CN106366579B - One kind is based on ethyl cellulose/castor oil supramolecular composite film and preparation method thereof - Google Patents

One kind is based on ethyl cellulose/castor oil supramolecular composite film and preparation method thereof Download PDF

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CN106366579B
CN106366579B CN201610810989.1A CN201610810989A CN106366579B CN 106366579 B CN106366579 B CN 106366579B CN 201610810989 A CN201610810989 A CN 201610810989A CN 106366579 B CN106366579 B CN 106366579B
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ethyl cellulose
castor oil
added
composite film
product
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CN106366579A (en
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李守海
夏建陵
毛伟
黄坤
李梅
杨雪娟
许利娜
杨小华
张燕
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Institute of Chemical Industry of Forest Products of CAF
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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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
    • 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
    • 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
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/26—Cellulose ethers
    • C08J2301/28—Alkyl ethers
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

One kind is based on ethyl cellulose/castor oil supramolecular composite film and preparation method thereof, intermediate product A is made in a certain amount of ricinoleic acid and epichlorohydrin reaction, then product B is made through epoxy ring opening reaction in a certain amount of intermediate product A and small molecule monomer, is finally blended with the ethyl cellulose for being dissolved in glacial acetic acid and ethyl cellulose/castor oil supramolecular composite film is made.Ethyl cellulose/castor oil supramolecular composite film prepared by the present invention is applied to Material Field, has a wide range of applications in food, medicine and other fields.Ethyl cellulose/castor oil supramolecular composite film is a kind of completely newer environmental type supramolecular composite film, with many excellent properties of ethyl cellulose and castor oil；The composite membrane of preparation has many advantages, such as preferable mechanical property, water resistance, obdurability, degradability；Preparation process is simple, and condition mitigates, and uses cheap reproducible vegetable fat and cellulose for raw material, the excellent composite membrane of processability.

Description

One kind is based on ethyl cellulose/castor oil supramolecular composite film and preparation method thereof
Technical field
The invention belongs to Material Field, more particularly to it is a kind of based on ethyl cellulose/castor oil supramolecular composite film and its Preparation method.
Background technology
Cellulose is studied by many scholars in recent years as natural reproducible resource most abundant on the earth.Fiber Element has good biocompatibility, hypotoxicity and a degradability, and the water imbibition, comfortable and easy to wear etc. that cellulosic material has had Advantage.Ethyl cellulose (EC) as one of cellulose derivative is water-insoluble one kind, nonionic, thermoplastic fiber Plain alkyl ether has chemical-resistant resistance, salt tolerant, alkaline-resisting and heat-staple characteristic, is most widely used water-insoluble cellulose One of derivative.These excellent features make it be widely used to the fields such as chemical industry, food, medicine, environmental protection, building, material. But toughness and wrinkle resistance difference are two big disadvantages existing for ethyl cellulose, therefore made at present frequently with organism-based raw material flexible The cellulose blending film of standby toughness.
Supramolecular composite film obtained is blended by ethyl cellulose and modified castor oil, have good thermal stability, Higher flexibility and good wrinkle resistance；In addition the excellent thermal stability of supramolecular composite film and flexibility absolutely prove the two Between have good synergistic effect.In addition, along with economic fast development and people to environmental protection and health perception Continuous enhancing, while fossil feedstock class product and intermediate product all have strong impulse taste, are unsuitable for people's Long Term Contact, because This replaces non-renewable petroleum to be current being badly in need of completing of the task using inexpensive nontoxic reproducible biological grease.
A kind of ethyl cellulose/castor oil supramolecular composite film is prepared using biological grease, not only increases composite membrane Toughness, but also non-edible vegetable oil fat high-valued industry development using it is upper have important research significance.
