CN106750553B - Biodegradable composite material and preparation method and application - Google Patents
Biodegradable composite material and preparation method and application Download PDFInfo
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- CN106750553B CN106750553B CN201710121299.XA CN201710121299A CN106750553B CN 106750553 B CN106750553 B CN 106750553B CN 201710121299 A CN201710121299 A CN 201710121299A CN 106750553 B CN106750553 B CN 106750553B
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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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- 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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- 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 material and preparation methods and application.The composite material is using pure epoxy soybean oil resin as adhesive, and it is blended with plant fibre base material, prepare the composite board of high-content plant fiber, its preparation method to destroy the fascicular texture of the plant fiber material, obtains the plant fiber that draw ratio is 400~1000 the following steps are included: pre-process to plant fiber material, it is placed it in water again and high shear dispersion is uniform, it filters, drying obtains plant fibre base material；Polyacid or polyphenol curing agent are dissolved in the first solvent, epoxidized soybean oil is then added, heating stirring prepares performed polymer, adds the second solvent after cooling, obtain epoxidized soybean oil prepolymer solution；The epoxidized soybean oil prepolymer solution is blended with the plant fibre base material, solvent flashing obtains blend, by the blend in a mold carry out segmentation hot-press solidifying to get.The composite material that the present invention is prepared has good biological degradability, good tensile strength, hydrophobicity and thermal stability.
Description
Technical field
The present invention relates to field of compound material, more particularly to a kind of biodegradable composite material and preparation method
And application.
Background technique
In the case where the crisis of resource and environmental pollution that petroleum base packaging material is brought, research novel environmentally-friendly biological can drop
Solution packaging material has become researchers one important project field, and domestic and foreign scholars have also carried out a large amount of research to this
And achieve more research achievement.Wherein there is corrugation by packaging material representative made from raw material of plant fiber
Paper, honeycomb paper, plant fiber/starch composite material, plant fiber/plastics composite material, paper mould, cellophane etc.,
These materials are mainly use waste paper fibre, paper pulp and crop material etc. to pass through the skills such as foaming, extrusion, hot pressing and curtain coating for raw material
Art machine-shaping has good biological degradability and environment friendly, is the research hotspot of modern packaging material.
However, these still remain some defects, such as corrugated paper, bee by packaging material made from raw material of plant fiber
Nest paper and paper mould etc. are serious to Forest resources dynamics, also be easy to cause water pollution, while this kind of materials water-resistant is very poor；It plants
Fibres/starch material there are complex process, material property is not ideal enough and water imbibition is strong the disadvantages of, and cellophane system
Have during standby difficult forming, it is at high cost and not environmentally the problems such as, there is also biodegradables for plant fiber/plastics material
Difference, the deficiencies of interface cohesion is poor.Therefore, it can be seen that the research and development of packaging material biodegradable for plant fiber, are still deposited
It needs further to solve in more problem.The promotion of its comprehensive performance, 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 are gradually developed and are usually applied quickly to packing timber
The fields such as material, Medical Devices, daily necessities, agricultural, automobile, ship.Wherein epoxidized soybean oil as industrialized product
Through having obtained the preparation of extensive research, especially thermosetting resin in the preparation of new material, but still generally existing resin
The problem of intensity difference.
Summary of the invention
Based on this, the present invention provides a kind of preparation methods of biodegradable composite material, and what is be prepared is compound
Material has good biological degradability, good tensile strength, hydrophobicity and thermal stability.
Specific technical solution is as follows:
A kind of preparation method of biodegradable composite material, comprising the following steps:
The preparation of plant fibre base material: pre-processing plant fiber material, to destroy the plant fiber material
Fascicular texture (achievees the purpose that a point fibre), obtains the plant fiber A that draw ratio is 400~1000, the plant fiber A is placed in
In water and high shear dispersion is uniform, filters, and drying obtains plant fibre base material；
The preparation of epoxidized soybean oil performed polymer: curing agent is dissolved in the first solvent, and epoxidized soybean oil is then added, heating
Stirring adds the second solvent after cooling, obtains epoxidized soybean oil prepolymer solution；The curing agent is polynary acids curing agent
And/or polyatomic phenol curing agent；
The preparation of composite material: the epoxidized soybean oil prepolymer solution is blended with the plant fibre base material, volatilization
Solvent obtains blend, solidifies again after the blend is carried out precuring in a mold to get described biodegradable
Composite material.It can be by way of spraying and impregnating by the epoxidized soybean oil prepolymer solution and the plant fibre base material
It is blended.
