CN105754308A - Acetylated cellulose nanocrystalline composite modified biomass-based polyester material and preparation method thereof - Google Patents
Acetylated cellulose nanocrystalline composite modified biomass-based polyester material and preparation method thereof Download PDFInfo
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- CN105754308A CN105754308A CN201610159964.XA CN201610159964A CN105754308A CN 105754308 A CN105754308 A CN 105754308A CN 201610159964 A CN201610159964 A CN 201610159964A CN 105754308 A CN105754308 A CN 105754308A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
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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
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- C08L2201/06—Biodegradable
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The invention belongs to the field of natural high polymer materials and particularly relates to an acetylated cellulose nanocrystalline composite modified biomass-based polyester material and a preparation method thereof. The acetylated cellulose nanocrystalline composite modified biomass-based polyester material is prepared from acetylated cellulose nanocrystalline and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) in the weight ratio being (3-30):100 through compositing. The preparation method comprises steps as follows: poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and an acetylated cellulose nanocrystalline solution are mixed and put into a polytetrafluoroethylene mold for film casting, a solvent is evaporated at the room temperature, and the acetylated cellulose nanocrystalline composite modified biomass-based polyester material is obtained after vacuum drying. The tensile strength and the Young modulus of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) are remarkably improved after composite modification by acetylated cellulose nanocrystalline, the strength and the rigidity of the material are improved, and the application range of the material is effectively broadened.
Description
Technical field
The invention belongs to natural macromolecular material field, be specifically related to a kind of acetylation of cellulose nanocomposite modified biomass base
Polyester material and preparation method thereof.
Background technology
Cellulose is the natural polysaccharide macromolecule that nature is widely present, and is the structural polymerization being prevalent in various plant
Thing.For the structure of cellulose, mainly it is made up of crystallization and amorphous regions.Amorphous regions is sensitive to hydrolysising condition,
Can be completely removed under certain condition, remaining more complete rigid crystalline region becomes Cellulose nanocrystal.With inorganic nano
Particle is compared, and Cellulose nanocrystal has many merits, as being easy to get, low cost, nano effect, high-specific surface area and modulus,
The most disposable, biodegradable, bio-compatible and active surface groupings etc..Particularly Cellulose nanocrystal has the most raw
Thing compatibility, multiple biologically active, adsorption function and biodegradability etc., can be used for packaging material for food, medical dressing,
Additive for paper making, water process the functional materials such as exchange of particles resin, slow releasing carrier of medication.Therefore, Cellulose nanocrystal is numerous
Advantage gives it and is widely applied prospect at material science.On the other hand, in order to adapt to different substrates material system, for
The surface of Cellulose nanocrystal is modified and has been carried out for many years with the nanocrystalline intrinsic surface Quality Research of transformation.Acetylation of cellulose is received
The product that meter Jing is Cellulose nanocrystal to be obtained after esterification with acetic anhydride, have equally high-crystallinity, high-modulus, can be again
Raw, biodegradable, advantages of environment protection, can serve as nanometer reinforcer to improve the performance of polymeric material and by extensively
General concern.But, the degree of acetylation controlling Cellulose nanocrystal and the research utilizing its modified biomass base polyester material are the freshest
Relate to.
Biodegradable material refers to pass through light degradation, chemical degradation, the various ways such as biodegradable, and material degradation is paired
Environmentally friendly lower-molecular substance, has the material of good Practical Performance.Biodegradable material includes natural material and synthesis material
Material, natural material includes starch, cellulose, chitin and their derivative, and synthetic material usually contains hydrolyzable official's energy
Group (such as: ester bond, urea bond, amido link, ehter bond etc.), as poly butyric ester, PLA, poly butylene succinate,
Polycaprolactone etc..Poly butyric ester is a kind of biodegradable polyester synthesis material, industrial main by bacterium (such as:
Alcaligenes eutrophus, azotobacter vinelandii, methylotrophic bacteria etc.) synthesize, but the fragility of existing poly butyric ester is relatively big,
Which greatly limits the poly butyric ester range of application at Material Field.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is therefore intended that provide a kind of acetylation of cellulose nanocomposite modified biomass base
Polyester material and preparation method thereof.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, it is characterised in that received by acetylation of cellulose
Meter Jing and biomass-based polyester material are combined and are prepared from, and described biomass-based polyester material is poly-(3-hydroxybutyrate ester-co-4-
Butyric ester), the weight part ratio of described acetylation of cellulose nanocrystalline and poly-(3-hydroxybutyrate ester-co-4-butyric ester)
It is 3～30:100.
