CN112480273A - Vegetable oil modified ethyl cellulose and preparation method thereof - Google Patents
Vegetable oil modified ethyl cellulose and preparation method thereof Download PDFInfo
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- CN112480273A CN112480273A CN202011320141.3A CN202011320141A CN112480273A CN 112480273 A CN112480273 A CN 112480273A CN 202011320141 A CN202011320141 A CN 202011320141A CN 112480273 A CN112480273 A CN 112480273A
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- vegetable oil
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical class CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 38
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 31
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 31
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 31
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 235000012424 soybean oil Nutrition 0.000 claims description 14
- 239000003549 soybean oil Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims 4
- 238000001035 drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 238000002144 chemical decomposition reaction Methods 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010813 internal standard method Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 244000068988 Glycine max Species 0.000 description 6
- 235000010469 Glycine max Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- -1 fatty acid triglycerides Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
- C08B3/10—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate with five or more carbon-atoms, e.g. valerate
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The vegetable oil modified ethyl cellulose is obtained by carrying out alcoholysis reaction on ethyl cellulose and vegetable oil through hydroxyl of an ethyl cellulose structure under the catalytic action of sodium methoxide. By regulating and controlling the content of the vegetable oil in the alcoholysis reaction, the modified ethyl cellulose material with different mechanical properties, transparency, pyrolysis properties and chemical degradation properties can be obtained. The material has potential application value in the fields of food packaging, children toys and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of modified ethyl cellulose, and particularly relates to vegetable oil modified ethyl cellulose and a preparation method thereof.
Background
Ethyl Cellulose is an important natural polymer material, also called Cellulose ether, abbreviated as EC (abbreviation of Ethyl Cellulose). White fine-grained thermoplastic solids, standard commercial products, contain 47% to 48% ethoxy, a relative density of 1.07, and a moisture uptake of 20%. Stable to heat, does not generate gelation when heated, has a softening point of 100-130 ℃, and has good film-forming property. Is soluble in many organic solvents and can be used in combination with resins, waxes, oils and plasticizers. Its properties are related to the ethoxy content, with high ethoxy contents increasing its solubility in organic solvents, while its softening point and hygroscopicity decrease. Obtained by reacting alkali cellulose with ethyl chloride or diethyl sulfate. Used as coating, film, plastic, rubber substitute, printing ink, insulating material, adhesive, textile finishing agent, etc. The modification method of the ethyl cellulose comprises a physical method and a chemical method, wherein the physical method is mainly used for changing the mechanical property, the flame retardant property and the like of the ethyl cellulose material by adding a plasticizer, a flame retardant and the like; the chemical modification means that a corresponding modified ethyl cellulose material is obtained through a chemical reaction, for example, hydroxyl on the chemical structure of the ethyl cellulose is utilized to perform esterification reaction and alcoholysis reaction, and the modified ethyl cellulose material is converted into structures such as carboxyl, aldehyde and ketone groups through chemical oxidation, and the ethyl cellulose can be functionalized by utilizing the structural change, so that more new performances can be endowed to the ethyl cellulose. The modified ethyl cellulose with the long fatty hydrocarbon chain can be obtained by esterification reaction of ethyl cellulose and long-chain fatty acid, the tensile strength of the modified ethyl cellulose is gradually reduced along with the increase of the branched chain, the elongation at break is obviously increased, and the purpose of internal plasticization is achieved. The oxidation modes are divided into selective oxidation and nonselective oxidation. Among them, since the position of non-selective oxidation and the resulting functional group cannot be determined controllably, it is often subjected to selective oxidation. By selective oxidation, i.e. selective oxidation of primary or secondary hydroxyl groups with different oxidizing agents is meant. The former gives monofunctional species, while the latter gives difunctional species. The performance of cellulose in the aspects of adsorptivity and the like can be greatly improved by oxidizing the cellulose.
Vegetable oils are important natural source platform compounds, and the main component is fatty acid triglycerides, wherein the 3 aliphatic hydrocarbon chains are usually derived from fatty acids with 14-22 carbon atoms, including saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons and polyunsaturated aliphatic hydrocarbons, and are represented by oleic acid, linoleic acid, linolenic acid, palmitic acid, eleostearic acid and the like. The ester bond of the vegetable oil can generate alcoholysis reaction to prepare polyol, the unsaturated bond can generate epoxidation reaction to prepare epoxy plasticizer, and Diels-Alder reaction can be carried out to synthesize various chemical intermediates. Thus, vegetable oils can be used to synthesize a wide variety of fine chemicals such as plasticizers, polyols, biodiesel, fatty alcohols, lubricants, and downstream products such as glycerin, and polymeric materials such as polyurethanes, polyamides, polyesters, coatings, and the like.
