CN109970556B - Vegetable oil-based polyacid alcohol ether ester and preparation method and application thereof - Google Patents
Vegetable oil-based polyacid alcohol ether ester and preparation method and application thereof Download PDFInfo
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- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 100
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 100
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 66
- -1 alcohol ether ester Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002699 waste material Substances 0.000 claims abstract description 54
- 239000004626 polylactic acid Substances 0.000 claims abstract description 45
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 35
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000008157 edible vegetable oil Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000004821 distillation Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
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- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001746 injection moulding Methods 0.000 claims description 16
- 239000012024 dehydrating agents Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000843 powder Substances 0.000 claims description 7
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- 238000006317 isomerization reaction Methods 0.000 claims description 6
- 230000004224 protection Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
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- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 2
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- 238000007670 refining Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003208 petroleum Substances 0.000 abstract description 6
- 125000001033 ether group Chemical group 0.000 abstract description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 25
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 10
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- 230000008569 process Effects 0.000 description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- 239000008035 bio-based plasticizer Substances 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
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- 239000007924 injection Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
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- 231100000419 toxicity Toxicity 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
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- 230000006750 UV protection Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
Abstract
The invention discloses a vegetable oil-based polyacid alcohol ether ester, a preparation method and application thereof. The molecular structure of the vegetable oil-based alcohol ether ester contains ester and ether groups with large polarity and good flexibility, so that the vegetable oil-based alcohol ether ester has the advantages of good compatibility with polylactic acid and PVC, high plasticizing efficiency, small addition amount and the like, can completely replace the traditional petroleum-based plasticizer dioctyl terephthalate, is a plasticizer with excellent performance of polylactic acid and PVC, and realizes the resource utilization of waste. In addition, the PVC material plasticized by the vegetable oil-based polyacid alcohol ether ester has excellent uvioresistant performance and good practicability.
Description
Technical Field
The invention belongs to the technical field of novel plasticizers and preparation thereof, and relates to a method for preparing a bio-based plasticizer by using recovered waste edible vegetable oil and application of the bio-based plasticizer in polylactic acid plastic and PVC materials, in particular to a method for preparing vegetable oil-based poly (acid-alcohol ether ester) by using waste edible vegetable oil and application methods of the product and plasticized polylactic acid, PVC and other materials.
Background
The waste edible oil is non-edible recovered oil and mainly comes from the catering industry. According to statistics, the amount of the waste edible oil in the world exceeds 500 million tons every year, and the method has very important significance for effectively recovering, safely storing and efficiently recycling the waste oil. These waste edible oils and fats are commonly used as feed for poultry in developing countries. However, the waste grease may have harmful substances due to high temperature, and is transferred to human bodies by means of food chain transfer. Thus, the developed economies of the European Union have prohibited this way of reusing waste vegetable oils in 2002 (Kulkarni et al. Ind. Eng. chem. Res.2006,45(9), 2901-2913.). In such circumstances, many workers have attempted to convert waste edible oils into valuable greases, syngas, and biodiesel. Wherein the biodiesel prepared by using the waste edible oil is successfully applied to industrial production due to higher added value. However, the structural composition of waste oils and fats has a significant impact on the quality of biodiesel, which limits the large-scale application of waste edible oils (Gui et al. energy,2008,33, 1646-1653.).
The use of waste edible oils to prepare high quality, renewable, non-toxic and degradable bio-based plasticizers is a viable and efficient process. On the one hand, the annual demand for plasticizers exceeds 6400 ten thousand tons. On the other hand, conventional petroleum-based plasticizers (such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl terephthalate (DOTP)) have the disadvantages of toxicity, non-regeneration, and difficult degradation, and the preparation of renewable, degradable, and low (non-) toxicity bio-based plasticizers is an inevitable choice.