By such scheme, the nanocrystalline product obtained through esterification with acetic anhydride for Cellulose nanocrystal of described acetylation of cellulose
Thing, its structure is club shaped structure, and draw ratio is about 9～10, and crystallinity index is more than 80%, and surface degree of acetylation is up to
62.5%～63.5%.
By such scheme, the nanocrystalline preparation method of described acetylation of cellulose comprises the steps: that (1) is by Cellulose nanocrystal
Powder is scattered in solvent, ultrasonically treated after obtain Cellulose nanocrystal suspension；(2) acetic anhydride is scattered in solvent, so
After be added drop-wise in Cellulose nanocrystal suspension occur esterification, after reaction terminates, be down to greenhouse, product is scrubbed,
Acetylation of cellulose is obtained nanocrystalline after freeze-drying.
By such scheme, acetic anhydride: the mol ratio of the surface hydroxyl of Cellulose nanocrystal is 40～80:1, described surface hydroxyl
Amount is to have 1.20mmol in every gram of Cellulose nanocrystal.
By such scheme, the condition of described esterification is: nitrogen is protected, and reaction temperature is 80 DEG C, and the reaction time is 8 hours.
By such scheme, described solvent is anhydrous pyridine.
The preparation method of above-mentioned acetylation of cellulose nanocomposite modified biomass base polyester material, it is characterised in that include as
Lower step: (1) weighs that acetylation of cellulose is nanocrystalline to be dissolved in solvent, ultrasonically treated after be added thereto to poly-(3-hydroxybutyrate
Ester-co-4-butyric ester), obtain suspension after mixing；(2) suspension mixed is poured into polytetrafluoroethylene (PTFE) mould
In tool, treat that solvent evaporates final vacuum completely and is dried removing solvent and moisture further, obtain acetylation of cellulose nanocomposite and change
The biomass-based polyester material of property.
By such scheme, the described ultrasonically treated condition of step (1) is: under room temperature, ultrasonic time is 10 minutes/time, ultrasonic
Number of times 3 times.
By such scheme, the process conditions of step (1) described mixing are: under room temperature, and continuing magnetic force stirs, and rotating speed is 600rpm.
By such scheme, the described vacuum drying technique of step (2) is: be vacuum dried 24 hours under the conditions of 60 DEG C.
In the present invention, the nanocrystalline composite modified process to poly-(3-hydroxybutyrate ester-co-4-butyric ester) of acetylation of cellulose
In, introduce acetyl group owing to acetylation of cellulose is nanocrystalline and have and poly-(3-hydroxybutyrate ester-co-4-butyric ester) point
The hydrophobic group (ester group and alkyl) that son is identical, so that the hydrophobicity on its surface and poly-(3-hydroxybutyrate ester-co-4-hydroxyl
Base butyrate) hydrophobicity of matrix is close, it is ensured that and both compatibility also advantageously forms interaction sites, and with
Acetylation modification degree to increase, the interaction sites of formation is the most.On the other hand, the acetylation of Cellulose nanocrystal
The reaction condition of middle gentleness makes Cellulose nanocrystal as the rigid crystalline structure of the substantive characteristics of reinforcer and Rod-like shape
It is maintained.Being based on above 2 points, acetylation of cellulose is nanocrystalline to poly-(3-hydroxybutyrate ester-co-4-butyric ester)
After composite modified, the significantly enhancing that the mechanical property of nano composite material just obtains.
