CN105754308B - A kind of acetylation of cellulose nanocomposite modified biomass base polyester material and preparation method thereof - Google Patents
A kind of acetylation of cellulose nanocomposite modified biomass base polyester material and preparation method thereof Download PDFInfo
- Publication number
- CN105754308B CN105754308B CN201610159964.XA CN201610159964A CN105754308B CN 105754308 B CN105754308 B CN 105754308B CN 201610159964 A CN201610159964 A CN 201610159964A CN 105754308 B CN105754308 B CN 105754308B
- Authority
- CN
- China
- Prior art keywords
- acetylation
- cellulose
- polyester material
- nanocrystalline
- base polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to natural macromolecular material field, and in particular to a kind of acetylation of cellulose nanocomposite modified biomass base polyester material and preparation method thereof.The acetylation of cellulose nanocomposite modified biomass base polyester material is nanocrystalline and poly- by acetylation of cellulose（3 butyric ester co, 4 butyric esters）It is 3 ~ 30 by weight：100 compound are prepared.Its preparation method is：Will be poly-（3 butyric ester co, 4 butyric esters）With acetylation of cellulose nanocrystal solution mixing be placed on Teflon mould carry out casting film-forming, after evaporation of the solvent at room temperature, then it is vacuum dried after obtain acetylation of cellulose nanocomposite modified biomass base polyester material.It is modified through acetylation of cellulose nanocomposite, gather（3 butyric ester co, 4 butyric esters）Tensile strength, Young's modulus be significantly improved, the increase of the intensity of material, rigidity increase, have effectively expanded the application range of material.
Description
Technical field
The invention belongs to natural macromolecular material field, and in particular to a kind of acetylation of cellulose nanocomposite is modified life
Material base polyester material and preparation method thereof.
Background technology
Cellulose is the natural polysaccharide macromolecule that nature is widely present, and is the structure being prevalent in various plants
Property polymer.For the structure of cellulose, mainly it is made of crystallization and amorphous regions.Amorphous regions are quick to hydrolysising condition
Sense, can be completely removed, remaining more complete rigid crystalline region becomes Cellulose nanocrystal under certain condition.With nothing
Machine nano-particle is compared, and Cellulose nanocrystal possesses many merits, is such as easy to get, low cost, nano effect, high-specific surface area and mould
Amount, relatively disposable, biodegradable, bio-compatible and active surface groupings etc..Particularly Cellulose nanocrystal has preferable
Biocompatibility, multiple biological activities, adsorption function and biodegradability etc., available for packaging material for food, Medical coating
The functional materials such as material, additive for paper making, water process exchange of particles resin, slow releasing carrier of medication.Therefore, the crowd of Cellulose nanocrystal
More advantages assign it and are widely applied prospect in materials science field.On the other hand, in order to adapt to different substrates material system, pin
The surface modification of Cellulose nanocrystal has been carried out for many years with changing nanocrystalline intrinsic surface Quality Research.Acetyl fibre
Element is nanocrystalline product that to be Cellulose nanocrystal obtain with acetic anhydride after esterification, equally with high-crystallinity, high-modulus,
Renewable, biodegradable, advantages of environment protection, may be used as nanometer reinforcer improving the performance of polymeric material and
By extensive concern.But the plain nanocrystalline degree of acetylation of control fiber and grinding using its modified biomass base polyester material
Study carefully but to rarely have and be related to.
Biodegradable material refers to can be by diversified forms such as light degradation, chemical degradation, biodegradations, by material degradation
Into the lower-molecular substance of environmental sound, the material with good practical performance.Biodegradable material include natural material and
Synthetic material, natural material include starch, cellulose, chitin and their derivative, and synthetic material usually contains can water
Solve functional group (such as：Ester bond, urea bond, amido link, ehter bond etc.), as poly butyric ester, polylactic acid, poly butylene succinate,
Polycaprolactone etc..Poly butyric ester is a kind of biodegradable polyester synthesis material, industrially mainly by bacterium (such as：
Alcaligenes eutrophus, azotobacter vinelandii, methylotrophic bacteria etc.) synthesize, but the brittleness of existing poly butyric ester is larger, this
It greatly limit application range of the poly butyric ester in Material Field.
