CN106750553A - Biodegradable composite and its preparation method and application - Google Patents
Biodegradable composite and its preparation method and application Download PDFInfo
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- CN106750553A CN106750553A CN201710121299.XA CN201710121299A CN106750553A CN 106750553 A CN106750553 A CN 106750553A CN 201710121299 A CN201710121299 A CN 201710121299A CN 106750553 A CN106750553 A CN 106750553A
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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
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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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
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The present invention relates to a kind of biodegradable composite and its preparation method and application.The preparation method of the composite is comprised the following steps：Plant fiber material is pre-processed, to destroy the fascicular texture of the plant fiber material, draw ratio is obtained and is 400~1000 string, then be placed in water and high shear dispersion is uniform, suction filtration, drying obtains plant fibre base material；Curing agent is dissolved in the first solvent, epoxidized soybean oil is subsequently adding, heating stirring adds the second solvent, obtains epoxidized soybean oil prepolymer solution after cooling；The epoxidized soybean oil prepolymer solution and the plant fibre base material are blended, solvent flashing obtains blend, are solidified again after the blend is carried out into precuring in a mold, obtained final product.The composite that the present invention is prepared possesses good biological degradability, good tensile strength, hydrophobicity and heat endurance.
Description
Technical field
The present invention relates to field of compound material, more particularly to a kind of biodegradable composite and preparation method thereof
And application.
Background technology
In the case of the crisis of resource and environmental pollution that petroleum base packaging material bring, research novel environmentally-friendly biological can drop
Solution packaging material have become the important problem field of researchers one, and domestic and foreign scholars have also carried out substantial amounts of research to this
And achieve more achievement in research.Representative packaging material have corrugation obtained in wherein with string as raw material
Paper, honeycomb paper, string/starch composite material, plant fiber/plastics composite material, paper mould, cellophane etc.,
These materials are mainly that to use waste paper fibre, paper pulp and crop material etc. be raw material by the skill such as foaming, extrusion, hot pressing and curtain coating
Art machine-shaping, possesses good biological degradability and environment friendly, is the study hotspot of modern packaging material.
However, still there are some defects, such as corrugated paper, honeybee in these packaging material obtained in string as raw material
Nest paper and paper mould etc. are serious to Forest resources dynamics, also easily cause water pollution, while this kind of materials water-resistant extreme difference；Plant
The shortcomings of there is not ideal enough complex process, material property and strong water imbibition in fibres/starch material, and cellophane system
Have during standby difficult forming, high cost and not environmentally the problems such as, plant fiber/plastics material there is also biodegradable
The deficiencies such as difference, interface cohesion difference.Therefore, it can be seen that for the research and development of the biodegradable packaging material of string, still depositing
Need further to solve in more problem.The lifting of its combination property, the simplification of preparation process are that this kind of material is able to extensively
The research tendency of application.
The materials such as plant oil-based thermoplastic resin, thermosetting resin have gradually been developed and have been usually applied quickly packing timber
The fields such as material, Medical Devices, commodity, agricultural, automobile, ship.Wherein epoxidized soybean oil as industrialized product
Through having obtained extensive research in the preparation of new material, the especially preparation of thermosetting resin, but still generally existing resin
The problem of intensity difference.
The content of the invention
Based on this, the invention provides a kind of preparation method of biodegradable composite, what is prepared is compound
Material possesses good biological degradability, good tensile strength, hydrophobicity and heat endurance.
Concrete technical scheme is as follows：
A kind of preparation method of biodegradable composite, comprises the following steps：
The preparation of plant fibre base material：Plant fiber material is pre-processed, to destroy the plant fiber material
Fascicular texture (reaches a point fine purpose), obtains the string A that draw ratio is 400~1000, and the string A is placed in
Simultaneously high shear dispersion is uniform in water, suction filtration, drying, obtains plant fibre base material；
The preparation of epoxidized soybean oil performed polymer：Curing agent is dissolved in the first solvent, epoxidized soybean oil is subsequently adding, heated
Stirring, adds the second solvent after cooling, obtain epoxidized soybean oil prepolymer solution；The curing agent is polynary acids curing agent
And/or polyatomic phenol curing agent；
The preparation of composite：The epoxidized soybean oil prepolymer solution and the plant fibre base material are blended, are volatilized
Solvent, obtains blend, is solidified again after the blend is carried out into precuring in a mold, obtains final product described biodegradable
Composite.Can be by way of spraying and impregnating by the epoxidized soybean oil prepolymer solution and the plant fibre base material
Blending.