Beneficial effects of the present invention is as follows: (1) present invention uses the acetylation of cellulose that acetylation modification degree is higher nanocrystalline
Poly-(3-hydroxybutyrate ester-co-4-butyric ester) is carried out composite modified, modified poly-(3-hydroxybutyrate ester-co-4-hydroxyl
Base butyrate) material, its hot strength, Young's modulus improved significantly, and the intensity of material increases, rigidity increases,
Toughness reduces, and has effectively expanded the range of application of material, described acetylation of cellulose nanocomposite modified biomass base polyester
Material can be processed as film, sheet material, section bar or container etc. with straight forming, it is also possible to as packaging material, bio-medical material
Or engineering plastics etc.；(2) present invention has prepared higher second by the esterification controlling acetic anhydride and Cellulose nanocrystal
The acetylation of cellulose of acylated substitution value is nanocrystalline, nanocrystalline further with this acetylation of cellulose, passes through casting molding processes
Prepare poly-(3-hydroxybutyrate ester-co-4-butyric ester) that acetylation of cellulose nanocomposite is modified, whole preparation side
Method has that technique is simple, with low cost, environmental friendliness, quickness and high efficiency and the advantage of highly compatible.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but present disclosure is not
It is limited only to the following examples.
In following example, the nanocrystalline preparation method of described acetylation of cellulose comprises the steps: that (1) is by cellulose nanometer
Crystalline flour end is scattered in anhydrous pyridine, ultrasonically treated after obtain Cellulose nanocrystal suspension；(2) acetic anhydride is scattered in anhydrous
In pyridine, being then added drop-wise in Cellulose nanocrystal suspension occur esterification, after reaction terminates, be down to room temperature, reaction is produced
Thing is scrubbed, it is nanocrystalline to obtain acetylation of cellulose after freeze-drying.
Wherein, described acetic anhydride is 40:1 with the molar ratio of the surface hydroxyl of Cellulose nanocrystal；The bar of described esterification
Part is: nitrogen is protected, and reaction temperature is 80 DEG C, and the reaction time is 5 hours；The acetylation of cellulose prepared is nanocrystalline
Acetylation modification degree be 62.9%.
Described acetic anhydride is 80:1 with the molar ratio of the surface hydroxyl of Cellulose nanocrystal；The condition of described esterification is:
Nitrogen is protected, and reaction temperature is 80 DEG C, and the reaction time is 5 hours；The acetyl that the acetylation of cellulose for preparing is nanocrystalline
Changing substitution value is 63.2%.
Embodiment 1
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, is prepared via a method which to obtain:
(1) by acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%) 3 parts, poly-(3-hydroxyl
Butyrate-co-4-butyric ester) 100 parts, choose acetylation of cellulose (3-hydroxybutyrate ester-co-4-hydroxyl nanocrystalline, poly-
Butyrate), be scattered in nanocrystalline for acetylation of cellulose in chloroform, sonicated after (ultrasonic number of times 3 times, ultrasonic
Time 10min/ time) obtain acetylation of cellulose nanocrystal suspension；
(2) poly-(3-hydroxybutyrate ester-co-4-butyric ester) is joined in acetylation of cellulose nanocrystal suspension, hold
Continuous magnetic agitation, the blend being uniformly mixed after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved；
(3) blend mixed is poured in Teflon mould, keep 24 hours under room temperature, treat that solvent is complete
It is vacuum dried under the conditions of 60 DEG C after evaporation 24 hours and removes solvent and moisture further, obtain acetylation of cellulose nanocomposite
Modified biomass base polyester material.
The acetyl on the CMT6503 instrument of tester company prepared by the present embodiment is newly thought carefully in Shenzhen according to GB4456-84
Cellulose nanocomposite modified biomass base polyester material carries out Mechanics Performance Testing, and rate of extension is 5mm/min, test
Result shows: after deacetylation Cellulose nanocrystal is composite modified, and biomass-based polyester material is in hot strength, Young's modulus
The performance of aspect is significantly improved, and concrete numerical value is shown in Table 1.
Embodiment 2
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, is prepared via a method which to obtain:
(1) by acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%) 6 parts, poly-(3-hydroxyl
Butyrate-co-4-butyric ester) 100 parts, choose acetylation of cellulose (3-hydroxybutyrate ester-co-4-hydroxyl nanocrystalline, poly-
Butyrate), be scattered in nanocrystalline for acetylation of cellulose in chloroform, sonicated after (ultrasonic number of times 3 times, ultrasonic
Time 10min/ time) obtain acetylation of cellulose nanocrystal suspension；
(2) poly-(3-hydroxybutyrate ester-co-4-butyric ester) is joined in acetylation of cellulose nanocrystal suspension, hold
Continuous magnetic agitation, the blend being uniformly mixed after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved；
(3) blend mixed is poured in Teflon mould, keep 24 hours under room temperature, treat that solvent steams completely
It is vacuum dried under the conditions of 60 DEG C after Faing 24 hours and removes solvent and moisture further, obtain acetylation of cellulose nanocomposite and change
The biomass-based polyester material of property.