The content of the invention
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide a kind of acetylation of cellulose nanocomposite is modified life
Material 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 by acetyl chemical fibre
The nanocrystalline and biomass-based polyester material of dimension element is compound to be prepared, and the biomass-based polyester material is poly- (3-hydroxybutyrate
Ester-co-4- butyric esters), the acetylation of cellulose is nanocrystalline and poly- (3-hydroxybutyrate ester-co-4- butyric esters)
Weight part ratio be 3~30：100.
By such scheme, the acetylation of cellulose is nanocrystalline to be obtained for Cellulose nanocrystal with acetic anhydride through esterification
Product, its structure is club shaped structure, and draw ratio is about 9~10, crystallinity index be more than 80%, surface degree of acetylation is up to
62.5%~63.5%.
By such scheme, the nanocrystalline preparation method of the acetylation of cellulose includes the following steps：(1) cellulose is received
Rice crystalline flour end is scattered in solvent, and Cellulose nanocrystal suspension is obtained after supersound process；(2) acetic anhydride is scattered in solvent
In, then it is added drop-wise in Cellulose nanocrystal suspension and esterification occurs, after reaction, is down to greenhouse, reaction product warp
It is nanocrystalline that acetylation of cellulose is obtained after washing, freeze-drying.
By such scheme, acetic anhydride：The molar ratio of the surface hydroxyl of Cellulose nanocrystal is 40~80:1, the surface hydroxyl
The amount of base is that have 1.20mmol in every gram of Cellulose nanocrystal.
By such scheme, the condition of the esterification is：Nitrogen is protected, and reaction temperature is 80 DEG C, and the reaction time is small for 8
When.
By such scheme, the 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 the following steps：(1) weigh that acetylation of cellulose is nanocrystalline to be dissolved in solvent, add poly- (3- hydroxyls after supersound process thereto
Base butyrate-co-4- butyric esters), suspension is obtained after mixing；(2) uniformly mixed suspension is poured into poly- four
In vinyl fluoride mould, it is dried in vacuo after solvent evaporating completely and further removes solvent and moisture, obtained acetylation of cellulose and receive
The brilliant compound modified biomass base polyester material of rice.
By such scheme, the condition of step (1) described supersound process is：At room temperature, ultrasonic time is 10 minutes/time, is surpassed
Sound number 3 times.
By such scheme, the process conditions of step (1) described mixing are：At room temperature, continuing magnetic force stirs, and rotating speed is
600rpm。
By such scheme, step (2) the vacuum drying technique is：When vacuum drying 24 is small under the conditions of 60 DEG C.
In the present invention, acetylation of cellulose is nanocrystalline to change poly- the compound of (3-hydroxybutyrate ester-co-4- butyric esters)
Property during, introduce acetyl group since acetylation of cellulose is nanocrystalline and have and poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Butyrate) the identical hydrophobic group of molecule (ester group and alkyl), so that the hydrophobicity on its surface and poly- (3-hydroxybutyrate
Ester-co-4- butyric esters) hydrophobicity of matrix is close, ensure that both compatibilities and advantageously form interaction
Site, and as the increase of acetylation modification degree, the interaction sites of formation are more.On the other hand, Cellulose nanocrystal
Acetylation in gentle reaction condition cause rigid crystalline of the Cellulose nanocrystal as the substantive characteristics of reinforcer
Structure and Rod-like shape are maintained.Be based on 2 points of the above, acetylation of cellulose it is nanocrystalline to it is poly- (3-hydroxybutyrate ester-
Co-4- butyric esters) it is composite modified after, the mechanical property of nanocomposite just significantly enhancing.