In wherein some embodiments, the plant fiber material is selected from flaxen fiber, bamboo fibre, wood-fibred, crops straw
At least one of stalk and bagasse.
In wherein some embodiments, the polynary acids curing agent is selected from oxalic acid, citric acid, maleic acid, fourth two
At least one of acid, butane tetracarboxylic acid, the polyatomic phenol curing agent are tannic acid.
In wherein some embodiments, the polynary acids curing agent is citric acid or butane tetracarboxylic acid.
In wherein some embodiments, first solvent is water and/or dehydrated alcohol, and second solvent is acetone
And/or ethyl alcohol, the heating stirring be 60~100 DEG C at a temperature of stir 10~30min.
In wherein some embodiments, the step of the preparation of composite material described in the pressure of precuring be 1~10MPa,
Temperature is 120~160 DEG C, and the time is 5~30min；The cured pressure is 0.5~5MPa, and temperature is 140~180 DEG C, when
Between be not less than 2h.
In wherein some embodiments, the step of the preparation of composite material described in the pressure of precuring be 4~6MPa, when
Between be 5~15min；The cured pressure is 0.8~1.2MPa, and temperature is 160~180 DEG C, and the time is 2~4h.
In wherein some embodiments, pretreated method described in the preparation step of plant fibre base material is grinding, height
Shear homogeneous or steam blasting.
Epoxy in wherein some embodiments, in epoxidized soybean oil described in the preparation step of epoxidized soybean oil performed polymer
The molar ratio of carboxylic acid group in group and the polynary acids curing agent is 1:0.5~1:2；Or in the epoxidized soybean oil
Epoxy group and the polyatomic phenol curing agent in phenolic hydroxyl group molar ratio be 1:0.8~1:1.6.
Epoxy in wherein some embodiments, in epoxidized soybean oil described in the preparation step of epoxidized soybean oil performed polymer
The molar ratio of carboxylic acid group in group and the polynary acids curing agent is 1:0.8~1:1.2；Or the epoxidized soybean oil
In epoxy group and the polyatomic phenol curing agent in phenolic hydroxyl group molar ratio be 1:1.2~1:1.6.
In wherein some embodiments, polynary acids curing agent and institute described in the preparation step of epoxidized soybean oil performed polymer
The mass ratio for stating the first solvent is 10:1~2:1；Or the mass ratio of the polyatomic phenol curing agent and first solvent is
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。
In wherein some embodiments, polynary acids curing agent described in the preparation step of epoxidized soybean oil performed polymer and
The mass ratio of one solvent is 4:1~2:1；Or the mass ratio of the polyatomic phenol curing agent and first solvent be 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.
In wherein some embodiments, the step of the preparation of composite material described in epoxidized soybean oil prepolymer solution
The mass ratio of epoxidized soybean oil performed polymer and the plant fibre base material is 0.1-1:1, i.e., the described plant fibre base material is described
Mass percent in biodegradable composite material is 50~90.9%.
In wherein some embodiments, the step of the preparation of composite material described in epoxidized soybean oil prepolymer solution
The mass ratio of epoxidized soybean oil performed polymer and the plant fibre base material is 0.4-0.8:1, i.e., the described plant fibre base material is in institute
Stating the mass percent in biodegradable composite material is 55.6~71.4%.
In wherein some embodiments, the step of the preparation of composite material described in epoxidized soybean oil prepolymer solution
The mass ratio of epoxidized soybean oil performed polymer and the plant fibre base material is 0.55-0.65:1, i.e., the described plant fibre base material exists
Mass percent in the biodegradable composite material is 60.6~64.5%.
The present invention also provides a kind of biodegradable composite materials.
Specific technical solution is as follows:
The biodegradable composite material being prepared by above-mentioned preparation method.
The present invention also provides the applications of above-mentioned biodegradable composite material.
Specific technical solution is as follows:
Above-mentioned biodegradable composite material is preparing the application in packaging material.