Wherein in some embodiments, the plant fiber material is selected from flaxen fiber, bamboo fibre, wood-fibred, crops straw
At least one in stalk and bagasse.
Wherein in some embodiments, the polynary acids curing agent is selected from oxalic acid, citric acid, maleic acid, fourth two
At least one in acid, BTCA, the polyatomic phenol curing agent is tannic acid.
Wherein in some embodiments, the polynary acids curing agent is citric acid or BTCA.
Wherein in some embodiments, first solvent is water and/or absolute ethyl alcohol, and second solvent is acetone
And/or ethanol, the heating stirring is 10~30min of stirring at a temperature of 60~100 DEG C.
Wherein in some embodiments, the step of the preparation of composite described in the pressure of precuring be 1~10MPa,
Temperature is 120~160 DEG C, and the time is 5~30min；The pressure of the solidification is 0.5~5MPa, and temperature is 140~180 DEG C, when
Between be not less than 2h.
Wherein in some embodiments, the step of the preparation of composite described in the pressure of precuring be 4~6MPa, when
Between be 5~15min；The pressure of the solidification is 0.8~1.2MPa, and temperature is 160~180 DEG C, and the time is 2~4h.
Wherein in some embodiments, the method pre-processed described in the preparation process of plant fibre base material is grinding, height
Shearing homogeneous or steam blasting.
Wherein in some embodiments, the epoxy described in the preparation process of epoxidized soybean oil performed polymer in epoxidized soybean oil
The mol ratio of the hydroxy-acid group in group and the polynary acids curing agent is 1:0.5~1:2；Or in the epoxidized soybean oil
Epoxide group and the polyatomic phenol curing agent in the mol ratio of phenolic hydroxyl group be 1:0.8~1:1.6.
Wherein in some embodiments, the epoxy described in the preparation process of epoxidized soybean oil performed polymer in epoxidized soybean oil
The mol ratio of the hydroxy-acid group in group and the polynary acids curing agent is 1:0.8~1:1.2；Or the epoxidized soybean oil
In epoxide group and the polyatomic phenol curing agent in the mol ratio of phenolic hydroxyl group be 1:1.2~1:1.6.
Wherein in some embodiments, polynary acids curing agent and institute described in the preparation process of epoxidized soybean oil performed polymer
The mass ratio for stating the first solvent is 10:1~2:1；Or the polyatomic phenol curing agent is with the mass ratio of first solvent
1：6~1:10；And/or the concentration of epoxidized soybean oil performed polymer is 0.05~0.5g/ in the epoxidized soybean oil prepolymer solution
ml。
Wherein in some embodiments, polynary acids curing agent described in the preparation process of epoxidized soybean oil performed polymer and
The mass ratio of one solvent is 4:1~2:1；Or the polyatomic phenol curing agent and the mass ratio of first solvent are 1:7~
1:9；And/or the concentration of epoxidized soybean oil performed polymer is 0.1~0.3g/ml in the epoxidized soybean oil prepolymer solution.
Wherein in some embodiments, the step of the preparation of composite described in epoxidized soybean oil prepolymer solution
Epoxidized soybean oil performed polymer is 0.1-1 with the mass ratio of the plant fibre base material:1, i.e., described plant fibre base material is described
Mass percent in biodegradable composite is 50~90.9%.
Wherein in some embodiments, the step of the preparation of composite described in epoxidized soybean oil prepolymer solution
Epoxidized soybean oil performed polymer is 0.4-0.8 with the mass ratio of the plant fibre base material:1, i.e., described plant fibre base material is in institute
It is 55.6~71.4% to state the mass percent in biodegradable composite.
Wherein in some embodiments, the step of the preparation of composite described in epoxidized soybean oil prepolymer solution
Epoxidized soybean oil performed polymer is 0.55-0.65 with the mass ratio of the plant fibre base material:1, i.e., described plant fibre base material exists
Mass percent in the biodegradable composite is 60.6~64.5%.