At present, many researches on preparing high-quality plasticizers from fresh vegetable oil are carried out. For example, Li et al (Material & design.2017,122(15),366-375.) have reported that the addition of maleic anhydride to tung oil by using the double bond in tung oil followed by esterification with methanol gives the corresponding methyl ester of tung oil-maleic acid. Chen et al (ACS curable chem. eng.,2018,6(1), 642-. The research on preparing the bio-based plasticizer by using the waste edible vegetable oil as the raw material is relatively less. Because the components in the edible oil are more complex after being used at high temperature and the content of double bonds is lower (the conjugated double bonds are lower), the difficulty is increased for further modification research. Recently, Feng et al (J.clean.Prod.189, 334-343.) reported the use of waste cooking oil to make polycarboxylic esters and use them on PVC materials to replace traditional dioctyl phthalate (DOP). The research result shows that the plasticizer has good plasticizing performance, but the synthesis process condition is harsh, and the intermediate product fatty acid methyl ester is obtained by distillation at 250 ℃ under the vacuum condition. Furthermore, Zheng et al (j.clean.prod.186, 1021-1030.) applied new plasticizers by way of methyl esters of waste cooking oils and epoxidation to PVC materials. However, the compatibility of the epoxy waste edible oil methyl ester with PVC is poor, and only part of the toxic DOP based on petroleum can be replaced. More importantly, the plasticizers are only used for plasticizing PVC materials, and the application of the plasticizers in polylactic acid materials is not reported in relevant documents.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention aims to provide a method for preparing vegetable oil-based polyol ether ester by using waste edible vegetable oil, which has the characteristics of easiness in operation, environmental protection, waste utilization and the like. The invention also aims to provide the vegetable oil-based polyol ether ester prepared by the method, which has the characteristics of good compatibility, high plasticizing efficiency and the like. The invention also aims to provide the vegetable oil-based polyol ether ester as a plasticizer for plasticizing polylactic acid and PVC materials.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a method for preparing vegetable oil-based polyacid alcohol ether ester by using waste edible vegetable oil comprises the steps of taking waste edible vegetable oil as a raw material, firstly carrying out hydrolysis and isomerization reaction, then carrying out Diels-Alder addition reaction with maleic anhydride to obtain vegetable oil-based polyacid, and carrying out esterification reaction on the vegetable oil-based polyacid and dihydric alcohol monoalkyl ether to synthesize the vegetable oil-based polyacid alcohol ether ester; wherein, the molar ratio of the vegetable oil-based polyacid to the dihydric alcohol monoalkyl ether is as follows: 1: 1-5; the structural general formula of the dihydric alcohol monoalkyl ether is as follows:
in the formula, n is: 1 to 5, R1Is H or CH3，R2Is C1-6An alkyl group.
The method for preparing the vegetable oil-based polyol ether ester by using the waste edible vegetable oil comprises the following steps:
1) adding sodium hydroxide and an ethanol-water solution into a reactor, stirring and heating to 60-70 ℃, then dropwise adding waste edible vegetable oil into a reaction system, reacting for 2-5h, adjusting the pH of the system to 2-3 by using 0.5-1mol/L hydrochloric acid, and continuing to react for 1-5h to finish the reaction; the hydrolysis temperature is too high, and the reflux is too violent, so that part of ethanol is volatilized, and the resource waste is caused; if the hydrolysis temperature is too low, the hydrolysis reaction does not proceed completely, resulting in a low yield of the monoacid. Extracting the reaction mixture with a solvent (one of diethyl ether, ethyl acetate and n-hexane) to obtain an organic phase, and washing with deionized water; finally, removing the solvent and water by a reduced pressure distillation mode to obtain viscous dark liquid;