Beneficial effects of the present invention are as follows：(1) present invention is received using the higher acetylation of cellulose of acetylation modification degree
Meter Jing to poly- (3-hydroxybutyrate ester-co-4- butyric esters) modification for composite, it is modified it is poly- (3-hydroxybutyrate ester-
Co-4- butyric esters) material, its tensile strength, Young's modulus significantly improved, the intensity increase of material, just
Property increase, toughness reduce, effectively expanded the application range of material, the acetylation of cellulose nanocomposite modification biological
Matter base polyester material can be processed as film, sheet material, section bar or container etc. with straight forming, be also used as packaging material, biology
Medical material or engineering plastics etc.；(2) present invention is by controlling the esterification of acetic anhydride and Cellulose nanocrystal to be prepared
The acetylation of cellulose of higher degree of acetylation is nanocrystalline, further nanocrystalline using the acetylation of cellulose, passes through
Poly- (3-hydroxybutyrate ester-co-4- the hydroxybutyric acids of acetylation of cellulose nanocomposite modification are prepared in casting molding processes
Ester), whole preparation method has the advantages that simple technique, of low cost, environmental-friendly, quickness and high efficiency and highly compatible.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
In following embodiments, the nanocrystalline preparation method of the acetylation of cellulose includes the following steps：(1) by cellulose
Manocrystalline powders are scattered in anhydrous pyridine, and Cellulose nanocrystal suspension is obtained after supersound process；(2) acetic anhydride is scattered in
In anhydrous pyridine, then it is added drop-wise in Cellulose nanocrystal suspension and esterification occurs, after reaction, is down to room temperature, instead
Answer that product is washed, to obtain acetylation of cellulose nanocrystalline after freeze-drying.
Wherein, the molar ratio of the acetic anhydride and the surface hydroxyl of Cellulose nanocrystal is 40:1；The esterification is anti-
The condition answered is：Nitrogen is protected, and reaction temperature is 80 DEG C, when the reaction time is 5 small；The acetylation of cellulose nanometer being prepared
Brilliant acetylation modification degree is 62.9%.
The molar ratio of the acetic anhydride and the surface hydroxyl of Cellulose nanocrystal is 80:1；The bar of the esterification
Part is：Nitrogen is protected, and reaction temperature is 80 DEG C, when the reaction time is 5 small；The nanocrystalline second of the acetylation of cellulose that is prepared
Acylated 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 3 parts of acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%), poly- (3- hydroxyls
Base butyrate-co-4- butyric esters) 100 parts, choose that acetylation of cellulose is nanocrystalline, poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Base butyrate), it is scattered in acetylation of cellulose is nanocrystalline in chloroform, (ultrasonic number 3 times, ultrasound after sonicated
Time 10min/ times) obtain acetylation of cellulose nanocrystal suspension；
(2) poly- (3-hydroxybutyrate ester-co-4- butyric esters) is added to acetylation of cellulose nanocrystal suspension
In, continuing magnetic force stirring, uniformly mixed be total to is obtained after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Mixed thing；
(3) uniformly mixed blend is poured into Teflon mould, when holding 24 is small at room temperature, treats that solvent is complete
Solvent and moisture are further removed when vacuum drying 24 is small under the conditions of 60 DEG C after evaporation, obtains acetylation of cellulose nanocomposite
Modified biomass base polyester material.
Newly think carefully on the CMT6503 instruments of test equipment company to manufactured in the present embodiment in Shenzhen according to GB4456-84
The progress Mechanics Performance Testing of acetylation of cellulose nanocomposite modified biomass base polyester material, rate of extension 5mm/min,
Test result is shown：After deacetylation Cellulose nanocrystal is composite modified, biomass-based polyester material is in tensile strength, Young
Performance in terms of modulus 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 6 parts of acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%), poly- (3- hydroxyls
Base butyrate-co-4- butyric esters) 100 parts, choose that acetylation of cellulose is nanocrystalline, poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Base butyrate), it is scattered in acetylation of cellulose is nanocrystalline in chloroform, (ultrasonic number 3 times, ultrasound after sonicated
Time 10min/ times) obtain acetylation of cellulose nanocrystal suspension；
(2) poly- (3-hydroxybutyrate ester-co-4- butyric esters) is added to acetylation of cellulose nanocrystal suspension
In, continuing magnetic force stirring, uniformly mixed be total to is obtained after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Mixed thing；
(3) uniformly mixed blend is poured into Teflon mould, when holding 24 is small at room temperature, treats that solvent is complete
Solvent and moisture are further removed when vacuum drying 24 is small under the conditions of 60 DEG C after evaporation, obtains acetylation of cellulose nanocomposite
Modified biomass base polyester material.