Present invention also offers a kind of biodegradable composite.
Concrete technical scheme is as follows：
The biodegradable composite prepared by above-mentioned preparation method.
Present invention also offers the application of above-mentioned biodegradable composite.
Concrete technical scheme is as follows：
Application of the above-mentioned biodegradable composite in packaging material are prepared.
Biodegradable composite of the invention and its preparation method and application has advantages below and beneficial effect：
1st, with epoxy soybean oil resin to being modified by the string after pretreatment point fibre, be obtained to give birth to the present invention
The novel environment-friendly composite material of thing degraded, wherein, epoxy soybean oil resin is solid in polyacid or polyhydric phenols by epoxidized soybean oil
Prepared under conditions of agent.The chemical crossbond of the composite is mainly ester bond and ehter bond, easily by soil in it is micro-
Enzyme attack secreted by biology and degrade, thus possess good biological degradability.Prepared with preparation method of the invention
Composite also there is good tensile strength simultaneously, with relatively low water absorption rate and larger contact angle, hydrophobicity is good,
In addition excellent interfacial bonding property is also equipped with, with excellent combination property.
2nd, the crosslinking of the epoxy soybean oil resin prepared as curing agent using polyacid and polyhydric phenols in existing method
Low, intensity difference is spent, using more difficulty, the concern being subject in the field is less, and the present invention is by the epoxy soybean oil resin to planting
Fibres are modified the environment friendly composite material that can prepare excellent combination property, realize the efficient utilization to this resinoid.
3rd, the epoxy soybean oil resin in the present invention possesses amphipathic, and its reason is that it both has hydrophobic aliphatic acid alkane
Base long-chain, there is also the hydroxyl and the complete carboxyl of unreacted remained after epoxide group open loop.Resin is in string matrix
During middle crosslinking curing, carboxylic acid and hydroxyl isopolarity group have preferable Chemical Physics to be combined with string, form preferable
Interface compatibility.Compared with traditional oil based polyalcohol (polyethylene, polypropylene etc.), it is not necessary to which extra processing procedure is with regard to energy
Good interface cohesion is reached, so as to lift the combination property of prepared composite.
4th, the composite prepared by the present invention, renewable resource of its raw material sources in nature, and it is cheap easy
, be conducive to mitigating the dependence to petroleum resources, overcome petroleum base resin resource exhaustion caused in use, ring
The problems such as border is polluted.Its biological degradability is good, is conducive to mitigating the burden of environment, to promoting low-carbon environment-friendly and sustainable economic
Development is significant.
5th, in the preparation process of composite of the present invention in addition to curing agent, it is not necessary to add other catalyst, choose
Solvent is cheap, low toxicity, easily reclaim, solidification process is simple and environmentally-friendly, easily realizes industrialization, is its large-scale preparation and application
There is provided certain basis.
6th, the composite that the present invention is prepared is applied as packaging material, solving conventional packaging material can
Biological degradability, water resistance, interfacial bonding property and mechanical property are difficult to the problem taken into account, and are expected to enter in packaging material field
The extensive exploitation of row and application, are research and the broader thinking of application extension of new packaging material.
Brief description of the drawings
Fig. 1 is the graph of stretch performance of biodegradable composite prepared by the present invention；
Fig. 2 is the contact angle figure of biodegradable composite prepared by the present invention；
Fig. 3 is the water absorption rate variation diagram of biodegradable composite prepared by the present invention.
Specific embodiment
The present invention is illustrated below by way of instantiation, but the present invention is not merely defined in these examples.
Embodiment 1
The present embodiment provides a kind of biodegradable composite, and its preparation method is comprised the following steps：
(1) preparation of plant fibre base material：About 1cm sisal fibers long are pre-processed with steam blasting, to destroy
Its fascicular texture, obtains sisal fiber (the Steam explosion of the steam blasting of draw ratio larger (400~1000)
Sisal fiber, SESF).SESF is placed in water and is uniformly dispersed at a high speed with high shear dispersion machine, the mass ratio of SESF and water
It is 1：100, suction filtration, drying are finally carried out, obtain the SESF base materials that thickness is 0.5mm.