Biodegradable composite material and preparation method and application of the invention has the following advantages and beneficial effects:
1, the present invention is modified the plant fiber after pretreatment point is fine with epoxy soybean oil resin, and being made can give birth to
The novel environment-friendly composite material of object degradation, wherein epoxy soybean oil resin is solid in polyacid or polyphenol by epoxidized soybean oil
It is prepared under conditions of agent.The chemical crossbond of the composite material is mainly ester bond and ehter bond, is easy by micro- in soil
Enzyme attack secreted by biology and degrade, thus have good biological degradability.It is prepared with preparation method of the invention
Composite material simultaneously also have good tensile strength, have lower water absorption rate and biggish contact angle, hydrophobicity is good,
Furthermore it is also equipped with excellent interfacial bonding property, there is excellent comprehensive performance.
2, the crosslinking for the epoxy soybean oil resin being prepared using polyacid and polyphenol as curing agent in existing method
Low, intensity difference is spent, application is more difficult, and less in the concern that the field is subject to, the present invention is by the epoxy soybean oil resin to plant
Fibres are modified the environment friendly composite material that can prepare excellent combination property, realize the efficient utilization to this resinoid.
3, the epoxy soybean oil resin in the present invention has amphipathic, the reason is that it had both had hydrophobic fatty acid alkane
Base long-chain, there is also the remaining hydroxyl of institute and the complete carboxyls of unreacted after epoxy group open loop.Resin is in plant fiber matrix
When middle crosslinking curing, carboxylic acid and hydroxyl isopolarity group are formed preferable in conjunction with plant fiber having preferable Chemical Physics
Interface compatibility.Compared with traditional petroleum based polyalcohol (polyethylene, polypropylene etc.), additional treatment process energy is not needed
Reach good interface cohesion, to promote the comprehensive performance of prepared composite material.
4, the composite material prepared by the present invention, renewable resource of the raw material sources in nature, and it is cheap easy
, be conducive to mitigate the dependence to petroleum resources, resource exhaustion, ring caused by overcoming petroleum base resin in use
The problems such as border is polluted.Its biological degradability is good, is conducive to the burden for mitigating environment, to promoting low-carbon environment-friendly and sustainable economic
Development is of great significance.
5, it in the preparation process of composite material of the present invention in addition to curing agent, does not need that other catalyst are added, choose
Solvent is cheap, low toxicity, Yi Huishou, solidification process is simple and environmentally-friendly, easily realizes industrialization, is its large-scale preparation and application
Provide certain basis.
6, the composite material 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 of taking into account, be expected to packaging material field into
The extensive exploitation of row and application are the research and the broader thinking of application extension of new packaging material.
Detailed description of the invention
Fig. 1 is the graph of stretch performance of biodegradable composite material prepared by the present invention；
Fig. 2 is the contact angle figure of biodegradable composite material prepared by the present invention；
Fig. 3 is the water absorption rate variation diagram of biodegradable composite material prepared by the present invention.
Specific embodiment
Illustrate the present invention below by way of specific example, but the present invention is not merely defined in these examples.
Embodiment 1
The present embodiment provides a kind of biodegradable composite materials, and preparation method includes the following steps:
(1) preparation of plant fibre base material: the sisal fiber of about 1cm long is pre-processed with steam blasting, to destroy
Its fascicular texture obtains sisal fiber (the Steam explosion of the steam blasting of major diameter bigger (400~1000)
Sisal fiber, SESF).SESF is placed in water and uses high shear dispersion machine high speed dispersion uniform, the mass ratio of SESF and water
It for 1:100, finally filtered, dried, obtain the SESF substrate with a thickness of 0.5mm.
(2) preparation of ESOCA performed polymer: taking 4 parts of CA (citric acid) to be dissolved in 1 part of deionized water at 90 DEG C, complete to CA
ESO (epoxidized soybean oil) is added after fully dissolved, blend is stirred into 15min at 90 DEG C, translucent performed polymer is obtained, finally exists
Acetone is added in performed polymer after cooling, obtains the ESOCA prepolymer solution that concentration is 0.2g/ml；The quality of ESO is by ESO
Epoxy group and the molar ratio of carboxylic acid group in CA are obtained by 1:1 is calculated.
(3) preparation of SESF/ESOCA composite material: taking ESOCA prepolymer solution to be uniformly sprayed on SESF substrate, control
The mass ratio of ESOCA performed polymer processed and SESF substrate is 0.6:1, by ESOCA performed polymer and SESF substrate after acetone volatilization
Blend is placed in mold, and at 120 DEG C, precuring 10min under the conditions of 5Mpa is placed under conditions of 1Mpa then at 160 DEG C
Solidify 2h in baking oven, obtain SESF/ESOCA composite material, in obtained composite material, the mass percent of ESOCA resin is
37.5% (i.e. the mass percent of plant fibre base material is 62.5%), is denoted as SESF/ESOCA37.5.