The acetylation on the CMT6503 instrument of tester company prepared by the present embodiment is newly thought carefully in Shenzhen according to GB4456-84
Cellulose nanocrystal compound modified biomass base polyester material carries out Mechanics Performance Testing, and rate of extension is 5mm/min, test knot
Fruit display: modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in terms of hot strength, Young's modulus
Performance be significantly improved, concrete numerical value is shown in Table 1.
Embodiment 3
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, is prepared via a method which to obtain:
(1) by acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%) 9 parts, poly-(3-hydroxyl
Butyrate-co-4-butyric ester) 100 parts, choose acetylation of cellulose (3-hydroxybutyrate ester-co-4-hydroxyl nanocrystalline, poly-
Butyrate), be scattered in nanocrystalline for acetylation of cellulose in chloroform, sonicated after (ultrasonic number of times 3 times, ultrasonic
Time 10min/ time) obtain acetylation of cellulose nanocrystal suspension；
(2) poly-(3-hydroxybutyrate ester-co-4-butyric ester) is joined in acetylation of cellulose nanocrystal suspension, hold
Continuous magnetic agitation, the blend being uniformly mixed after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved；
(3) blend mixed is poured in Teflon mould, keep 24 hours under room temperature, treat that solvent is complete
It is vacuum dried under the conditions of 60 DEG C after evaporation 24 hours and removes solvent and moisture further, obtain acetylation of cellulose nanocomposite
Modified biomass base polyester material.
The acetyl on the CMT6503 instrument of tester company prepared by the present embodiment is newly thought carefully in Shenzhen according to GB4456-84
Cellulose nanocomposite modified biomass base polyester material carries out Mechanics Performance Testing, and rate of extension is 5mm/min, test
Result shows: modified through acetylation of cellulose nanocomposite, and biomass-based polyester material is in hot strength, Young's modulus side
The performance in face is significantly improved, and concrete numerical value is shown in Table 1.
Embodiment 4
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, is prepared via a method which to obtain:
(1) by acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%) 15 parts, poly-(3-hydroxyl
Base butyrate-co-4-butyric ester) 100 parts, choose acetylation of cellulose (3-hydroxybutyrate ester-co-4-hydroxyl nanocrystalline, poly-
Base butyrate), it is scattered in nanocrystalline for acetylation of cellulose in chloroform, it is sonicated that (ultrasonic number of times 3 times surpasses afterwards
Sound time 10min/ time) obtain acetylation of cellulose nanocrystal suspension；
(2) poly-(3-hydroxybutyrate ester-co-4-butyric ester) is joined in acetylation of cellulose nanocrystal suspension, hold
Continuous magnetic agitation, the blend being uniformly mixed after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved；
(3) blend mixed is poured in Teflon mould, keep 24 hours under room temperature, treat that solvent is complete
It is vacuum dried under the conditions of 60 DEG C after evaporation 24 hours and removes solvent and moisture further, obtain acetylation of cellulose nanocomposite
Modified biomass base polyester material.
The acetyl on the CMT6503 instrument of tester company prepared by the present embodiment is newly thought carefully in Shenzhen according to GB4456-84
Cellulose nanocomposite modified biomass base polyester material carries out Mechanics Performance Testing, and rate of extension is 5mm/min, test
Result shows: modified through acetylation of cellulose nanocomposite, and biomass-based polyester material is in hot strength, Young's modulus side
The performance in face is significantly improved, and concrete numerical value is shown in Table 1.
Embodiment 5
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, is prepared via a method which to obtain:
(1) by acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%) 20 parts, poly-(3-hydroxyl
Base butyrate-co-4-butyric ester) 100 parts, choose acetylation of cellulose (3-hydroxybutyrate ester-co-4-hydroxyl nanocrystalline, poly-
Base butyrate), it is scattered in nanocrystalline for acetylation of cellulose in chloroform, sonicated (ultrasonic number of times 3 times, ultrasonic
Time 10min/ time) after obtain acetylation of cellulose nanocrystal suspension；
(2) poly-(3-hydroxybutyrate ester-co-4-butyric ester) is joined in acetylation of cellulose nanocrystal suspension, hold
Continuous magnetic agitation, the blend being uniformly mixed after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved；
(3) blend mixed is poured in Teflon mould, keep 24 hours under room temperature, treat that solvent is complete
It is vacuum dried under the conditions of 60 DEG C after evaporation 24 hours and removes solvent and moisture further, obtain acetylation of cellulose nanocomposite
Modified biomass base polyester material.