(2) preparation of ESOCA performed polymers：Take 4 parts of CA (citric acid) to be dissolved at 90 DEG C in 1 part of deionized water, treat that CA is complete
ESO (epoxidized soybean oil) is added after CL, blend is stirred into 15min at 90 DEG C, obtain translucent performed polymer, finally existed
Acetone is added in performed polymer after cooling, the ESOCA prepolymer solutions that concentration is 0.2g/ml are obtained；The quality of ESO is pressed in ESO
Epoxide group is 1 with the mol ratio of hydroxy-acid group in CA:1 calculated obtained by.
(3) preparation of SESF/ESOCA composites：Take ESOCA prepolymer solutions to be uniformly sprayed on SESF base materials, control
ESOCA performed polymers processed are 0.6 with the mass ratio of SESF base materials：1, after after acetone volatilization by ESOCA performed polymers and SESF base materials
Blend is placed in mould, and at 120 DEG C, precuring 10min under the conditions of 5Mpa, then at 160 DEG C, is placed under conditions of 1Mpa
Solidify 2h in baking oven, obtain SESF/ESOCA composites, in obtained composite, the mass percent of ESOCA resins is
37.5% (i.e. the mass percent of plant fibre base material is 62.5%), is designated as SESF/ESOCA37.5.
Embodiment 2
The present embodiment provides a kind of biodegradable composite, its preparation method substantially with embodiment 1, except control
ESOCA performed polymers are 0.4 with the mass ratio of SESF base materials：1, other steps and parameter are consistent with embodiment 1, obtained composite wood
The mass percent of ESOCA resins is 28.6% (i.e. the mass percent of plant fibre base material is 71.4%) in material, is designated as
SESF/ESOCA28.6。
Embodiment 3
The present embodiment provides a kind of biodegradable composite, its preparation method substantially with embodiment 1, except control
ESOCA performed polymers are 0.8 with the mass ratio of SESF base materials：1, other steps and parameter are consistent with embodiment 1, obtained composite wood
The mass percent of ESOCA resins is 44.4% (i.e. the mass percent of plant fibre base material is 55.6%) in material, is designated as
SESF/ESOCA44.4。
Embodiment 4
The present embodiment provides a kind of biodegradable composite, its preparation method substantially with embodiment 1, except used
String is Eucalyptus (Eucalyptus wood, EW) fiber, obtains Eucalyptus Fibers (the Steam explosion of steam blasting
Eucalyptus wood, SEEW), other steps and parameter are consistent with embodiment 1, ESOCA resins in obtained composite
Mass percent is 37.5%, is designated as SEEW/ESOCA37.5.
Embodiment 5
The present embodiment provides a kind of biodegradable composite, its preparation method substantially with embodiment 1, except sisal hemp
The preprocess method of fiber is different, and the present embodiment is that sisal fiber is pre-processed by high shear homogenous disperse machine, is obtained
The string (High shear sisal fibre, HSSF) of high shear treatment, other steps and parameter and embodiment 1 one
Cause, the mass percent of ESOCA resins is that 37.5% (i.e. the mass percent of plant fibre base material is in obtained composite
62.5%), it is designated as HSSF/ESOCA37.5.
Embodiment 6
The present embodiment provides a kind of biodegradable composite, and its preparation method is comprised the following steps：
(1) with embodiment 1 the step of (1) is identical.
(2) preparation of ESOMA performed polymers：Take 4 parts of MA (maleic acid) to be dissolved at 90 DEG C in 1 part of ionized water, treat
MA adds ESO to stir after being completely dissolved, and blend is stirred into 15min at 90 DEG C, obtains translucent performed polymer, finally exists
Acetone is added in performed polymer after cooling, the ESOCA prepolymer solutions that concentration is 0.2g/ml are obtained；The quality of ESO is pressed in ESO
Epoxide group is 1 with the mol ratio of hydroxy-acid group in MA:1 calculated obtained by.
(3) preparation of SESF/ESOMA composites：Preparation process with the step of embodiment 1 (3) is consistent, controls ESOMA
Performed polymer is 0.6 with the mass ratio of SESF base materials：1, in obtained composite, the mass percent of ESOMA resins is
37.5% (i.e. the mass percent of plant fibre base material is 62.5%), is designated as SESF/ESOMA37.5.
