameters of CNC, CNC-g-C16 and CNC-g-CL are not much different, and are around 200nm and 30 nm; CNC-g-CL differs from CNC and CNC-g-C16 in that the surface has a distinct polymer structure, the phase structure of CNC surface grafted polycaprolactone.
The infrared spectrum test was performed on sample 1, sample 2, and sample 3, and the infrared spectrum is shown in fig. 2. As can be seen from FIG. 2, the IR spectrum of sample 2-CNC-g-C16 was 3334cm-1The position is an O-H stretching vibration absorption peak, which indicates that hydroxyl in the CNC is not completely replaced, and the length is 2920cm-1At a distance of 2848cm-1The position is a telescopic vibration absorption peak of C-H in methylene, which indicates that hexadecanoyl chloride is successfully grafted on the surface of CNC-g-C16; 3000-4000cm in infrared spectrum of sample 3-CNC-g-CL-1The absorption peak at (B) disappeared, indicating that the hydroxyl group on the CNC surface was almost completely replaced, 1745cm-1And (3) a C ═ O stretching vibration absorption peak, which indicates that caprolactone has been successfully grafted onto CNC.
Example 2
A preparation method of a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material comprises the following steps: 0.5 wt% sample 2: placing the CNC-g-C16 and the PHBV matrix material in a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and at a rotating speed of 60r/min to obtain the poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material, which is marked as PHBV/CNC-g-C16 composite material.
Example 3
A preparation method of a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material comprises the following steps: 1 wt% sample 2: placing the CNC-g-C16 and the PHBV matrix material in a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and at a rotating speed of 60r/min to obtain the poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material, which is marked as PHBV/CNC-g-C16 composite material.
Example 4
A preparation method of a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material comprises the following steps: 2 wt% sample 2: placing the CNC-g-C16 and the PHBV matrix material in a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and at a rotating speed of 60r/min to obtain the poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material, which is marked as PHBV/CNC-g-C16 composite material.
Example 5
A preparation method of a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material comprises the following steps: 0.5 wt% sample 3: placing the CNC-g-CL and PHBV matrix material in a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and at a rotating speed of 60r/min to obtain the poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material, which is marked as PHBV/CNC-g-CL composite material.
Example 6
A preparation method of a poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material comprises the following steps: 1 wt% sample 3: placing the CNC-g-CL and PHBV matrix material in a torque rheometer, and carrying out melt blending for 5min at 180 ℃ and at a rotating speed of 60r/min to obtain the poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material, which is marked as PHBV/CNC-g-CL composite material.
Comparative example 1
Pure PHBV material.
Comparative example 2
A preparation method of a poly (beta-hydroxybutyrate valerate)/nanocrystalline cellulose composite material comprises the following steps: 1 wt% sample 1: placing the CNC and the PHBV matrix material in a torque rheometer, and melting and blending the materials for 5min at 180 ℃ and 60r/min of rotation speed to obtain the poly (beta-hydroxybutyrate valerate)/nanocrystalline cellulose composite material which is marked as the PHBV/CNC composite material.
When the differential scanning calorimetry test is carried out on comparative example 1 and examples 2-6 at the temperature rising and falling rate of 7K/min, the DSC curve is shown in figure 3, and as can be seen from figure 3, the crystallization temperature of the composite material is increased along with the increase of the contents of CNC, CNC-g-C16 and CNC-g-CL, which indicates that the addition of CNC, CNC-g-C16 and CNC-g-CL plays a role in heterogeneous nucleation on the crystallization process of PHBV and promotes the crystallization process of PHBV.
When the differential scanning calorimetry test is carried out on example 3, example 6, comparative example 1 and comparative example 2 at the temperature reduction rate of 7K/min, the DSC curve is shown in figure 4, and the CNC, the CNC-g-C16 and the CNC-g-CL all promote the non-isothermal crystallization process of the PHBV according to the figure 4. Compared with pure PHBV, the PHBV/CNC, PHBV/CNC-g-C16 and PHBV/CNC-g-CL composite materials have higher crystallization temperature. The crystallization temperatures of the PHBV/CNC-g-C16 and the PHBV/CNC-g-CL are slightly lower than that of the PHBV/CNC, wherein the crystallization temperature of the PHBV/CNC-g-CL is the lowest. This indicates that CNC surface grafting of different functional groups has some effect on the crystallization process of PHBV. The chain structure of the CNC surface is damaged by surface modification, the flexible long carbon chain is arranged on the surface of the CNC-g-C16, and the polycaprolactone molecular chain is arranged on the surface of the CNC-g-CL, so that the CNC-g-C16, the CNC-g-CL and the PHBV molecular chain have better compatibility.
