CN106009571B - A kind of preparation method of polycaprolactone/Cellulose nanocrystal composite material - Google Patents
A kind of preparation method of polycaprolactone/Cellulose nanocrystal composite material Download PDFInfo
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- CN106009571B CN106009571B CN201610561571.1A CN201610561571A CN106009571B CN 106009571 B CN106009571 B CN 106009571B CN 201610561571 A CN201610561571 A CN 201610561571A CN 106009571 B CN106009571 B CN 106009571B
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- cellulose nanocrystal
- polycaprolactone
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/10—Esters of organic acids
- C08J2401/12—Cellulose 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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
A kind of preparation method of polycaprolactone/Cellulose nanocrystal composite material; it is related to the preparation method of biodegradable composite material; microcrystalline cellulose is formed Cellulose nanocrystal body by the present invention through acidolysis; Cellulose nanocrystal body is obtained into acetylation of cellulose nanocrystal by acetylated modification again; then acetylation of cellulose nanocrystal and polycaprolactone are dissolved in organic solvent again; obtain mixed solution; mixed solution is salivated again and is formed a film; through drying, polycaprolactone/Cellulose nanocrystal composite material is obtained.The present invention can avoid the irreversible reunion of Cellulose nanocrystal body, and the acetylation of cellulose nanocrystal finally obtained is more preferable in matrix dispersiveness.
Description
Technical field
The present invention relates to the preparation method of biodegradable composite material, more particularly to cellulose modified polycaprolactone production
Technical field.
Background technology
With the development of society, the use of a large amount of non-degradable plastics result in serious environmental pollution, therefore biology can
Degradable material has obtained extensive attention.Polycaprolactone（PCL）It is a kind of high molecular material of totally biodegradable, quilt at present
Apply to operation suture thread, packaging material, low temperature damping material, engineering plastics etc..But non-modified polycaprolactone material
Mechanical property have it is clearly disadvantageous：The fracture strength of polycaprolactone is relatively low, constrains its use scope as engineering plastics；
Glass transition temperature is too low；Dynamic thermo-mechanical property is poor, is used as low temperature in use, intensity is substantially relatively low.Therefore it is big
Quantity research person uses the means such as filling, blending, grafting to prepare polycaprolactone composite material to improve its performance.
The conventional method of modifying of polycaprolactone is rigid filled to fill, such as carbon nanotubes, graphene oxide, glass fibre
Deng, but these method costs for preparing composite material are excessive, the compatibility of filler and matrix is poor, filler cannot degrade,
Hardly result in the material that financial cost is low, performance is good.
The content of the invention
For the deficiencies in the prior art, the present invention proposes a kind of polycaprolactone for being easy to degrade, intensity is high, economic
The preparation method of composite material.
Microcrystalline cellulose is formed Cellulose nanocrystal body by the present invention through acidolysis, then Cellulose nanocrystal body is passed through acetyl
Change modification and obtain acetylation of cellulose nanocrystal, be then again dissolved in acetylation of cellulose nanocrystal with polycaprolactone
In solvent, mixed solution is obtained, then mixed solution is salivated and is formed a film, through drying, obtains polycaprolactone/Cellulose nanocrystal body
Composite material.
The present invention prepares Cellulose nanocrystal body by raw material acidolysis of microcrystalline cellulose, continuously carries out acetylated modification,
Can be to avoid the irreversible reunion of Cellulose nanocrystal body, the acetylation of cellulose nanocrystal finally obtained is in matrix dispersiveness
More preferably.
Acetylation of cellulose nanocrystal is formed modified polycaprolactone as filler by the present invention, is designed from material property
Aspect set out, there is the existing oil loving group of Cellulose nanocrystal body of acetyl group, it is while peculiar but also with nano material
Nano effect, polycaprolactone and acetylation of cellulose nanocrystal form strong interfacial interaction.
The preparation method of composite material generally comprises：Melt blending, solution blending etc., the side of present invention selection solution blending
Method, the composite material homogeneity being prepared are good.
Polycaprolactone and acetylation of cellulose nanocrystal form strong interfacial interaction in composite material of the present invention,
Therefore the mixing quality ratio of acetylation of cellulose nanocrystal and polycaprolactone of the present invention is 1~20: 80~99.Acetylation
Cellulose nanocrystal body dosage highest setting is 20%.