Embodiment 7
The present embodiment provides a kind of biodegradable composite, and its preparation method is comprised the following steps：
(1) with embodiment 1 the step of (1) is identical.
(2) preparation of ESOBTCA performed polymers：Take 4 parts of BTCA (BTCA) be dissolved at 90 DEG C 1 part of deionized water and
In 1 part of mixed thing solvent of absolute ethyl alcohol, add ESO to stir after BTCA is completely dissolved, blend is stirred at 90 DEG C
15min, obtains translucent performed polymer, finally adds acetone in performed polymer after the cooling period, and it is 0.2g/ml's to obtain concentration
ESOBTCA prepolymer solutions；It is 1 that the quality of ESO presses ESO epoxide epoxy group groups with the mol ratio of hydroxy-acid group in BTCA:1 is counted
Calculate gained.
(3) preparation of SESF/ESOBTCA composites：Preparation process with the step of embodiment 1 (3) is consistent, control
ESOBTCA performed polymers are 0.6 with the mass ratio of SESF base materials:1, in obtained composite, the quality percentage of ESOBTCA resins
Than being 37.5% (i.e. the mass percent of plant fibre base material is 62.5%), SESF/ESOBTCA37.5 is designated as.
Embodiment 8
The present embodiment provides a kind of biodegradable composite, and its preparation method is comprised the following steps：
(1) with embodiment 1 the step of (1) is identical.
(2) preparation of ESOTA performed polymers：Take 1 part of TA (tannic acid) to be dissolved in 8 parts of absolute ethyl alcohols, be subsequently adding ESO stirrings
Uniformly, blend is stirred into 30min at 75 DEG C, obtains brown color clear prepolymer liquid solution, finally performed polymer after the cooling period
Ethanol is added in solution, the ESOTA prepolymer solutions that concentration is 0.2g/ml are obtained；The quality of ESO press ESO epoxide epoxy group groups with
The mol ratio of phenolic hydroxyl group is 1 in TA:1.4 calculated obtained by.
(3) preparation of SESF/ESOTA composites：ESOTA prepolymer solutions are uniformly sprayed on SESF base materials, are controlled
ESOTA performed polymers processed are 0.6 with the mass ratio of SESF base materials：1, after after ethanol volatilization by ESOTA performed polymers and SESF base materials
Mixture is placed in mould, and at 160 DEG C, then precuring 10min under the conditions of 5Mpa is placed under conditions of 180 DEG C, 1Mpa
Solidify 2h in baking oven, obtain SESF/ESOTA composites, in obtained composite, the mass percent of ESOTA resins is
37.5% (i.e. the mass percent of plant fibre base material is 62.5%), is designated as SESF/ESOTA37.5.
The performance test of embodiment 9
Biodegradable composite prepared by embodiment 1-8 is carried out into following performance test：
1st, tensile property test：
Tester is the desk-top universal testing machine (instron5566) of Instron Corporation of the U.S., is carried out with it
The test of tensile property.Test condition：22 DEG C of temperature, humidity 30%RH, gauge length 20mm, rate of extension is 2mm/min, repeats 5
It is secondary to average.
Tensile property test result is as shown in figure 1, can be seen that the tensile strength of pure ESO resins by extension test result
Be below 1MPa, the tensile strength of SESF plant fibre base materials is 5.3MPa, by ESO resins modified its tensile strength most
Height is promoted to 31.2MPa.Wherein for the ESOCA resins of different content, tensile strength reaches maximum when content is 37.5%, main
If due to ESO resins exist it is amphipathic, good interface cohesion can be formed with string, string is played well
Cementation, ESO resin contents increase bond effect enhancing, but too high ESO resin contents can be because of its own intensity not
Foot causes the reduction of the tensile strength of composite.Secondly tensile strength influence of the different curing agent on composite also differs
Cause, more preferably, the interface cohesion with string is also stronger, and its intensity can be higher for its solidification effect in curing agent more than carboxyl-content
Some.And polyhydric phenols curing agent, easily by resin-coating, is not easy between string because its phenolic hydroxyl group steric hindrance is larger
Interface cohesion, causes intensity slightly to reduce.