Castor oil is China the most common type oil crops, is widely distributed in the ground such as China northeast, North China, annual output position It ranks the third of the world, because of its abundance, therefore in the fields such as coating, plastics, polyurethane and rubber extensive application.In castor oil Containing a large amount of carboxyls, a variety of chemical reactions, such as transesterification can occur for ester group and double bond, dehydration, and pyrolysis, epoxidation, esterification are anti- It answers, addition reaction etc..Therefore new active group and final is introduced by epoxidation reaction using the ricinoleic acid containing carboxyl Ethyl cellulose/castor oil supramolecular composite film is made.Environmentally friendly, the safe and energy-efficient ethyl cellulose/castor oil oversubscription of exploitation Sub- composite membrane is one of Main way of future development.
Invention content
The technical issues of solution：There are the disadvantages such as poor toughness, wrinkle resistance be low for single ethyl cellulose, to improve it Modified castor oil is introduced into ethyl cellulose by disadvantage, the present invention, to enhance the toughness of ethyl cellulose and crease-resistant Property, one kind is devised based on ethyl cellulose/castor oil supramolecular composite film and preparation method thereof, and it is compound to be expected to raising supermolecule The toughness and wrinkle resistance of film.Reaction condition is mild in the synthesis process for this method, and product stability obtained is good.
Technical solution：A kind of preparation method based on ethyl cellulose/castor oil supramolecular composite film, by following steps system ：Ricinoleic acid is added in reaction vessel, then according to ricinoleic acid and epoxychloropropane molar ratio 1:8~10 ratio Epoxychloropropane is added, adds the triphenylphosphine of 0.5~1.0wt.% of above-mentioned reaction raw materials gross mass, 115~120 DEG C of reactions 2h；It is cooled to 55~65 DEG C, is added and originates the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid, 55~ 2.5~3.5h is stirred at 65 DEG C；Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A；It will be intermediate Product A and 0.5%~1.5% catalyst for accounting for reactant gross mass are added in reactor, are warming up to 40~50 DEG C, then To its dropwise addition small molecule monomer, the molar ratio of the small molecule monomer and intermediate product A are 1~1.2:1, after being added dropwise, 70 ~80 DEG C of 3~5h of reaction, are made product B；Ethyl cellulose is weighed in reaction vessel, then according to ethyl cellulose:Solvent Mass ratio be 1:10~17 are added solvents, and 5~7h is stirred at 55~65 DEG C, after ethyl cellulose is completely dissolved to get to Ethyl cellulose solution；Then product B and ethyl cellulose are matched according to different quality containing and is uniformly mixed.
Above-mentioned catalyst is triphenylphosphine, N, N dimethyl benzylamine, tetraethylammonium bromide, benzyltrimethylammonium chloride, tetramethyl Base ammonium bromide or cetyl trimethylammonium bromide.
Above-mentioned small molecule monomer is dibutylphosphoric acid ester, mercaptoethanol or diethyl phosphate.
Above-mentioned solvent is glacial acetic acid.
The mass fraction of above-mentioned product B and ethyl cellulose proportioning for 10%/90%, 20%/80%, 30%/70%, 40%/60% or 50%/50%.
The above method be prepared based on ethyl cellulose/castor oil supramolecular composite film.
Advantageous effect：1) water-insoluble ethyl cellulose is dissolved as solvent using glacial acetic acid, relieves common organic solvent Benzene, toluene etc. are injured caused by human body.2) supramolecular composite film is prepared as raw material using castor oil and cellulose, elasticity can Control, and composite membrane obtained in terms of the wrinkle resistance and toughness on be expected to improve single cellulose membrane lacking in these two aspects Point, and the comprehensive performance of ethyl cellulose/castor oil supramolecular composite film is improved simultaneously.3) crude vegetal castor oil is used For raw material, by simply hydrolyzing, being esterified, epoxy addition etc. polyol is obtained by the reaction, raw material sources are abundant, prepare work Skill is simple, not only saves the consumption of the energy, and environmentally friendly in the synthesis process, and slow down excessively disappearing for petrochemical industry resource Consumption.
Description of the drawings
Fig. 1 is the infrared spectrum of ethyl cellulose and different proportion ethyl cellulose castor oil supramolecular composite film.Ethyl 1736cm in cellulose castor oil composite membrane-1Place is the characteristic peak of ester carbonyl group, illustrates that ethyl cellulose is uniformly mixed with product A, Composite membrane is uniform.