Newly think carefully on the CMT6503 instruments of test equipment company to manufactured in the present embodiment in Shenzhen according to GB4456-84
The progress Mechanics Performance Testing of acetylation of cellulose nanocomposite modified biomass base polyester material, rate of extension 5mm/min,
Test result is shown：Modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in tensile strength, Young mould
Performance in terms of amount is significantly improved, and 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 9 parts of acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%), poly- (3- hydroxyls
Base butyrate-co-4- butyric esters) 100 parts, choose that acetylation of cellulose is nanocrystalline, poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Base butyrate), it is scattered in acetylation of cellulose is nanocrystalline in chloroform, (ultrasonic number 3 times, ultrasound after sonicated
Time 10min/ times) obtain acetylation of cellulose nanocrystal suspension；
(2) poly- (3-hydroxybutyrate ester-co-4- butyric esters) is added to acetylation of cellulose nanocrystal suspension
In, continuing magnetic force stirring, uniformly mixed be total to is obtained after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Mixed thing；
(3) uniformly mixed blend is poured into Teflon mould, when holding 24 is small at room temperature, treats that solvent is complete
Solvent and moisture are further removed when vacuum drying 24 is small under the conditions of 60 DEG C after evaporation, obtains acetylation of cellulose nanocomposite
Modified biomass base polyester material.
Newly think carefully on the CMT6503 instruments of test equipment company to manufactured in the present embodiment in Shenzhen according to GB4456-84
The progress Mechanics Performance Testing of acetylation of cellulose nanocomposite modified biomass base polyester material, rate of extension 5mm/min,
Test result is shown：Modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in tensile strength, Young mould
Performance in terms of amount 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 15 parts of acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%), poly- (3- hydroxyls
Base butyrate-co-4- butyric esters) 100 parts, choose that acetylation of cellulose is nanocrystalline, poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Base butyrate), it is scattered in acetylation of cellulose is nanocrystalline in chloroform, (ultrasonic number 3 times, ultrasound after sonicated
Time 10min/ times) obtain acetylation of cellulose nanocrystal suspension；
(2) poly- (3-hydroxybutyrate ester-co-4- butyric esters) is added to acetylation of cellulose nanocrystal suspension
In, continuing magnetic force stirring, uniformly mixed be total to is obtained after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Mixed thing；
(3) uniformly mixed blend is poured into Teflon mould, when holding 24 is small at room temperature, treats that solvent is complete
Solvent and moisture are further removed when vacuum drying 24 is small under the conditions of 60 DEG C after evaporation, obtains acetylation of cellulose nanocomposite
Modified biomass base polyester material.
Newly think carefully on the CMT6503 instruments of test equipment company to manufactured in the present embodiment in Shenzhen according to GB4456-84
The progress Mechanics Performance Testing of acetylation of cellulose nanocomposite modified biomass base polyester material, rate of extension 5mm/min,
Test result is shown：Modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in tensile strength, Young mould
Performance in terms of amount 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 20 parts of acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%), poly- (3- hydroxyls
Base butyrate-co-4- butyric esters) 100 parts, choose that acetylation of cellulose is nanocrystalline, poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Base butyrate), it is scattered in acetylation of cellulose is nanocrystalline in chloroform, sonicated (ultrasonic number 3 times, when ultrasonic
Between 10min/ times) after obtain acetylation of cellulose nanocrystal suspension；
(2) poly- (3-hydroxybutyrate ester-co-4- butyric esters) is added to acetylation of cellulose nanocrystal suspension
In, continuing magnetic force stirring, uniformly mixed be total to is obtained after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Mixed thing；
(3) uniformly mixed blend is poured into Teflon mould, when holding 24 is small at room temperature, treats that solvent is complete
Solvent and moisture are further removed when vacuum drying 24 is small under the conditions of 60 DEG C after evaporation, obtains acetylation of cellulose nanocomposite
Modified biomass base polyester material.