The acetylation on the CMT6503 instrument of tester company prepared by the present embodiment is newly thought carefully in Shenzhen according to GB4456-84
Cellulose nanocrystal compound modified biomass base polyester material carries out Mechanics Performance Testing, and rate of extension is 5mm/min, test knot
Fruit display: modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in terms of hot strength, Young's modulus
Performance be significantly improved, concrete numerical value is shown in Table 1.
Embodiment 6
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, is prepared via a method which to obtain:
(1) by acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%) 25 parts, poly-(3-hydroxyl
Base butyrate-co-4-butyric ester) 100 parts, choose acetylation of cellulose (3-hydroxybutyrate ester-co-4-hydroxyl nanocrystalline, poly-
Base butyrate), it is scattered in nanocrystalline for acetylation of cellulose in chloroform, sonicated (ultrasonic number of times 3 times, ultrasonic
Time 10min/ time) after obtain acetylation of cellulose nanocrystal suspension；
(2) poly-(3-hydroxybutyrate ester-co-4-butyric ester) is joined in acetylation of cellulose nanocrystal suspension, hold
Continuous magnetic agitation, the blend being uniformly mixed after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved；
(3) blend mixed is poured in Teflon mould, keep 24 hours under room temperature, treat that solvent is complete
It is vacuum dried under the conditions of 60 DEG C after evaporation 24 hours and removes solvent and moisture further, obtain acetylation of cellulose nanocomposite
Modified biomass base polyester material.
The acetylation on the CMT6503 instrument of tester company prepared by the present embodiment is newly thought carefully in Shenzhen according to GB4456-84
Cellulose nanocrystal compound modified biomass base polyester material carries out Mechanics Performance Testing, and rate of extension is 5mm/min, test knot
Fruit display: modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in terms of hot strength, Young's modulus
Performance be significantly improved, concrete numerical value is shown in Table 1.
Embodiment 7
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material, is prepared via a method which to obtain:
(1) by acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%) 30 parts, poly-(3-hydroxyl
Base butyrate-co-4-butyric ester) 100 parts, choose acetylation of cellulose (3-hydroxybutyrate ester-co-4-hydroxyl nanocrystalline, poly-
Base butyrate), it is scattered in nanocrystalline for acetylation of cellulose in chloroform, sonicated (ultrasonic number of times 3 times, ultrasonic
Time 10min/ time) after obtain acetylation of cellulose nanocrystal suspension；
(2) poly-(3-hydroxybutyrate ester-co-4-butyric ester) is joined in acetylation of cellulose nanocrystal suspension, hold
Continuous magnetic agitation, the blend being uniformly mixed after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved；
(3) blend mixed is poured in Teflon mould, keep 24 hours under room temperature, treat that solvent is complete
It is vacuum dried under the conditions of 60 DEG C after evaporation 24 hours and removes solvent and moisture further, obtain acetylation of cellulose nanocomposite
Modified biomass base polyester material.
The acetyl on the CMT6503 instrument of tester company prepared by the present embodiment is newly thought carefully in Shenzhen according to GB4456-84
Cellulose nanocomposite modified biomass base polyester material carries out Mechanics Performance Testing, and rate of extension is 5mm/min, test
Result shows: modified through acetylation of cellulose nanocomposite, and biomass-based polyester material is in hot strength, Young's modulus side
The performance in face is significantly improved, and concrete numerical value is shown in Table 1.
Comparative example
A kind of biomass-based polyester material, is prepared via a method which to obtain: take 100 parts of poly-(3-hydroxybutyrate ester-co-4-hydroxyls
Butyrate) join in chloroform, after poly-(3-hydroxybutyrate ester-co-4-butyric ester) is completely dissolved, pour polytetrafluoro into
In ethene mould, keep 24 hours at room temperature；At 60 DEG C, 24 hours it are vacuum dried further after solvent evaporates completely
Remove solvent and moisture, obtain biomass-based polyester material.Tester company is newly thought carefully in Shenzhen according to GB4456-84
The bacterium synthesizing polyester material on CMT6503 instrument obtained comparative example carries out Mechanics Performance Testing, and rate of extension is 5
Mm/min, mechanical property the results are shown in Table 1.