Specific implementation mode
Certain embodiments are given below so that the present invention will be further described, but following embodiment is protected to the present invention The limitation of range illustrates that field technology personnel make some nonessential modifications and adaptations according to the content of present invention and still belong to this hair Bright protection content.
Embodiment 1
The ricinoleic acid of certain mass is added in reactor, then according to ricinoleic acid and epoxychloropropane molar ratio 1：Epoxychloropropane is added in 8 ratio, adds the triphenylphosphine of above-mentioned reactant gross mass 1.0wt.%, 120 DEG C of reaction 2h； 60 DEG C are cooled to, the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid with starting is added, is stirred at 60 DEG C 3h.Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A.By a certain amount of intermediate product A and account for 1.0% triphenylphosphine of reactant gross mass is added in reactor, is warming up to 45 DEG C, and di(2-ethylhexyl)phosphate fourth then is added dropwise to it The molar ratio of ester, the dibutylphosphoric acid ester and intermediate product A are 1：1, after being added dropwise, product B is made in 75 DEG C of reaction 4h；Claim Take a certain amount of ethyl cellulose in reaction vessel, then according to ethyl cellulose:The mass ratio of glacial acetic acid is 1：17 are added Glacial acetic acid stirs 6h at 60 DEG C, to get to ethyl cellulose solution after ethyl cellulose is completely dissolved；Then by product B and Ethyl cellulose is matched according to mass fraction 50%/50% and is uniformly mixed, and is subsequently poured into mold, room temperature curing 6h, then again Resolidification 2h after being increased to 80 DEG C is then down to room temperature and obtains ethyl cellulose/castor oil supramolecular composite film.
Embodiment 2
The ricinoleic acid of certain mass is added in reactor, then according to ricinoleic acid and epoxychloropropane molar ratio 1：Epoxychloropropane is added in 9 ratio, adds the triphenylphosphine of above-mentioned reactant gross mass 0.5wt.%, 115 DEG C of reaction 2h； 55 DEG C are cooled to, the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid with starting is added, is stirred at 55 DEG C 2.5h.Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A.By a certain amount of intermediate product A and 0.5% N of reactant gross mass is accounted for, N dimethyl benzylamine is added in reactor, is warming up to 40 DEG C, and phosphorus then is added dropwise to it The molar ratio of diethyl phthalate, the diethyl phosphate and intermediate product A are 1.2:1, after being added dropwise, 80 DEG C of reaction 5h are made Product B；A certain amount of ethyl cellulose is weighed in reaction vessel, is then according to the mass ratio of ethyl cellulose/glacial acetic acid 1:10 are added glacial acetic acid, stir 5h at 55 DEG C, to get to ethyl cellulose solution after ethyl cellulose is completely dissolved；Then Intermediate product B and ethyl cellulose are matched according to mass fraction 40%/60% and are uniformly mixed, is subsequently poured into mold, room temperature Cure 6h, resolidification 2h after being then increased to 80 DEG C again, being then down to room temperature, to obtain ethyl cellulose/castor oil supermolecule multiple Close film.
Embodiment 3
The ricinoleic acid of certain mass is added in reactor, then according to ricinoleic acid and epoxychloropropane molar ratio 1：Epoxychloropropane is added in 10 ratio, adds the triphenylphosphine of above-mentioned reactant gross mass 0.6wt.%, 118 DEG C of reactions 2h；65 DEG C are cooled to, the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid with starting is added, is stirred at 65 DEG C Mix 3.5h.Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A.By a certain amount of intermediate product A It is added in reactor with 1.5% tetraethylammonium bromide for accounting for reactant gross mass, is warming up to 50 DEG C, mercapto then is added dropwise to it The molar ratio of base ethyl alcohol, the dibutylphosphoric acid ester and intermediate product A are 1.1:1, after being added dropwise, production is made in 70 DEG C of reaction 3h Object B；A certain amount of ethyl cellulose is weighed in reaction vessel, is then 1 according to the mass ratio of ethyl cellulose/glacial acetic acid: 15 are added glacial acetic acid, stir 7h at 65 DEG C, to get to ethyl cellulose solution after ethyl cellulose is completely dissolved；Then will Product B and ethyl cellulose are matched according to mass fraction 30%/70% to be uniformly mixed, and is subsequently poured into mold, room temperature curing 6h, Resolidification 2h after being then increased to 80 DEG C again is then down to room temperature and obtains ethyl cellulose/castor oil supramolecular composite film.