Newly think carefully on the CMT6503 instruments of test equipment company to manufactured in the present embodiment in Shenzhen according to GB4456-84
The progress Mechanics Performance Testing of acetylation of cellulose nanocomposite modified biomass base polyester material, rate of extension 5mm/min,
Test result is shown：Modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in tensile strength, Young mould
Performance in terms of amount is significantly improved, and 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 25 parts of acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%), poly- (3- hydroxyls
Base butyrate-co-4- butyric esters) 100 parts, choose that acetylation of cellulose is nanocrystalline, poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Base butyrate), it is scattered in acetylation of cellulose is nanocrystalline in chloroform, sonicated (ultrasonic number 3 times, when ultrasonic
Between 10min/ times) after obtain acetylation of cellulose nanocrystal suspension；
(2) poly- (3-hydroxybutyrate ester-co-4- butyric esters) is added to acetylation of cellulose nanocrystal suspension
In, continuing magnetic force stirring, uniformly mixed be total to is obtained after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Mixed thing；
(3) uniformly mixed blend is poured into Teflon mould, when holding 24 is small at room temperature, treats that solvent is complete
Solvent and moisture are further removed when vacuum drying 24 is small under the conditions of 60 DEG C after evaporation, obtains acetylation of cellulose nanocomposite
Modified biomass base polyester material.
Newly think carefully on the CMT6503 instruments of test equipment company to manufactured in the present embodiment in Shenzhen according to GB4456-84
The progress Mechanics Performance Testing of acetylation of cellulose nanocomposite modified biomass base polyester material, rate of extension 5mm/min,
Test result is shown：Modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in tensile strength, Young mould
Performance in terms of amount is significantly improved, and 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 30 parts of acetylation of cellulose nanocrystalline (degree of acetylation is respectively 62.9% and 63.2%), poly- (3- hydroxyls
Base butyrate-co-4- butyric esters) 100 parts, choose that acetylation of cellulose is nanocrystalline, poly- (3-hydroxybutyrate ester-co-4- hydroxyls
Base butyrate), it is scattered in acetylation of cellulose is nanocrystalline in chloroform, sonicated (ultrasonic number 3 times, when ultrasonic
Between 10min/ times) after obtain acetylation of cellulose nanocrystal suspension；
(2) poly- (3-hydroxybutyrate ester-co-4- butyric esters) is added to acetylation of cellulose nanocrystal suspension
In, continuing magnetic force stirring, uniformly mixed be total to is obtained after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Mixed thing；
(3) uniformly mixed blend is poured into Teflon mould, when holding 24 is small at room temperature, treats that solvent is complete
Solvent and moisture are further removed when vacuum drying 24 is small under the conditions of 60 DEG C after evaporation, obtains acetylation of cellulose nanocomposite
Modified biomass base polyester material.
Newly think carefully on the CMT6503 instruments of test equipment company to manufactured in the present embodiment in Shenzhen according to GB4456-84
The progress Mechanics Performance Testing of acetylation of cellulose nanocomposite modified biomass base polyester material, rate of extension 5mm/min,
Test result is shown：Modified through acetylation of cellulose nanocomposite, biomass-based polyester material is in tensile strength, Young mould
Performance in terms of amount 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 hydroxybutyric acid ester) it is added in chloroform, fallen after poly- (3-hydroxybutyrate ester-co-4- butyric esters) is completely dissolved
Enter in Teflon mould, when holding 24 is small at room temperature；When vacuum drying 24 is small at 60 DEG C after solvent evaporating completely
Solvent and moisture are further removed, obtains biomass-based polyester material.Test equipment public affairs are newly thought carefully in Shenzhen according to GB4456-84
Mechanics Performance Testing is carried out to the bacterium synthesizing polyester material that comparative example obtains on the CMT6503 instruments of department, rate of extension is
5mm/min, mechanical property the results are shown in Table 1.