2nd, contact angle test：
Contact angle instrument is the Surface Tension Surface contact angle tester of German dataphysics companies
(OCA40Micro), each sample tests five points, averages.
Contact angle test result as shown in Fig. 2 as seen from Figure 2, the contact angle of pure ESO resins be substantially at 70 °~
Between 80 °, less than 90 °, stronger hydrophily is shown, while because the differential curing ESO resin surfaces for obtaining of curing agent connect
Feeler there is also slight difference.Secondly, for SESF base materials, because of its extremely strong water imbibition and larger porosity, do not obtain
Contact angular data, and by after ESO resin modifieds, contact angle dramatically increases (composite shown in four figures of Fig. 2 top halfs
Surface contact angle respectively be 130.1 °, 109.6 °, 108.9 °, 129.4 °), show good hydrophobicity.Mainly
Because the polar group of ESO resin beds causes that composite material surface resin is presented more length with plant fibre surface hydroxy combining
Alkyl chain increases so as to cause contact angle.Additionally, SESF/ESOMA37.5 contact angles also have maleic acid two the reason for larger
Individual carboxyl both participates in curing reaction so that system polar group is less compared with other systems, so as to cause contact angle bigger.SESF/
The reason for ESOTA37.5 contact angles are larger is, because unreacted phenolic hydroxyl group steric hindrance is larger, to be easily wrapped in inside resin, is caused
Surface polar groups are also on the low side so that contact angle is relatively bigger.
3rd, water absorption rate test：
Testing sample is cut into the batten of 20mm × 20mm, is weighed after drying.Then it is immersed into deionized water, every one
Taken out after the section time, surface moisture is wiped with blotting paper, weighed, until quality no longer changes, record it in different time points
Weight amount, its absorptivity X=(Wh-Wd)/Wd × 100%.
Wd is weight when composite (testing sample) is dried in formula, and Wh is after composite (testing sample) absorbs water
Weight, each sample test five times, takes its average value.
Water absorption rate test result is as shown in figure 3, as seen from Figure 3, SESF plant fibre base materials are fast with the water suction being exceedingly fast
Degree reaches 580%, and after ESO resins are added, its water absorption rate is remarkably decreased, and pure ESO resins water absorption rate is respectively less than 9%.
In polyacid curative systems, with increasing for carboxyl quantity, more preferably, secondly polar group increases and causes interface to tie solidification effect
Get togather, so that water absorption rate constantly declines, the water absorption rate of tri- kinds of system composites of MA, CA and BTCA is respectively 31%,
16.2% and 15.4.And TA systems cause water absorption rate to have a certain degree of rising also because its interface cohesion is slightly worse, its value is
20.6%.
As can be seen that its solidification effect of different curing agent is different, the content of system polar group is also different, causes ESO trees
Fat is also different from the interface cohesion of string, therefore the water absorption rate of gained composite, tensile strength and surface contact angle are equal
Slightly difference.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of biodegradable composite, it is characterised in that comprise the following steps：
The preparation of plant fibre base material：Plant fiber material is pre-processed, to destroy the pencil of the plant fiber material
Structure, obtains the string A that draw ratio is 400~1000, the string A is placed in water and high shear dispersion is equal
Even, suction filtration, drying obtains plant fibre base material；
The preparation of epoxidized soybean oil performed polymer：Curing agent is dissolved in the first solvent, epoxidized soybean oil is subsequently adding, heating is stirred
Mix, the second solvent is added after cooling, obtain epoxidized soybean oil prepolymer solution；The curing agent is polynary acids curing agent
And/or polyatomic phenol curing agent；
The preparation of composite：The epoxidized soybean oil prepolymer solution and the plant fibre base material are blended, solvent flashing,
Blend is obtained, is solidified again after the blend is carried out into precuring in a mold, obtained final product described biodegradable compound
Material.
2. the preparation method of biodegradable composite according to claim 1, it is characterised in that the polyacid
Class curing agent is selected from least one in oxalic acid, citric acid, maleic acid, succinic acid, BTCA, the polyatomic phenol
Curing agent is tannic acid.