Embodiment 2
The present embodiment provides a kind of biodegradable composite materials, and preparation method is substantially with embodiment 1, in addition to control
The mass ratio of ESOCA performed polymer and SESF substrate is that 0.4:1, other steps and parameter and embodiment 1 are consistent, composite wood obtained
The mass percent of ESOCA resin is 28.6% (i.e. the mass percent of plant fibre base material is 71.4%) in material, is denoted as
SESF/ESOCA28.6。
Embodiment 3
The present embodiment provides a kind of biodegradable composite materials, and preparation method is substantially with embodiment 1, in addition to control
The mass ratio of ESOCA performed polymer and SESF substrate is that 0.8:1, other steps and parameter and embodiment 1 are consistent, composite wood obtained
The mass percent of ESOCA resin is 44.4% (i.e. the mass percent of plant fibre base material is 55.6%) in material, is denoted as
SESF/ESOCA44.4。
Embodiment 4
The present embodiment provides a kind of biodegradable composite materials, and preparation method is substantially with embodiment 1, in addition to used
Plant fiber 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 resin in composite material obtained
Mass percent is 37.5%, is denoted as SEEW/ESOCA37.5.
Embodiment 5
The present embodiment provides a kind of biodegradable composite materials, and preparation method is substantially with embodiment 1, in addition to sisal hemp
The preprocess method of fiber is different, and the present embodiment is to be pre-processed by high shear homogenous disperse machine to sisal fiber, obtains
The plant fiber (High shear sisal fibre, HSSF) of high shear treatment, other steps and parameter and embodiment 1 one
It causes, the mass percent of ESOCA resin is 37.5% (i.e. the mass percent of plant fibre base material is in composite material obtained
62.5%), it is denoted as HSSF/ESOCA37.5.
Embodiment 6
The present embodiment provides a kind of biodegradable composite materials, and preparation method includes the following steps:
(1) identical as (1) the step of embodiment 1.
(2) preparation of ESOMA performed polymer: taking 4 parts of MA (maleic acid) to be dissolved in 1 part of ionized water at 90 DEG C, to
MA is added ESO after being completely dissolved and stirs evenly, and blend is stirred 15min at 90 DEG C, translucent performed polymer is obtained, finally exists
Acetone is added in performed polymer after cooling, obtains the ESOCA prepolymer solution that concentration is 0.2g/ml；The quality of ESO is by ESO
Epoxy group and the molar ratio of carboxylic acid group in MA are obtained by 1:1 is calculated.
(3) preparation of SESF/ESOMA composite material: it is consistent with the preparation process of 1 step of embodiment (3), control ESOMA
The mass ratio of performed polymer and SESF substrate is 0.6:1, and in obtained composite material, the mass percent of ESOMA resin is
37.5% (i.e. the mass percent of plant fibre base material is 62.5%), is denoted as SESF/ESOMA37.5.
Embodiment 7
The present embodiment provides a kind of biodegradable composite materials, and preparation method includes the following steps:
(1) identical as (1) the step of embodiment 1.
(2) preparation of ESOBTCA performed polymer: take 4 parts of BTCA (butane tetracarboxylic acid) be dissolved at 90 DEG C 1 part of deionized water and
In the mixed object solvent of 1 part of dehydrated alcohol, ESO is added after BTCA is completely dissolved and stirs evenly, blend is stirred at 90 DEG C
15min obtains translucent performed polymer, and acetone finally is added in performed polymer after the cooling period, and obtaining concentration is 0.2g/ml's
ESOBTCA prepolymer solution；The quality of ESO is based on 1:1 is carried out by the molar ratio of carboxylic acid group in ESO epoxide epoxy group group and BTCA
Calculate gained.
(3) preparation of SESF/ESOBTCA composite material:, control consistent with the preparation process of 1 step of embodiment (3)
The mass ratio of ESOBTCA performed polymer and SESF substrate is 0.6:1, in obtained composite material, the quality percentage of ESOBTCA resin
Than being denoted as SESF/ESOBTCA37.5 for 37.5% (i.e. the mass percent of plant fibre base material is 62.5%).
Embodiment 8
The present embodiment provides a kind of biodegradable composite materials, and preparation method includes the following steps:
(1) identical as (1) the step of embodiment 1.