The mechanical property of 1 acetylation of cellulose nanocomposite modified biomass base polyester material of table
As it can be seen from table 1, poly- (3-hydroxybutyrate ester-co-4- hydroxyl modified through acetylation of cellulose nanocomposite
Base butyrate) tensile strength, Young's modulus significantly improved, the intensity of material and rigidity increase, and toughness reduces,
The application range of material is effectively expanded, the acetylation of cellulose nanocomposite modified biomass base polyester material can be with
Straight forming is processed as film, sheet material, section bar or container etc., is also used as packaging material, bio-medical material or engineering plastic
Material etc..Meanwhile the nanocrystalline height of acetylation of cellulose contains in acetylation of cellulose nanocomposite modified biomass base polyester material
The realization of amount, largely reduces the cost of material, with more preferable application prospect.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change or change therefore amplified
Move within still in the protection domain of the invention.
Claims (9)
1. a kind of acetylation of cellulose nanocomposite modified biomass base polyester material, it is characterised in that by acetyl fibre
The nanocrystalline and biomass-based polyester material of element is compound to be prepared, and the biomass-based polyester material is poly-（3-hydroxybutyrate ester-
Co-4- butyric esters）, the acetylation of cellulose is nanocrystalline and poly-（3-hydroxybutyrate ester-co-4- butyric esters）Weight
Amount part is compared for 3 ~ 30：100；The acetylation of cellulose is nanocrystalline to be prepared for Cellulose nanocrystal with acetic anhydride by esterification
Obtained product, its structure are club shaped structure, and draw ratio is 9 ~ 10, and crystallinity index is more than 80%, and surface degree of acetylation is
62.9%~63.5%。
2. acetylation of cellulose nanocomposite modified biomass base polyester material according to claim 1, its feature exist
In the nanocrystalline preparation method of the acetylation of cellulose includes the following steps：（1）Cellulose nanocrystal powder is scattered in molten
In agent, Cellulose nanocrystal suspension is obtained after supersound process；（2）Acetic anhydride is scattered in solvent, is then added drop-wise to fiber
Esterification occurs in plain nanocrystal suspension, after reaction, is down to room temperature, reaction product is washed, is obtained after freeze-drying
It is nanocrystalline to acetylation of cellulose.
3. acetylation of cellulose nanocomposite modified biomass base polyester material according to claim 2, its feature exist
In acetic anhydride：The molar ratio of the surface hydroxyl of Cellulose nanocrystal is 40 ~ 80:1, in every gram of Cellulose nanocrystal, the surface
The amount of hydroxyl is 1.20mmol.
4. acetylation of cellulose nanocomposite modified biomass base polyester material according to claim 2, its feature exist
In the condition of the esterification is：Nitrogen is protected, and reaction temperature is 80 DEG C, when the reaction time is 8 small.
5. acetylation of cellulose nanocomposite modified biomass base polyester material according to claim 2, its feature exist
In the solvent is anhydrous pyridine.
6. the preparation side of any acetylation of cellulose nanocomposite modified biomass base polyester material of claim 1 ~ 5
Method, it is characterised in that include the following steps：（1）Weigh that acetylation of cellulose is nanocrystalline to be dissolved in solvent, be ultrasonically treated it is backward its
Middle add is gathered（3-hydroxybutyrate ester-co-4- butyric esters）, suspension is obtained after mixing；（2）It is outstanding by what is be uniformly mixed
Supernatant liquid is poured into Teflon mould, is dried in vacuo after solvent evaporating completely and is further removed solvent and moisture, obtains second
Acylated cellulose nanocomposite modified biomass base polyester material.
7. preparation method according to claim 6, it is characterised in that step（1）The condition of the supersound process is：Room temperature
Under, ultrasonic time is 10 minutes/time, ultrasonic number 3 times.
8. preparation method according to claim 6, it is characterised in that step（1）The process conditions of the mixing are：Room temperature
Under, continuing magnetic force stirring, rotating speed is 600 rpm.