2) taking viscous dark liquid, potassium hydroxide and ethylene glycol, firstly reacting for 10-12h at the temperature of 165-190 ℃ under stirring, then adding deionized water to react for 0.5-1h at the temperature of 90-110 ℃, and then cooling the reaction temperature to room temperature. The side reaction is increased when the isomerization temperature is too high or the isomerization time is too long, so that the color of the product is deepened; if the isomerization temperature is too low or the reaction time is too short, the content of the conjugate acid in the mixture is low; acidifying the system pH to 2-3 with hydrochloric acid; extracting the organic phase with solvent (one of diethyl ether, ethyl acetate and n-hexane), and washing with deionized water; finally, removing the solvent and water by reduced pressure distillation to obtain conjugated waste edible vegetable oil acid;
3) taking conjugated waste edible vegetable oil, amino acid, maleic anhydride, hydroquinone and acetic acid, reacting for 5-7h at 105-130 ℃ under the protection of nitrogen, adding deionized water, continuing to react for 0.5-1h under the reflux condition, and cooling the system to room temperature. The addition temperature is too high or the addition time is too long, so that side reactions are increased easily; if the temperature is too low or the time is too short, the addition reaction is not complete and the yield of the polyacid is low. Extracting the organic phase of the reaction mixture with a solvent (one of diethyl ether, ethyl acetate and n-hexane), and washing with deionized water; finally, removing the solvent and water by using a reduced pressure distillation mode to obtain the waste edible vegetable oil-based polyacid;
4) taking waste edible vegetable oil-based polyacid, dihydric alcohol monoalkyl ether, a catalyst (one of p-toluenesulfonic acid, sulfuric acid, tetrabutyl titanate, stannous chloride and cation exchange resin, the using amount is 0.5-5 wt% (calculated by the mass of the vegetable oil-based polyacid)), a dehydrating agent (one of toluene or cyclohexane, 40-70 wt% (calculated by the mass of the vegetable oil-based polyacid)), and finishing the reaction after 5-8h at the temperature of 120 ℃ plus 150 ℃; if the temperature is too high or the reaction time is too long, the color of the product is deepened, and the side reactions are increased; if the temperature is too low or the reaction time is too short, the esterification reaction is incomplete, resulting in a low yield of the objective product. Refining to remove excessive diol monoalkyl ether and dehydrating agent, and then NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; and finally, dehydrating by reduced pressure distillation to obtain the vegetable oil-based polyacid alcohol ether ester.
The vegetable oil polyacid alcohol ether ester is obtained by the method for preparing the vegetable oil polyacid alcohol ether ester by utilizing the waste edible vegetable oil; the components of the composition comprise:
wherein R is1H or CH3，R2＝C1-C6An alkyl group, n is 1 to 5.
The vegetable oil-based polyol ether ester is used as a plasticizer.
The vegetable oil-based polyol ether ester plasticizer provided by the application has two typical uses, wherein one of the two typical uses is plasticized polylactic acid plastic: mixing and extruding polylactic acid and vegetable oil-based polyol ether ester in an extruding machine; then preparing a polylactic acid sample mixed with the vegetable oil-based polyol ether ester on an injection molding machine according to the requirement to prepare a required product; wherein the mass ratio of the vegetable oil-based alcohol ether ester to the polylactic acid is as follows: 5-20: 100.
The other is a plasticized PVC material: adding PVC powder and a heat stabilizer into vegetable oil polyol ether ester serving as a plasticizer, mechanically premixing, mixing and extruding the mixture to prepare the PVC material with the ultraviolet resistance
Has the advantages that: compared with the prior art, the method for preparing the high-performance vegetable oil based poly (alcohol ether ester) ester by using the recycled waste edible oil as the raw material has the characteristics of environmental protection, waste utilization and the like. The molecular structure of the synthesized vegetable oil-based poly (alcohol ether) ester contains ester and ether groups with large polarity and good flexibility, so that the synthesized vegetable oil-based poly (alcohol ether) ester has the advantages of good compatibility with polylactic acid, PVC and the like, high plasticizing efficiency and the like, can completely replace the traditional petroleum-based plasticizer dioctyl terephthalate, is a plasticizer with excellent performance for polylactic acid and PVC materials, and realizes the resource utilization of wastes. In addition, the PVC material plasticized by the vegetable oil-based polyacid alcohol ether ester has excellent uvioresistant performance and good practicability.