Embodiment 4
The ricinoleic acid of certain mass is added in reactor, then according to ricinoleic acid and epoxychloropropane molar ratio 1：Epoxychloropropane is added in 8 ratio, adds the triphenylphosphine of above-mentioned reactant gross mass 0.7wt.%, 117 DEG C of reaction 2h； 58 DEG C are cooled to, the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid with starting is added, is stirred at 58 DEG C 2.8h.Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A.By a certain amount of intermediate product A and 0.8% benzyltrimethylammonium chloride for accounting for reactant gross mass is added in reactor, is warming up to 48 DEG C, is then added dropwise to it The molar ratio of diethyl phosphate, the diethyl phosphate and intermediate product A are 1.2:1, after being added dropwise, 75 DEG C of reaction 3h, system Obtain product B；A certain amount of ethyl cellulose is weighed in reaction vessel, then according to ethyl cellulose:The mass ratio of glacial acetic acid It is 1:12 are added glacial acetic acid, stir 6h at 58 DEG C, to get to ethyl cellulose solution after ethyl cellulose is completely dissolved；So Product B and ethyl cellulose are matched according to mass fraction 20%/80% afterwards and are uniformly mixed, is subsequently poured into mold, room temperature is solid Change 6h, resolidification 2h after being then increased to 80 DEG C again, being then down to room temperature, to obtain ethyl cellulose/castor oil supermolecule compound Film.
Embodiment 5
The ricinoleic acid of certain mass is added in reactor, then according to ricinoleic acid and epoxychloropropane molar ratio 1：Epoxychloropropane is added in 9 ratio, adds the triphenylphosphine of above-mentioned reactant gross mass 0.8wt.%, 118 DEG C of reaction 2h； 62 DEG C are cooled to, the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid with starting is added, is stirred at 62 DEG C 3.2h.Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A.By a certain amount of intermediate product A and 1.2% 4 bromide for accounting for reactant gross mass is added in reactor, is warming up to 46 DEG C, and phosphoric acid then is added dropwise to it The molar ratio of dibutyl ester, the dibutylphosphoric acid ester and intermediate product A are 1:1, after being added dropwise, product is made in 76 DEG C of reaction 5h B；A certain amount of ethyl cellulose is weighed in reaction vessel, then according to ethyl cellulose:The mass ratio of glacial acetic acid is 1:14 Glacial acetic acid is added, stirs 5.5h at 56 DEG C, to get to ethyl cellulose solution after ethyl cellulose is completely dissolved；Then will Product B and ethyl cellulose are matched according to mass fraction 10%/90% to be uniformly mixed, and is subsequently poured into mold, room temperature curing 6h, Resolidification 2h after being then increased to 80 DEG C again is then down to room temperature and obtains ethyl cellulose/castor oil supramolecular composite film.
Embodiment 6
The ricinoleic acid of certain mass is added in reactor, then according to ricinoleic acid and epoxychloropropane molar ratio 1：Epoxychloropropane is added in 10 ratio, adds the triphenylphosphine of above-mentioned reactant gross mass 0.9wt.%, 119 DEG C of reactions 2h；64 DEG C are cooled to, the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid with starting is added, is stirred at 64 DEG C Mix 3.0h.Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A.By a certain amount of intermediate product A Be added in reactor with 0.8% cetyl trimethylammonium bromide for accounting for reactant gross mass, be warming up to 40 DEG C, then to The molar ratio of its dropwise addition mercaptoethanol, the diethyl phosphate and intermediate product A are 1.2:1, after being added dropwise, 75 DEG C of reactions Product B is made in 4.5h；A certain amount of ethyl cellulose is weighed in reaction vessel, then according to ethyl cellulose:Glacial acetic acid Mass ratio is 1:16 are added glacial acetic acid, stir 5.5h at 58 DEG C, to get to ethyl cellulose after ethyl cellulose is completely dissolved Solution；Then product B and ethyl cellulose are matched according to mass fraction 50%/50% and are uniformly mixed, is subsequently poured into mold, Room temperature curing 6h, resolidification 2h after being then increased to 80 DEG C again are then down to room temperature and obtain ethyl cellulose/castor oil oversubscription Sub- composite membrane.