The mechanical property of table 1 acetylation of cellulose nanocomposite modified biomass base polyester material
As it can be seen from table 1 modified through acetylation of cellulose nanocomposite, poly-(3-hydroxybutyrate ester-co-4-hydroxybutyric acid
Ester) hot strength, Young's modulus improved significantly, the intensity of material and rigidity increase, and toughness reduces, effectively
Expanded the range of application of material, described acetylation of cellulose nanocomposite modified biomass base polyester material can directly become
Type is processed as film, sheet material, section bar or container etc., it is also possible to as packaging material, bio-medical material or engineering plastics etc..
Meanwhile, the reality of the nanocrystalline high-load of acetylation of cellulose in acetylation of cellulose nanocomposite modified biomass base polyester material
Existing, largely reduce the cost of material, be allowed to that there is more preferable application prospect.
Obviously, above-described embodiment is only by clearly demonstrating made example, and not restriction to embodiment.For institute
For the those of ordinary skill in genus field, can also make other changes in different forms on the basis of the above description.
Here without also cannot all of embodiment be given exhaustive.And the obvious change therefore amplified or variation still in
Within the protection domain of the invention.
Claims (10)
1. an acetylation of cellulose nanocomposite modified biomass base polyester material; it is characterized in that; it is prepared from by the nanocrystalline and biomass-based polyester material of acetylation of cellulose is compound; described biomass-based polyester material is poly-(3-hydroxybutyrate ester-co-4-butyric ester), and the weight part ratio of described acetylation of cellulose nanocrystalline and poly-(3-hydroxybutyrate ester-co-4-butyric ester) is 3 ~ 30:100.
Acetylation of cellulose nanocomposite modified biomass base polyester material the most according to claim 1; it is characterized in that; the nanocrystalline product prepared by esterification with acetic anhydride for Cellulose nanocrystal of described acetylation of cellulose; its structure is club shaped structure; draw ratio is about 9 ~ 10; crystallinity index is more than 80%, and surface degree of acetylation is 62.9% ~ 63.5%.
Acetylation of cellulose nanocomposite modified biomass base polyester material the most according to claim 2; it is characterized in that; the nanocrystalline preparation method of described acetylation of cellulose comprises the steps: that Cellulose nanocrystal powder is scattered in solvent by (1), ultrasonically treated after obtain Cellulose nanocrystal suspension；(2) being scattered in solvent by acetic anhydride, be then added drop-wise in Cellulose nanocrystal suspension occur esterification, after reaction terminates, be down to room temperature, product is scrubbed, it is nanocrystalline to obtain acetylation of cellulose after freeze-drying.
Acetylation of cellulose nanocomposite modified biomass base polyester material the most according to claim 3; it is characterized in that; acetic anhydride: the mol ratio of the surface hydroxyl of Cellulose nanocrystal is 40 ~ 80:1, in every gram of Cellulose nanocrystal, the amount of described surface hydroxyl is 1.20mmol.
Acetylation of cellulose nanocomposite modified biomass base polyester material the most according to claim 3, it is characterised in that the condition of described esterification is: nitrogen is protected, and reaction temperature is 80 DEG C, and the reaction time is 8 hours.
Acetylation of cellulose nanocomposite modified biomass base polyester material the most according to claim 3, it is characterised in that described solvent is anhydrous pyridine.
7. the preparation method of the arbitrary described acetylation of cellulose nanocomposite modified biomass base polyester material of claim 1 ~ 6; it is characterized in that; comprise the steps: that (1) weighs that acetylation of cellulose is nanocrystalline to be dissolved in solvent; it is added thereto to poly-(3-hydroxybutyrate ester-co-4-butyric ester) after ultrasonically treated, after mixing, obtains suspension；(2) suspension mixed is poured in Teflon mould, treat that solvent evaporates final vacuum completely and is dried removing solvent and moisture further, obtain acetylation of cellulose nanocomposite modified biomass base polyester material.