Drawings
FIG. 1 shows waste edible vegetable oil acids1H NMR spectrum;
FIG. 2 is a conjugated waste edible vegetable oil acid1H NMR spectrum;
FIG. 3 shows the polyacid of waste edible oil1H NMR spectrum;
FIG. 4 shows WFOPA-1 product obtained by esterifying polyacid of waste edible oil with ethylene glycol monomethyl ether1H NMR spectrum; phi in the figure represents other structures except carboxyl in WFOPA;
FIG. 5 shows the addition amount of WFOPA-3 and the glass transition temperature (T)g) A relationship diagram of (1);
FIG. 6 is a UV spectrum of a plasticized PVC sample.
Detailed Description
The invention is further described below by way of examples, but without being limited thereto.
The raw waste edible vegetable oils in the following examples were supplied by Darling Ingredients; ethylene glycol methyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, diethylene glycol butyl ether and propylene glycol methyl ether are all industrial grade and are produced by Jiangsu Yida chemical company Limited; potassium hydroxide (90%), maleic anhydride (99%), dioctyl terephthalate (DOTP) (. gtoreq.96.0%), p-toluenesulfonic acid (. gtoreq.98.5%), cyclohexane (. gtoreq.99.5) supplied by Sigma-Aldrich; stannous chloride, tetrabutyl titanate and toluene are provided by national drug group chemical reagent company Limited; acetic acid, hydroquinone, sodium hydroxide were supplied by Fisher Scientific; hydrochloric acid was supplied by EMD Millipore corporation; polylactic acid (3052D) is supplied by Nature works corporation; PVC powder (DG-1000K) was supplied by Tianjin Staphylea chemical Co.
Example 1
The method for synthesizing the vegetable oil-based polyolester ester comprises the following steps:
1) hydrolyzing the waste edible vegetable oil into vegetable oleic acid:
adding 16.0g of sodium hydroxide and 140mL of ethanol-water solution (1:1, V/V) into a 1L three-mouth round-bottom bottle, magnetically stirring and heating to 70 ℃, then adding 100.0g of waste edible plant oil into a reaction system, reacting for 2 hours, adjusting the pH of the system to 2-3 by using hydrochloric acid (1mol/L), and continuing to react for 1 hour to finish the reaction. And extracting the mixture by using ether to obtain an organic phase, and washing the organic phase for 3-5 times by using deionized water. Finally, the ether and water were removed by distillation under reduced pressure to give a viscous dark liquid, marked with WFOA and having a nuclear magnetic diagram as shown in FIG. 1; the gas chromatography results indicated that the WFOA had a composition of: c16:0 (0.8%), C18:0 (14.9%), C18:1 (43.0%), C18:2 (34.6%), C18:3 (6.7%), W (C18:1) + W (C18:2) content in the mixture is more than 77%, which is the main component in the mixed vegetable oleic acid, it can be seen that WFOA prepared is a mixture, the structural formula of the main compound is:
2) isomerization of vegetable oil acid:
50g of the vegetable oil acid prepared in step 1), 50g of potassium hydroxide and 200mL of ethylene glycol were put into a 500mL round-bottomed flask and reacted for 10 hours at 180 ℃ with magnetic stirring. Then 50mL of deionized water was added and the reaction was carried out at 100 ℃ for 30min, and the reaction temperature was lowered to room temperature. Acidifying the system pH to 2-3 with hydrochloric acid (1 mol/L). The organic phase was extracted with ether and washed with deionized water. Finally, removing ether and water by distillation under reduced pressure to obtain conjugated vegetable oil acid, which is marked by CWFOA and has a nuclear magnetic diagram shown in figure 2; the yield is 87.3%, and the main structure is as follows:
3) synthesis of vegetable oil-based polyacid:
50g of conjugated vegetable oil-based acid prepared in the step 2), 42.0g of maleic anhydride, 917.0mg of hydroquinone and 150mL of acetic acid are put into a round-bottomed bottle and reacted for 5 hours at the temperature of 120 ℃ under the protection of nitrogen. Then 25mL of deionized water is added to continue the reaction for 30min under the reflux condition, and the temperature of the system is reduced to room temperature. The organic phase is extracted with diethyl ether and washed with deionization. Finally, the ether and water were distilled off under reduced pressure to obtain vegetable oil polyacid having an acid value of 309.7mg/g as a mixture, which was represented by WFOPA, and whose nuclear magnetic diagram of the main component is shown in FIG. 3, and whose main structural formula is as follows:
4) synthesis of vegetable oil-based polyacid (ethylene glycol methyl ether):
30g of the plant oil-based polyacid prepared in the step 3), 38.1g of ethylene glycol methyl ether, 0.3g of p-toluenesulfonic acid and 21.0g of cyclohexane are added into a four-mouth bottle, and the reaction is finished after 5 hours at the temperature of 130-150 ℃. Recovering the dehydrating agent cyclohexane and unreacted ethylene glycol monomethyl ether by reduced pressure distillation, and then using 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; finally, dehydrating and drying in a reduced pressure distillation mode to obtain vegetable oil-based polyacid (ethylene glycol monomethyl ether) ester (WFOPA-1) 38.4 mPa.s; rho (20 ℃) is 0.92g/cm3The nuclear magnetic diagram is shown in FIG. 4, and the structural formula of the main components is as follows:
example 2
Using the vegetable oil-based polyacid in example 1, vegetable oil-based polyacid (diethylene glycol methyl ether) ester was synthesized by the following process:
30g of the vegetable oil-based polyacid, 60.1g of diethylene glycol methyl ether, 0.3g of p-toluenesulfonic acid and 21.0g of cyclohexane are added into a four-mouth bottle, azeotropic dehydration is carried out at the temperature of 130-150 ℃, and the reaction is finished after 5 h. Recovering the dehydrating agent cyclohexane and the unreacted diethylene glycol monomethyl ether by reduced pressure distillation, and then using 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; and finally, dehydrating and drying in a reduced pressure distillation mode to obtain vegetable oil-based polyacid (diethylene glycol methyl ether) (WFOPA-2), wherein eta (25 ℃) is: 37.8 mPa.s; rho (20 ℃) is 0.93g/cm3The structural formula of the main components is as follows:
example 3
Using the vegetable oil-based polyacid in example 1, vegetable oil-based polyacid (triethylene glycol methyl ether) ester was synthesized by the following process:
30g of the vegetable oil-based polyacid, 82.1g of triethylene glycol methyl ether, 0.3g of p-toluenesulfonic acid and 21.0g of cyclohexane are added into a four-mouth bottle, and the reaction is finished after 5 hours at the temperature of 130-150 ℃. Removing the dehydrating agent cyclohexane and unreacted triethylene glycol methyl ether by reduced pressure distillation, and then adding 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; and finally, dehydrating and drying in a reduced pressure distillation mode to obtain vegetable oil-based polyacid (triethylene glycol methyl ether) ester (WFOPA-3), wherein eta (25 ℃) is: 36.6 mPa.s; rho (20 ℃) is 0.94g/cm3The structural formula of the main components is as follows:
example 4
Using the vegetable oil-based polyacid in example 1, vegetable oil-based polyacid (triethylene glycol methyl ether) ester was synthesized by the following process:
30g of the vegetable oil-based polyacid, 82.1g of triethylene glycol methyl ether, 0.15g of p-toluenesulfonic acid and 21.0g of cyclohexane are added into a four-mouth bottle, and the reaction is finished after 8 hours at the temperature of 130-150 ℃. Removing the dehydrating agent cyclohexane and unreacted triethylene glycol methyl ether by reduced pressure distillation, and then adding 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; finally, dehydration and drying are carried out in a reduced pressure distillation mode to obtain the vegetable oil-based polyacid (triethylene glycol methyl ether) (WFOPA-3) with the yield of 79.3 percent.