The materials prepared in example 3, example 6, comparative example 1 and comparative example 2 were tested by a differential scanning calorimeter, and the relative crystallinity was calculated from the DSC curve obtained by the test, the curve being shown in fig. 5; the spherulite growth rates of the materials of examples 3, 6, 1, and 2 were measured using a polarization microscope, and the curves are shown in fig. 6. As can be seen from FIGS. 5 and 6, the crystallization time of PHBV/CNC, PHBV/CNC-g-C16 and PHBV/CNC-g-CL was less than that of pure PHBV, and it can be seen that CNC, CNC-g-C16 and CNC-g-CL can accelerate the crystallization process of PHBV.
The materials of examples 2-6 and comparative examples 1-2 were tested for tensile properties, the data are shown in table 1, and the tensile properties were tested according to the current GB/T1040 standard.
TABLE 1 tensile Property data for the materials of examples 2-6 and comparative examples 1-2
Tensile Strength (MPa)
Example 2 36.24
Example 3 36.67
Example 4 34.98
Example 5 36.88
Example 6 38.35
Comparative example 1 27.75
Comparative example 2 36.21
As can be seen from the data in Table 1, the reinforcing effect of the CNC-g-CL on the PHBV material within the range of 0.5-1 wt% is greater than that of the CNC-g-C16, and the CNC-g-CL and the PHBV molecular chain have better interaction.

Claims (4)

1. A preparation method of poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material is characterized in that modified nanocrystalline cellulose and poly (beta-hydroxybutyrate valerate) are placed in a torque rheometer and are melted and blended for 5min at 180 ℃ and 60r/min of rotation speed, and then the poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material is prepared;
the modified nanocrystalline cellulose is nanocrystalline cellulose with a modified surface and grafted with hexadecanoyl chloride or caprolactone; the modified nanocrystalline cellulose accounts for 1 wt% of the composite material;
the preparation method of the surface modified and grafted hexadecanoyl chloride nanocrystalline cellulose comprises the following steps: dispersing nanocrystalline cellulose in dimethyl sulfoxide, adding 1 wt% of sodium hydroxide aqueous solution, performing ultrasonic treatment, then performing magnetic stirring for 1h, dropwise adding hexadecanoyl chloride, performing magnetic stirring for 44 h at 60 ℃, after the reaction is finished, washing, dialyzing and freeze-drying a product to obtain nanocrystalline cellulose with a modified surface and grafted hexadecanoyl chloride;
the preparation method of the nanocrystalline cellulose with the surface modified and grafted caprolactone comprises the following steps:
(1) under the protection of nitrogen, mechanically stirring N-methylimidazole and 1-allyl chloride under the heating condition of 45-60 ℃, condensing and refluxing, reacting for 10-15h, and removing unreacted raw materials and impurities to prepare 1-allyl-3-methylimidazole chloride ionic liquid;
(2) dispersing nanocrystalline cellulose in the ionic liquid, stirring at 70-90 ℃ to obtain a uniform transparent solution, adding acetic anhydride, continuously reacting for 2-4h at 70-90 ℃, transferring the reaction liquid to a polymerization tube of a Schlenk operating system to perform gas inflation and deflation for 1-3 times, then adding caprolactone and catalyst amount of dimethylaminopyridine, reacting for 5-7h in an oil bath at 70-90 ℃ in the polymerization tube under the protection of nitrogen under magnetic stirring, washing a product after the reaction is finished, and drying to constant weight to obtain the nanocrystalline cellulose with the modified surface and the grafted caprolactone.
2. The method for preparing poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite according to claim 1, wherein the mass-to-volume ratio of nanocrystalline cellulose to dimethyl sulfoxide is 1g:100mL, the volume ratio of dimethyl sulfoxide to an aqueous solution of sodium hydroxide is 100:1, and the molar ratio of nanocrystalline cellulose to hexadecanoyl chloride is 1: 2.
3. The method for preparing poly (beta-hydroxybutyrate valerate)/modified nanocellulose composite of claim 1, wherein the volume ratio of N-methylimidazole and 1-allyl chloride in step (1) is 10 (10-15).
4. The method for preparing poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite according to claim 1, wherein the mass ratio of the nanocrystalline cellulose, the ionic liquid and the acetic anhydride in step (2) is 1 (20-25) to (2.3-2.8); the molar ratio of the nanocrystalline cellulose to the caprolactone is 1: 3.
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