Preparation method the most according to claim 7, it is characterised in that the described ultrasonically treated condition of step (1) is: under room temperature, ultrasonic time is 10 minutes/time, ultrasonic number of times 3 times.
Preparation method the most according to claim 7, it is characterised in that the process conditions of step (1) described mixing are: under room temperature, continuing magnetic force stirs, and rotating speed is 600 rpm.
Preparation method the most according to claim 7, it is characterised in that the described vacuum drying technique of step (2) is: be vacuum dried 24 hours under the conditions of 60 DEG C.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009571A (en) * | 2016-07-15 | 2016-10-12 | 扬州大学 | Preparation method of polycaprolactone/nanocellulose crystal composite material |
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| CN104403298A (en) * | 2014-11-24 | 2015-03-11 | 西北农林科技大学 | Biodegradable composite film and preparation method thereof |
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| CN103483786A (en) * | 2013-06-27 | 2014-01-01 | 浙江理工大学 | Fully-biodegradable composite membrane filled with nano silver/cellulose nanocrystal composite particles, and preparation method thereof |
| CN104403298A (en) * | 2014-11-24 | 2015-03-11 | 西北农林科技大学 | Biodegradable composite film and preparation method thereof |
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| CN106009571A (en) * | 2016-07-15 | 2016-10-12 | 扬州大学 | Preparation method of polycaprolactone/nanocellulose crystal composite material |
| CN106009571B (en) * | 2016-07-15 | 2018-05-04 | 扬州大学 | A kind of preparation method of polycaprolactone/Cellulose nanocrystal composite material |
| CN106519308A (en) * | 2016-10-12 | 2017-03-22 | 昆明理工大学 | Preparing method for hydroxypropyl methyl cellulose crosslinked membrane |
| CN106519308B (en) * | 2016-10-12 | 2019-02-05 | 昆明理工大学 | A kind of preparation method of hydroxypropyl methyl cellulose cross linking membrane |
| CN106699905A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Preparation method of high-carboxyl-functionality cellulose nanocrystals |
| WO2018126959A1 (en) * | 2017-01-03 | 2018-07-12 | 中国科学院金属研究所 | Cellulose type ii nanocrystalline particle and manufacturing method and application therefor |
| US11149095B2 (en) | 2017-01-03 | 2021-10-19 | Institute Of Metal Research Chinese Academy Of Sciences | Cellulose II nanocrystal particles and preparation method and use thereof |
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| CN109897554B (en) * | 2018-06-27 | 2021-01-12 | 湖北工业大学 | Cellulose nanocrystalline modified assembled external wall panel splicing seam bonding sealing material |
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| CN111808584B (en) * | 2019-04-11 | 2023-02-03 | 汉中聚智达远环能科技有限公司 | Unsaturated polyester plugging agent modified based on multi-arm initiator and cellulose nanocrystals and preparation method thereof |
| CN110128803A (en) * | 2019-04-24 | 2019-08-16 | 广东省医疗器械研究所 | A kind of preparation method of modified BCW/PHBV composite material |
| CN110591308A (en) * | 2019-08-27 | 2019-12-20 | 江苏理工学院 | Poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and preparation method thereof |
| CN110591308B (en) * | 2019-08-27 | 2021-11-16 | 江苏理工学院 | Poly (beta-hydroxybutyrate valerate)/modified nanocrystalline cellulose composite material and preparation method thereof |
| CN115068693A (en) * | 2021-03-11 | 2022-09-20 | 东北林业大学 | Bone repair foaming composite material and preparation method thereof |
| CN115068693B (en) * | 2021-03-11 | 2024-04-12 | 东北林业大学 | Bone repair foaming composite material and preparation method thereof |
| CN113193275A (en) * | 2021-05-27 | 2021-07-30 | 浙江华正能源材料有限公司 | Outer protective layer for aluminum plastic film, aluminum plastic film and lithium ion battery |
| CN117362946A (en) * | 2023-10-16 | 2024-01-09 | 江苏蜀扬春新材料科技有限公司 | Nanocellulose modified polyester composite material and preparation method thereof |
| CN117362946B (en) * | 2023-10-16 | 2024-05-03 | 江苏蜀扬春新材料科技有限公司 | Nanocellulose modified polyester composite material and preparation method thereof |
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