The performance boost of composite material depends primarily upon two factors：Filler scattered, filler in the base and matrix
Interaction.Therefore the quality of acetylation of cellulose nanocrystal and polycaprolactone of the present invention and mixing for organic solvent volume
Composition and division in a proportion is 1g: 5mL~6mL.Solvent is able to ensure that polycaprolactone is completely dissolved within this range；The viscosity of solution is only suitable
In the range of, the thin-film material into surfacing could be salivated, directly measuring its performance.
Preferable organic solvent is any one in dichloromethane, chloroform.Dichloromethane, chloroform are to gather oneself
The good solvent of lactone, polycaprolactone can dissolve in the short period of time, be easy to implement industrialized production.
Brief description of the drawings
Fig. 1 is the Tensile fracture electron scanning micrograph of embodiment 1.
Fig. 2 is the Tensile fracture electron scanning micrograph of comparative example 2.
Fig. 3 is comparative example 1, the tensile property test result figure of embodiment 1~3.
Fig. 4 is comparative example 1,1~3 modulus of embodiment and temperature relation figure.
Fig. 5 is comparative example 1,1~3 glass transition curve figure of embodiment.
Fig. 6 is comparative example 1, the rheology testing result figure of embodiment 1~5.
Embodiment
The present invention further advantage and effect by following embodiment continuing on.
In following example, the polycaprolactone trade mark is PCL6500, about 50000 g/mol of number-average molecular weight, melting temperature 55~
60 DEG C of Biodegradable high-molecular polyester.
Using existing known technology, microcrystalline cellulose is formed into Cellulose nanocrystal body through acidolysis, then by cellulose nanometer
Crystal passes through the acetylation of cellulose nanocrystal that acetylated modification substitution value is 2.36.
First, embodiment 1：
1st, dried polycaprolactone is mixed with acetylation of cellulose nanocrystal with 99: 1 mass ratio, uses trichlorine
Methane dissolves, the volume of chloroform（ml）With the quality of composite material（g）The ratio between be 5: 1.Salivation film forming after mixing, puts
Drying and moulding at room temperature.
2nd, discharging is injected into standard dog bone batten using miniature injection machine to test for tensile property；Other 80 DEG C of heat
Molded is the sheet material of 1 mm, for Dynamic thermo-mechanical property test and rheology testing.
2nd, embodiment 2 to 7：
The component ratio of embodiment 1 is adjusted, uses different organic solvents instead, changes the volume of organic solvent（ml）
With the quality of composite material（g）Ratio, specific table 1：
Table 1
3rd, comparative example 1：
1st, dried polycaprolactone is directly dissolved using chloroform, the volume of chloroform（ml）With composite material
Quality（g）The ratio between be 5:1.Salivation film forming after mixing, is placed in drying and moulding at room temperature, obtains pure polycaprolactone material.
2nd, discharging is injected into standard dog bone batten using miniature injection machine to test for tensile property；Other 80 DEG C of heat
Molded is the sheet material of 1 mm, for Dynamic thermo-mechanical property test and rheology testing.
4th, comparative example 2
1st, by dried polycaprolactone and microcrystalline cellulose with 99:1 mass ratio mixing, is dissolved using chloroform,
The volume of chloroform（ml）With the quality of composite material（g）The ratio between be 5:1.Salivation film forming after mixing, is placed at room temperature
Drying and moulding.
2nd, discharging is injected into standard dog bone batten using miniature injection machine to test for tensile property；Other 80 DEG C of heat
Molded is the sheet material of 1 mm, for Dynamic thermo-mechanical property test and rheology testing.
5th, analyze：
Table 2 is embodiment 1,2,3,6,7, and the tensile property test result of comparative example 1,2, as can be seen from the table, is added
The fracture of composite materials intensity of acetylation of cellulose nanocrystal is apparently higher than comparative example 1（Pure polylactic acid）；Except being broken
Lifting in terms of intensity, the elongation at break of composite material have also obtained significant increase.