The ethyl cellulose has excellent film forming performance, but the texture is brittle and easy to break, the flexibility of the ethyl cellulose film can be changed by adding the plasticizer, but the plasticizer is easy to volatilize and be extracted by a solvent in the use process, the performance and the service life of the ethyl cellulose material are seriously influenced, and the migration of the plasticizer can cause pollution to the environment.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides vegetable oil modified ethyl cellulose and a preparation method thereof, and the product can be used for preparing modified ethyl cellulose materials with different mechanical properties, transparency, pyrolysis properties and chemical degradation properties.
The technical scheme is as follows: the vegetable oil modified ethyl cellulose has the following chemical structural formula:
the preparation method of the vegetable oil modified ethyl cellulose is characterized in that the vegetable oil is directly subjected to alcoholysis reaction with hydroxyl of the ethyl cellulose in a solvent under the catalysis of sodium methoxide, and then the vegetable oil is precipitated in distilled water and methanol solution and dried in a vacuum drying oven to obtain the vegetable oil modified ethyl cellulose; the mass ratio of the vegetable oil to the ethyl cellulose is (0.1-2) to 1; the alcoholysis reaction temperature is 25-160 ℃; the alcoholysis reaction time is 0.15-48 h.
The vegetable oil is at least one of soybean oil, palm oil, rapeseed oil and tung oil.
The viscosity of the ethyl cellulose is at least one of 3-330 mPa.s.
The alcoholysis reaction temperature was 55 ℃.
The alcoholysis reaction time is 24 hours.
The mass ratio of the vegetable oil to the ethyl cellulose is (0.1-2) to 1.
The content of sodium methoxide used in the reaction is 0.1-10% of the total mass of the reaction system.
The solvent required by the reaction is one of benzene, toluene, ethylbenzene, xylene and tetrahydrofuran.
The ratio of the mass of the solvent to the total mass of the reactants is 1 (10-100).
Has the advantages that: the invention uses biomass resources, namely soybean oil and ethyl cellulose, to prepare the vegetable oil modified ethyl cellulose material, and directly uses the hydroxyl of the ethyl cellulose and the vegetable oil to carry out alcoholysis reaction under the catalytic action of sodium methoxide to obtain a product. By regulating and controlling the content of the vegetable oil in the alcoholysis reaction, the modified ethyl cellulose material with different mechanical properties, transparency, pyrolysis properties and chemical degradation properties can be obtained. The material has potential application value in the fields of food packaging, children toys and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of ethyl cellulose;
FIG. 2 nuclear magnetic hydrogen spectrum of vegetable oil modified ethyl cellulose of example 1;
FIG. 3 nuclear magnetic hydrogen spectrum of vegetable oil modified ethyl cellulose of example 3;
FIG. 4 nuclear magnetic hydrogen spectrum of vegetable oil modified ethyl cellulose of example 5;
FIG. 5 transmittance of vegetable oil modified ethylcellulose;
FIG. 6 thermogravimetric curve of vegetable oil modified ethylcellulose.
Detailed Description
Example 1
3g of soybean oil and 7g of ethyl cellulose are dissolved in 150mL of tetrahydrofuran, 0.1g of sodium methoxide is added, the temperature is controlled at 60 ℃, nitrogen is protected, and the mixture is stirred and reacted for 24 hours. The polymer was precipitated with 10 wt.% aqueous methanol, separated and dried to yield soybean oil-modified ethylcellulose. The content of unsaturated double bonds in the modified ethylcellulose was determined by the internal standard method using nuclear magnetic hydrogen spectroscopy, and the results are shown in table 1 and fig. 2.
Example 2
4g of soybean oil and 6g of ethyl cellulose are dissolved in 150mL of tetrahydrofuran, 0.1g of sodium methoxide is added, the temperature is controlled at 60 ℃, nitrogen is protected, and the mixture is stirred and reacted for 24 hours. The polymer was precipitated with 10 wt.% aqueous methanol, separated and dried to yield soybean oil-modified ethylcellulose. The content of unsaturated double bonds in the modified ethylcellulose was determined by the internal standard method using nuclear magnetic hydrogen spectroscopy, and the results are shown in table 1.
Example 3
5g of soybean oil and 5g of ethyl cellulose are dissolved in 150mL of tetrahydrofuran, 0.1g of sodium methoxide is added, the temperature is controlled at 60 ℃, nitrogen is protected, and the mixture is stirred and reacted for 24 hours. The polymer was precipitated with 10 wt.% aqueous methanol, separated and dried to yield soybean oil-modified ethylcellulose. The content of unsaturated double bonds in the modified ethylcellulose was determined by the internal standard method using nuclear magnetic hydrogen spectroscopy, and the results are shown in table 1 and fig. 3.
Example 4
6g of soybean oil and 4g of ethyl cellulose are dissolved in 150mL of tetrahydrofuran, 0.1g of sodium methoxide is added, the temperature is controlled at 60 ℃, nitrogen is protected, and the mixture is stirred and reacted for 24 hours. The polymer was precipitated with 10 wt.% aqueous methanol, separated and dried to yield soybean oil-modified ethylcellulose. The content of unsaturated double bonds in the modified ethylcellulose was determined by the internal standard method using nuclear magnetic hydrogen spectroscopy, and the results are shown in table 1.