(2) preparation of ESOTA performed polymer: taking 1 part of TA (tannic acid) to be dissolved in 8 parts of dehydrated alcohols, and ESO stirring is then added
Uniformly, blend is stirred into 30min at 75 DEG C, obtains brown color clear prepolymer liquid solution, finally performed polymer after the cooling period
Ethyl alcohol is added in solution, obtains the ESOTA prepolymer solution that concentration is 0.2g/ml；The quality of ESO by ESO epoxide epoxy group group with
The molar ratio of phenolic hydroxyl group is obtained by 1:1.4 is calculated in TA.
(3) preparation of SESF/ESOTA composite material: ESOTA prepolymer solution is uniformly sprayed on SESF substrate, control
The mass ratio of ESOTA performed polymer processed and SESF substrate is 0.6:1, by ESOTA performed polymer and SESF substrate after ethyl alcohol volatilization
Mixture is placed in mold, and at 160 DEG C, precuring 10min under the conditions of 5Mpa, is then placed under conditions of 180 DEG C, 1Mpa
Solidify 2h in baking oven, obtain SESF/ESOTA composite material, in obtained composite material, the mass percent of ESOTA resin is
37.5% (i.e. the mass percent of plant fibre base material is 62.5%), is denoted as SESF/ESOTA37.5.
9 performance test of embodiment
Biodegradable composite material prepared by embodiment 1-8 carries out following performance test:
1, tensile property is tested:
Test equipment is the desk-top universal testing machine (instron5566) of Instron Corporation, 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 2mm/min, 5 are repeated
It is secondary to be averaged.
Test results are shown in figure 1 for tensile property, the tensile strength of pure ESO resin it can be seen from extension test result
Be below 1MPa, the tensile strength of SESF plant fibre base material is 5.3MPa, by ESO resin its modified tensile strength most
Height is promoted to 31.2MPa.Wherein for the ESOCA resin of different content, tensile strength reaches maximum when content is 37.5%, main
If due to ESO resin there are it is amphipathic, good interface cohesion can be formed with plant fiber, plant fiber is played well
Cementation, ESO resin content increases bond effect enhancing, but excessively high ESO resin content can be because of its own intensity not
Foot causes the reduction of the tensile strength of composite material.Secondly different curing agent influence the tensile strength of composite material also different
It causes, its solidification effect in curing agent more than carboxyl-content is more preferable, and also stronger with the interface cohesion of plant fiber, intensity can be higher
It is some.And polyphenol curing agent is easy to be coated by resin because its phenolic hydroxyl group steric hindrance is larger, is not easy between plant fiber
Interface cohesion causes intensity slightly to reduce.
2, contact angle test:
Contact angle instrument is the Surface Tension Surface contact angle tester of dataphysics company, Germany
(OCA40Micro), each sample tests five points, is averaged.
Contact angle test result as shown in Fig. 2, as seen from Figure 2, the contact angle of pure ESO resin be substantially at 70 °~
Between 80 °, less than 90 °, stronger hydrophily is shown, while because the differential curing obtained ESO resin surface of curing agent connects
There is also slight differences for feeler.Secondly, because of its extremely strong water imbibition and larger porosity, not obtained for SESF substrate
Contact angular data, and after ESO resin modified, contact angle dramatically increases the (composite material as shown in the figure of the four of Fig. 2 top half
Surface contact angle respectively be 130.1 °, 109.6 °, 108.9 °, 129.4 °), show good hydrophobicity.Mainly
Since the polar group and plant fibre surface hydroxy combining of ESO resin layer make composite material surface resin that more length be presented
Alkyl chain is to cause contact angle to increase.In addition, there are also maleic acids two for the larger reason of SESF/ESOMA37.5 contact angle
A carboxyl both participates in curing reaction, so that system polar group is less compared with other systems, to cause contact angle bigger.SESF/
ESOTA37.5 contact angle is biggish the reason is that since unreacted phenolic hydroxyl group steric hindrance is larger, is easy to be wrapped in inside resin, cause
Surface polar groups are also on the low side, so that contact angle is relatively bigger.
3, water absorption rate test:
Sample to be tested is cut into the batten of 20mm × 20mm, is weighed after drying.Then it is immersed into deionized water, every one
It is taken out after the section time, wipes surface moisture with blotting paper, weighing records it in different time points until quality no longer changes
Weight amount, absorptivity X=(Wh-Wd)/Wd × 100%.