Example 5
The vegetable oil-based polyacid (triethylene glycol methyl ether) ester is synthesized by using the vegetable oil-based polyacid in the example 1 under the catalysis of tetrabutyl titanate, and the process is as follows:
30g of the vegetable oil-based polyacid, 82.1g of triethylene glycol methyl ether, 0.9g of tetrabutyl titanate and 21.0g of cyclohexane are added into a four-mouth bottle, and the reaction is finished after 5 hours at the temperature of 130-150 ℃. Removing the dehydrating agent cyclohexane and unreacted triethylene glycol methyl ether by reduced pressure distillation, and then adding 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; and finally, dehydrating and drying in a reduced pressure distillation mode to obtain the vegetable oil-based polyacid (triethylene glycol methyl ether) ester (WFOPA-3), wherein the yield is 85.2%.
Example 6
The vegetable oil-based polyacid (triethylene glycol methyl ether) ester is synthesized by using the vegetable oil-based polyacid in the example 1 under the catalysis of stannous chloride by the following process:
30g of the vegetable oil-based polyacid, 82.1g of triethylene glycol methyl ether, 1.5g of stannous chloride and 21.0g of cyclohexane are added into a four-mouth bottle, and the reaction is finished after 5 hours at the temperature of 130-. Removing the dehydrating agent cyclohexane and unreacted triethylene glycol methyl ether by reduced pressure distillation, and then adding 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; finally, dehydration and drying are carried out in a reduced pressure distillation mode to obtain the vegetable oil-based polyacid (triethylene glycol methyl ether) ester (WFOPA-3), and the yield is 88.0%.
Example 7
Using the vegetable oil-based polyacid in example 1, vegetable oil-based polyacid (triethylene glycol methyl ether) ester was synthesized by the following process:
30g of the vegetable oil-based polyacid, 27.2g of triethylene glycol methyl ether, 0.3g of p-toluenesulfonic acid and 21.0g of toluene are added into a four-mouth bottle, and the reaction is finished after 5 hours at the temperature of 130-150 ℃. Removing dehydrating agent toluene and unreacted triethylene glycol methyl ether by reduced pressure distillation, and then adding 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; finally, dehydration and drying are carried out in a reduced pressure distillation mode to obtain the vegetable oil-based polyacid (triethylene glycol methyl ether) ester (WFOPA-3) with the yield of 80.7 percent.
Example 8
Using the vegetable oil-based polyacid in example 1, vegetable oil-based polyacid (triethylene glycol methyl ether) ester was synthesized by the following process:
60g of the vegetable oil-based polyacid, 164.2g of triethylene glycol methyl ether, 0.6g of p-toluenesulfonic acid and 24.0g of toluene are added into a four-mouth bottle, and the reaction is finished after 5 hours at the temperature of 130-150 ℃. Removing dehydrating agent toluene and unreacted triethylene glycol methyl ether by reduced pressure distillation, and then adding 10 wt% of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; and finally, dehydrating and drying in a reduced pressure distillation mode to obtain the vegetable oil-based polyacid (triethylene glycol methyl ether) ester (WFOPA-3) with the yield of 78.6 percent.