Comparative example：
Experimental group 1：The tensile strength of the ethyl cellulose prepared by embodiment 1/castor oil supramolecular composite film and fracture Elongation is respectively 3.04MPa and 20.12%.
Experimental group 2：The tensile strength of the ethyl cellulose prepared by embodiment 2/castor oil supramolecular composite film and fracture Elongation is respectively 5.45MPa and 17.6%.
Experimental group 3：The tensile strength of the ethyl cellulose prepared by embodiment 3/castor oil supramolecular composite film and fracture Elongation is respectively 9.11MPa and 11.43%.
Experimental group 4：The tensile strength of the ethyl cellulose prepared by embodiment 4/castor oil supramolecular composite film and fracture Elongation is respectively 14.2MPa and 4.7%.
Comprehensive mechanical property analysis is carried out to above-mentioned 4 kinds of supramolecular composite films, measurement result is as described in table 1.
Table 1 takes the mechanical property of each experimental group to compare at random
Project Tensile strength/MPa Elongation at break/%
Experimental group 1 3.04 20.12
Experimental group 2 5.45 17.6
Experimental group 3 9.11 11.43
Experimental group 4 14.2 4.7
Note：Tensile property is controlled with reference to GB/T 1040.3-2006 plastic tensile test methods using CMT4000 type microcomputers Electronic universal tester (newly thinks carefully in Shenzhen) that the tensile property extension test speed for measuring material is 10mm/min, test temperature It is 25 DEG C.

Claims (2)

1. a kind of preparation method based on ethyl cellulose/castor oil supramolecular composite film, it is characterised in that by following steps system ：Ricinoleic acid is added in reaction vessel, then according to ricinoleic acid and epoxychloropropane molar ratio 1:8 ~ 10 ratio Epoxychloropropane is added, adds the triphenylphosphine of 0.5 ~ 1.0wt.% of above-mentioned reaction raw materials gross mass, 115 ~ 120 DEG C of reaction 2h； It is cooled to 55 ~ 65 DEG C, is added and originates the calcium oxide and sodium hydroxide for reacting carboxyl equimolar number in ricinoleic acid, 55 ~ 65 DEG C 2.5 ~ 3.5h of lower stirring；Most afterwards through filtering, revolving removes extra epoxychloropropane and obtains intermediate product A；By intermediate product A It is added in reactor with the catalyst for 0.5% ~ 1.5 % for accounting for reactant gross mass, the catalyst is triphenylphosphine, N, N bis- Methylbenzylamine, tetraethylammonium bromide, benzyltrimethylammonium chloride, 4 bromide or cetyl trimethylammonium bromide rise Then to 40 ~ 50 DEG C small molecule monomer is added dropwise to it in temperature, the small molecule monomer is dibutylphosphoric acid ester, mercaptoethanol or phosphoric acid The molar ratio of diethylester, the small molecule monomer and intermediate product A are 1 ~ 1.2:1, after being added dropwise, 70~80 DEG C of reactions 3 ~ Product B is made in 5h；Ethyl cellulose is weighed in reaction vessel, then according to ethyl cellulose:The mass ratio of solvent is 1:10 ~17 are added solvents, and the solvent is glacial acetic acid, and 5 ~ 7h is stirred at 55 ~ 65 DEG C, after ethyl cellulose is completely dissolved to get to Ethyl cellulose solution；Then product B and ethyl cellulose are matched according to different quality containing and is uniformly mixed, the product B Mass fraction proportioning with ethyl cellulose is 10%/90%, 20%/80%, 30%/70%, 40%/60% or 50%/50%.
2. claim 1 the method be prepared based on ethyl cellulose/castor oil supramolecular composite film.
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