Example 5
7g of soybean oil and 3g of ethyl cellulose are dissolved in 150mL of tetrahydrofuran, 0.1g of sodium methoxide is added, the temperature is controlled at 60 ℃, nitrogen is protected, and the mixture is stirred and reacted for 24 hours. The polymer was precipitated with 10 wt.% aqueous methanol, separated and dried to yield soybean oil-modified ethylcellulose. The content of unsaturated double bonds in the modified ethylcellulose was determined by the internal standard method using nuclear magnetic hydrogen spectroscopy, and the results are shown in table 1 and fig. 4.
Example 6
9g of soybean oil and 1g of ethyl cellulose are dissolved in 150mL of tetrahydrofuran, 0.1g of sodium methoxide is added, the temperature is controlled at 60 ℃, nitrogen is protected, and the mixture is stirred and reacted for 24 hours. The polymer was precipitated with 10 wt.% aqueous methanol, separated and dried to yield soybean oil-modified ethylcellulose. The content of unsaturated double bonds in the modified ethylcellulose was determined by the internal standard method using nuclear magnetic hydrogen spectroscopy, and the results are shown in table 1.
TABLE 1 determination of unsaturated double bond content in chemical structure of vegetable oil modified ethyl cellulose by nuclear magnetic hydrogen spectrum internal standard method
| Examples | Soybean oil/ethyl cellulose | Unsaturated double bond content |
| Example 1 | 30wt.％ | 0.0060 |
| Example 2 | 40wt.％ | 0.0181 |
| Example 3 | 50wt.％ | 0.0215 |
| Example 4 | 60wt.％ | 0.0320 |
| Example 5 | 70wt.％ | 0.0445 |
| Example 6 | 90wt.％ | 0.0898 |
By comparing the nuclear magnetic hydrogen spectrum of ethyl cellulose (fig. 1) and the nuclear magnetic hydrogen spectrum of modified ethyl cellulose (fig. 2-fig. 4), the nuclear magnetic absorption peak (chemical shift near 5.45 ppm) of protons from unsaturated double bond groups of soybean oil gradually increased with the increase of the content of soybean oil in the reaction. The content of unsaturated double bonds was measured by the internal standard method and the results are summarized in table 1, indicating that the content of unsaturated double bonds in the modified ethylcellulose gradually increased with the increase of the content of soybean oil in the reaction, indicating that the desired product was obtained. Fig. 5 and 6 show that as the soybean oil content increases during the alcoholysis reaction, the transparency of the modified ethylcellulose increases and the thermal stability decreases.
Claims (10)
1. The vegetable oil modified ethyl cellulose is characterized by having a chemical structural formula as follows:
2. the method for preparing the vegetable oil modified ethyl cellulose is characterized in that the vegetable oil modified ethyl cellulose is obtained by directly carrying out alcoholysis reaction on vegetable oil and hydroxyl of ethyl cellulose in a solvent under the catalysis of sodium methoxide, precipitating in distilled water and a methanol solution, and drying in a vacuum drying oven; the mass ratio of the vegetable oil to the ethyl cellulose is (0.1-2) to 1; the alcoholysis reaction temperature is 25-160 ℃; the alcoholysis reaction time is 0.15-48 h.
3. The method for producing a vegetable oil-modified ethylcellulose according to claim 2, characterized in that said vegetable oil is at least one of soybean oil, palm oil, rapeseed oil and tung oil.
4. The method for preparing vegetable oil-modified ethylcellulose according to claim 2, characterized in that said ethylcellulose has at least one viscosity ranging from 3 to 330 mpa.s.
5. The method for preparing vegetable oil-modified ethylcellulose according to claim 2, characterized in that the alcoholysis reaction temperature is 55 ℃.
6. The method for preparing vegetable oil modified ethyl cellulose according to claim 2, wherein the alcoholysis reaction time is 24 hours.
7. The method for preparing the vegetable oil-modified ethylcellulose according to claim 2, characterized in that the mass ratio of the vegetable oil to the ethylcellulose is (0.1-2): 1.
8. The method for preparing vegetable oil modified ethyl cellulose according to claim 2, wherein sodium methoxide is used in the reaction in an amount of 0.1-10% by weight based on the total weight of the reaction system.
9. The method for preparing vegetable oil modified ethyl cellulose according to claim 2, wherein the solvent required for the reaction is one of benzene, toluene, ethylbenzene, xylene, and tetrahydrofuran.
10. The method for preparing vegetable oil modified ethyl cellulose according to claim 9, wherein the ratio of the mass of the solvent to the total mass of the reactants is 1 (10-100).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011320141.3A CN112480273A (en) | 2020-11-23 | 2020-11-23 | Vegetable oil modified ethyl cellulose and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011320141.3A CN112480273A (en) | 2020-11-23 | 2020-11-23 | Vegetable oil modified ethyl cellulose and preparation method thereof |
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| CN112480273A true CN112480273A (en) | 2021-03-12 |
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