Wd is weight when composite material (sample to be tested) is dry in formula, and Wh is after composite material (sample to be tested) 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 material is fast with the water suction being exceedingly fast
Degree reaches 580%, and after it joined ESO resin, water absorption rate is remarkably decreased, and pure ESO resin water absorption rate is respectively less than 9%.?
In polyacid curative systems, with increasing for carboxyl quantity, solidification effect is more preferable, and secondly polar group, which increases, causes interface to tie
It gets togather, so that water absorption rate constantly declines, the water absorption rate of tri- kinds of system composite materials of MA, CA and BTCA is respectively 31%,
16.2% and 15.4.And TA system causes water absorption rate to have a degree of raising, value is also because its interface cohesion is slightly worse
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 tree
Rouge and the interface cohesion of plant fiber are also different, therefore the water absorption rate of gained composite material, tensile strength and surface contact angle are equal
Slightly difference.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies 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, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of biodegradable composite material, which comprises the following steps:
The preparation of plant fibre base material: pre-processing plant fiber material, to destroy the pencil of the plant fiber material
Structure obtains the plant fiber A that draw ratio is 400~1000, the plant fiber A is placed in water and high shear dispersion is equal
It is even, it filters, drying obtains plant fibre base material；
The preparation of epoxidized soybean oil performed polymer: curing agent is dissolved in the first solvent, and epoxidized soybean oil is then added, and heating is stirred
It mixes, 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 material: the epoxidized soybean oil prepolymer solution is blended with the plant fibre base material, the epoxy
The mass ratio of epoxidized soybean oil performed polymer and the plant fibre base material in soybean oil prepolymer solution is 0.1-1:1, volatilization
Solvent obtains blend, solidifies again after the blend is carried out precuring in a mold to get described biodegradable
Composite material.
2. the preparation method of biodegradable composite material according to claim 1, which is characterized in that the polyacid
Class curing agent is selected from least one of oxalic acid, citric acid, maleic acid, succinic acid, butane tetracarboxylic acid, the polyatomic phenol
Curing agent is tannic acid.
3. the preparation method of biodegradable composite material according to claim 1, which is characterized in that described first is molten
Agent is water and/or dehydrated alcohol, and second solvent is acetone and/or ethyl alcohol, and the heating stirring is the temperature at 60~100 DEG C
Degree is lower to stir 10~30min.
4. the preparation method of biodegradable composite material according to claim 1-3, which is characterized 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 cured pressure is 0.5~5MPa, and temperature is 140~180 DEG C, and the time is not less than 2h.
5. the preparation method of biodegradable composite material according to claim 1-3, which is characterized in that plant
Pretreated method described in the preparation step of fibres substrate is grinding, high shear homogeneous or steam blasting.
6. the preparation method of biodegradable composite material according to claim 1-3, which is characterized in that ring
In epoxy group and the polynary acids curing agent in epoxidized soybean oil described in the preparation step of oxygen soybean oil performed polymer
The molar ratio of carboxylic acid group is 1:0.5~1:2；Or the epoxy group in the epoxidized soybean oil and the polyatomic phenol solidify
The molar ratio of phenolic hydroxyl group in agent is 1:0.8~1:1.6.
7. the preparation method of biodegradable composite material according to claim 1-3, which is characterized in that ring
The mass ratio of polynary acids curing agent described in the preparation step of oxygen soybean oil performed polymer and first solvent is 10:1~2:
1；Or the mass ratio of the polyatomic phenol curing agent and first solvent is 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 biodegradable composite material according to claim 1-3, which is characterized in that multiple
Epoxidized soybean oil performed polymer and the plant in epoxidized soybean oil prepolymer solution described in the step of preparation of condensation material is fine
The mass ratio of Wiki material is 0.4-0.8:1.
9. the biodegradable composite material that the described in any item preparation methods of claim 1-8 are prepared.
10. biodegradable composite material as claimed in claim 9 is preparing the application in packaging material.
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| CN108084573A (en) * | 2017-12-08 | 2018-05-29 | 安徽京鸿密封件技术有限公司 | A kind of effective sealing ring of air conditioning for automobiles draining |
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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 |
| CN110229531B (en) * | 2019-07-11 | 2021-03-23 | 江南大学 | Completely bio-based epoxy resin 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 |
| 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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