3. the preparation method of biodegradable composite according to claim 1, it is characterised in that described first is molten
Agent is water and/or absolute ethyl alcohol, and second solvent is acetone and/or ethanol, and the heating stirring is the temperature at 60~100 DEG C
10~30min of the lower stirring of degree.
4. the preparation method of the biodegradable composite according to claim any one of 1-3, it is characterised in that multiple
The pressure of precuring described in the step of preparation of condensation material be 1~10MPa, temperature be 120~160 DEG C, the time be 5~
30min；The pressure of the solidification is 0.5~5MPa, and temperature is 140~180 DEG C, and the time is not less than 2h.
5. the preparation method of the biodegradable composite according to claim any one of 1-3, it is characterised in that plant
The method pre-processed described in the preparation process of fibres base material is grinding, high shear homogeneous or steam blasting.
6. the preparation method of the biodegradable composite according to claim any one of 1-3, it is characterised in that ring
In epoxide group described in the preparation process of oxygen soybean oil performed polymer in epoxidized soybean oil and the polynary acids curing agent
The mol ratio of hydroxy-acid group is 1:0.5~1:2；Or the epoxide group in the epoxidized soybean oil solidifies with the polyatomic phenol
The mol ratio of the phenolic hydroxyl group in agent is 1:0.8~1:1.6.
7. the preparation method of the biodegradable composite according to claim any one of 1-3, it is characterised in that ring
Polynary acids curing agent described in the preparation process of oxygen soybean oil performed polymer is 10 with the mass ratio of first solvent:1~2:
1；Or the polyatomic phenol curing agent and the mass ratio of first solvent are 1：6~1:10；And/or the epoxidized soybean oil
The concentration of epoxidized soybean oil performed polymer is 0.05~0.5g/ml in prepolymer solution.
8. the preparation method of the biodegradable composite according to claim any one of 1-3, it is characterised in that multiple
Epoxidized soybean oil performed polymer described in the step of preparation of condensation material in epoxidized soybean oil prepolymer solution is fine with the plant
The mass ratio of Wiki material is 0.1-1:1.
9. the biodegradable composite that the preparation method described in any one of claim 1-8 is prepared.
10. application of the biodegradable composite described in claim 9 in packaging material are prepared.
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| CN108148292A (en) * | 2017-12-08 | 2018-06-12 | 安徽京鸿密封件技术有限公司 | A kind of electric vehicle charging rifle AC charging socket seal circle |
| CN109159242A (en) * | 2018-09-17 | 2019-01-08 | 佛山市森昂生物科技有限公司 | A kind of preparation method of moisture-proof biomass fiber plate |
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| CN110229531A (en) * | 2019-07-11 | 2019-09-13 | 江南大学 | A kind of complete bio-based source epoxy resin composite material and preparation method thereof |
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| CN109159242A (en) * | 2018-09-17 | 2019-01-08 | 佛山市森昂生物科技有限公司 | A kind of preparation method of moisture-proof biomass fiber plate |
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| CN109320933B (en) * | 2018-10-16 | 2021-03-16 | 福建农林大学 | Reinforced and toughened bamboo fiber/polylactic acid composite material and preparation method thereof |
| CN110229531A (en) * | 2019-07-11 | 2019-09-13 | 江南大学 | A kind of complete bio-based source epoxy resin composite material and preparation method thereof |
| CN110229531B (en) * | 2019-07-11 | 2021-03-23 | 江南大学 | Completely bio-based epoxy resin composite material and preparation method thereof |
| CN113969065A (en) * | 2021-11-11 | 2022-01-25 | 蒋华 | Biodegradable composite material and preparation method thereof |
| CN113969065B (en) * | 2021-11-11 | 2023-10-24 | 仙桃康寿降解材料有限公司 | Biodegradable composite material and preparation method thereof |
| CN115991798A (en) * | 2023-02-16 | 2023-04-21 | 南京工业大学 | Bio-based hemicellulose film material and preparation method thereof |
| CN115991798B (en) * | 2023-02-16 | 2024-02-06 | 南京工业大学 | Bio-based hemicellulose film material and preparation method thereof |
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