9. preparation method according to claim 6, it is characterised in that step（2）The vacuum drying technique is：60
When vacuum drying 24 is small under the conditions of DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610159964.XA CN105754308B (en) | 2016-03-21 | 2016-03-21 | A kind of acetylation of cellulose nanocomposite modified biomass base polyester material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610159964.XA CN105754308B (en) | 2016-03-21 | 2016-03-21 | A kind of acetylation of cellulose nanocomposite modified biomass base polyester material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105754308A CN105754308A (en) | 2016-07-13 |
| CN105754308B true CN105754308B (en) | 2018-05-01 |
Family
ID=56346085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610159964.XA Expired - Fee Related CN105754308B (en) | 2016-03-21 | 2016-03-21 | A kind of acetylation of cellulose nanocomposite modified biomass base polyester material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105754308B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009571B (en) * | 2016-07-15 | 2018-05-04 | 扬州大学 | A kind of preparation method of polycaprolactone/Cellulose nanocrystal composite material |
| 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 |
| CN108264569B (en) * | 2017-01-03 | 2020-01-03 | 中国科学院金属研究所 | Cellulose II type nanocrystalline particles and preparation method and application thereof |
| CN107938332A (en) * | 2017-11-08 | 2018-04-20 | 浙江理工大学 | A kind of Cellulose nanocrystal must hydrophobic modification method |
| 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 |
| 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 |
| 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 |
| CN115068693B (en) * | 2021-03-11 | 2024-04-12 | 东北林业大学 | Bone repair foaming composite material and preparation method thereof |
| CN113193275B (en) * | 2021-05-27 | 2022-10-14 | 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-03-21 CN CN201610159964.XA patent/CN105754308B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105754308A (en) | 2016-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105754308B (en) | A kind of acetylation of cellulose nanocomposite modified biomass base polyester material and preparation method thereof | |
| Das et al. | A comprehensive review on recent advances in preparation, physicochemical characterization, and bioengineering applications of biopolymers | |
| Ojogbo et al. | Chemical and physical modifications of starch for renewable polymeric materials | |
| Patel et al. | Nanocellulose-based polymer hybrids and their emerging applications in biomedical engineering and water purification | |
| Wahid et al. | Bacterial cellulose and its potential for biomedical applications | |
| Scaffaro et al. | Polysaccharide nanocrystals as fillers for PLA based nanocomposites | |
| Rafique et al. | Chitosan functionalized poly (vinyl alcohol) for prospects biomedical and industrial applications: A review | |
| Kanimozhi et al. | In vitro cytocompatibility of chitosan/PVA/methylcellulose–Nanocellulose nanocomposites scaffolds using L929 fibroblast cells | |
| Mohan et al. | Biopolymers–application in nanoscience and nanotechnology | |
| Amara et al. | Nanocellulose-based composites for packaging applications | |
| Abhilash et al. | Biopolymers for biocomposites and chemical sensor applications | |
| Panaitescu et al. | Nanostructured biocomposites from aliphatic polyesters and bacterial cellulose | |
| Visakh et al. | Preparation of bionanomaterials and their polymer nanocomposites from waste and biomass | |
| Mincea et al. | Preparation, modification, and applications of chitin nanowhiskers: a review | |
| Grossman et al. | Biopolymer nanocomposites: processing, properties, and applications | |
| Lizundia et al. | Grafting of cellulose nanocrystals | |
| Anwer et al. | State-of-the-art advances in nanocomposite and bio-nanocomposite polymeric materials: A comprehensive review | |
| Zuber et al. | Chitin and chitosan based blends, composites and nanocomposites | |
| Jadhav et al. | Potential of polylactide based nanocomposites-nanopolysaccharide filler for reinforcement purpose: A comprehensive review | |
| Saba et al. | An overview on polylactic acid, its cellulosic composites and applications | |
| Karua et al. | Synthesis and characterization of starch/chitosan composites | |
| Lv et al. | Overview of preparation, modification, and application of tunicate-derived nanocellulose | |
| Trovatti | The future of bacterial cellulose and other microbial polysaccharides | |
| Fajardo et al. | Hydrogels nanocomposites based on crystals, whiskers and fibrils derived from biopolymers | |
| Visakh et al. | Natural polymers: their blends, composites and nanocomposites: state of art, new challenges and opportunities |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180501 Termination date: 20190321 |