Table 2
Embodiment 1 and comparative example 2, the mass fraction of filler is 1%, but but there is obvious in mechanical property
Difference.Fig. 1 and Fig. 2 is both Tensile fracture electron scanning micrographs respectively, is can be found that by both contrasts：This
Interfacial adhesion effect between the acetylation of cellulose nanocrystal and polycaprolactone matrix that are used in invention is stronger；Comparative example 2
Tensile fracture can clearly be seen that fault of construction between filler and matrix.Further analyzed with reference to Fig. 3, add acetyl chemical fibre
The composite material of the plain nanocrystal of dimension presents the phenomenon of strain hardening in larger elongation.
Two groups of results that Fig. 4 and Fig. 5 Dynamic thermo-mechanical properties are analyzed.Fig. 4 is the modulus and temperature relation of material,
Low-temperature region, the modulus of embodiment 1~3 are largely increased, this just compensate for strong when polycaprolactone is used as cryogenic material
The shortcomings that degree deficiency.The corresponding temperature of peak value of Fig. 5 curves is the glass transition temperature of material, and acetylation of cellulose is nanocrystalline
The addition of body makes the glass transition temperature of composite material increase more than 10 DEG C, this indicate that between filler and matrix there is
Obvious interaction, filler can hinder the movement of polycaprolactone macromolecular chain.
Fig. 6 is comparative example 1, the rheology testing result figure of embodiment 1~5, with acetylation of cellulose nanocrystal
The increase of mass percent, modulus increases composite material in the order of magnitude in the molten state, shows that filler uniformly divides in the base
Dissipate, there is stronger interface interaction.
Organic solvent is used instead dichloromethane in each example, equally can also obtain identical effect above.
Claims (2)
1. the preparation method of a kind of polycaprolactone/Cellulose nanocrystal composite material, it is characterised in that pass through microcrystalline cellulose
Acidolysis forms Cellulose nanocrystal body, then Cellulose nanocrystal body is obtained the acetyl that substitution value is 2.36 by acetylated modification
Acetylation of cellulose nanocrystal and polycaprolactone, are then dissolved in organic solvent by cellulose nanocrystal again, obtain
Mixed solution, then mixed solution is salivated and is formed a film, through drying, obtain polycaprolactone/Cellulose nanocrystal composite material；
The mixing quality ratio of the acetylation of cellulose nanocrystal and polycaprolactone is 1~20: 80~99；
The gross mass of the acetylation of cellulose nanocrystal and polycaprolactone and the mixing ratio of organic solvent volume are 1g: 5mL.
2. preparation method according to claim 1, it is characterised in that the organic solvent is dichloromethane, in chloroform
Any one.
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| CN107043525B (en) * | 2017-06-07 | 2018-12-28 | 扬州大学 | Polycaprolactone/cellulose composite material preparation method of controllable polycaprolactone crystallization |
| CN107216621A (en) * | 2017-07-18 | 2017-09-29 | 扬州大学 | A kind of preparation method of polyadipate butylene terephthalate composite |
| CN108250703A (en) * | 2018-03-01 | 2018-07-06 | 苏州维洛克电子科技有限公司 | A kind of cellulose-containing degradable polyester sheet material and preparation method thereof |
| RU2708396C1 (en) * | 2018-12-19 | 2019-12-06 | Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук | Biocompatible biodegradable osteoconductive polymer composite material for bone tissue regeneration |
| CN110670408B (en) * | 2019-10-17 | 2022-04-22 | 中国科学院理化技术研究所 | Hydrophobic slurry and preparation method and application thereof |
| CN111454556A (en) * | 2020-05-26 | 2020-07-28 | 扬州大学 | Preparation method of polycaprolactone nanofiber composite material |
| CN111748183A (en) * | 2020-06-23 | 2020-10-09 | 南宁学院 | Coupling modified CNF/PCL composite material and application thereof |
| WO2023180630A1 (en) | 2022-03-21 | 2023-09-28 | Aalto University Foundation Sr | Lignin nanoparticle stabilized composite material |
| CN114989582B (en) * | 2022-05-17 | 2024-05-03 | 福建省南安市帮登鞋业有限公司 | Preparation method for acetylation of cotton cellulose nanofiber/polycaprolactone composite material |
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| CN105601754A (en) * | 2016-01-06 | 2016-05-25 | 扬州大学 | Preparing method for acylated fiber nanocrystal |
| CN105754308A (en) * | 2016-03-21 | 2016-07-13 | 武汉理工大学 | Acetylated cellulose nanocrystalline composite modified biomass-based polyester material and preparation method thereof |
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