Example 9
Using the vegetable oil-based polyacid of example 1, vegetable oil-based polyacid (diethylene glycol butyl ether) ester was synthesized by the following procedure:
30g of the vegetable oil-based polyacid, 80.7g of diethylene glycol monobutyl ether, 0.3g of p-toluenesulfonic acid and 21.0g of cyclohexane are added into a four-mouth bottle, and the reaction is finished after 5 hours at the temperature of 130 ℃ and 150 ℃. The dehydrating agent cyclohexane and unreacted diethylene glycol monobutyl ether were removed by distillation under reduced pressure and then with 10% by weight of NaHCO3Washing the residual liquid by the solution until the pH value of the system is neutral; and finally, dehydrating and drying in a reduced pressure distillation mode to obtain vegetable oil-based polyacid (diethylene glycol monobutyl ether) (WFOPA-DEB), wherein eta (25 ℃) is: 37.2 mPa.s; rho (20 ℃) is 0.93g/cm3The structural formula of the main components is as follows:
example 10
Using the vegetable oil-based polyacid in example 1, vegetable oil-based polyacid (propylene glycol methyl ether) ester was synthesized by the following process:
30g of the vegetable oil-based polyacid, 74.6g of propylene glycol methyl ether, 0.3g of p-toluenesulfonic acid and 21.0g of cyclohexane are added into a four-mouth bottle, and the reaction is finished after 8 hours at the temperature of 120-130 ℃. The dehydrating agent cyclohexane and unreacted propylene glycol methyl ether were removed by distillation under reduced pressure and then 10% by weight of NaHCO was used3Washing the residual liquid by the solution until the pH value of the system is neutral; and finally, dehydrating and drying in a reduced pressure distillation mode to obtain vegetable oil-based polyacid (propylene glycol methyl ether) (WFOPA-MP), wherein eta (25 ℃) is as follows: 42.3 mPa.s; rho (20 ℃) is 0.93g/cm3The structural formula of the main components is as follows:
example 11
5 parallel PLA/WFOPA-1 (20%) samples were prepared as required for testing using a Haake extruder at 175 ℃ for 5min and a Haake injection molding machine (Haake MiniJet II, Karlsruhe, Germany) at 155 ℃ under 600bars according to the mass ratio of WFOPA-1 to polylactic acid (PLA), m (WFOPA-1): m (PLA): 20: 100.
5 parallel PLA/WFOPA-2 (20%) samples were prepared as required for testing using a Haake extruder at 175 ℃ for 5min and a Haake injection molding machine (Haake MiniJet II, Karlsruhe, Germany) at 155 ℃ under 600bars according to the mass ratio of WFOPA-2 to polylactic acid (PLA), formulation m (WFOPA-2): m (PLA): 20: 100.
WFOPA-3 and polylactic acid (PLA) were injection molded at a mass ratio of m (WFOPA-3): m (PLA): 5:100, according to the above extrusion and injection molding conditions, to obtain 5 parallel PLA/WFOPA-3 (5%) samples.
5 parallel PLA/WFOPA-3 (10%) samples were prepared by injection molding WFOPA-3 and polylactic acid (PLA) at the mass ratio of m (WFOPA-3): m (PLA): 10:100, according to the above extrusion and injection molding conditions.
WFOPA-3 and polylactic acid (PLA) were injection molded at a mass ratio of m (WFOPA-3): m (PLA): 15:100, according to the above extrusion and injection molding conditions, to obtain 5 parallel PLA/WFOPA-3 (15%) samples.
5 parallel PLA/WFOPA-3 (20%) samples were prepared by injection molding WFOPA-3 and polylactic acid (PLA) at a mass ratio of m (WFOPA-3) to m (PLA): 20:100, under the above extrusion and injection molding conditions.
5 parallel PLA/WFOPA-DEB (20%) samples were prepared by injection molding WFOPA-DEB and polylactic acid (PLA) at the mass ratio of m (WFOPA-DEB) to m (PLA): 20:100, under the above extrusion and injection molding conditions.
The melt extrusion molding was carried out under the above extrusion and injection molding conditions to obtain 5 parallel PLA/WFOPA-MP (20%) samples, each of which had a formulation of WFOPA-MP and polylactic acid (PLA) in a mass ratio of m (WFOPA-MP) to m (PLA) of 20: 100.
Comparative sample preparation. DOTP and polylactic acid (PLA) were mixed in a mass ratio, m (DOTP): m (PLA): 20:100, at 175 ℃ for 5min in a Haake extruder, and then 5 parallel PLA/DOTP (20%) samples were prepared as required for the test using a Haake MiniJet II, Karlsruhe, Germany at 155 ℃ and 600 bars.
TABLE 1 evaluation of application Properties
In the table, the number of the first and second,aglass transition temperature (T)g) Obtained from dynamic mechanical thermal analysis (DMA) curves;bthe volatility test is carried out according to the standard HG/T4455-supplement 2012 at 70 ℃ for 24hMeasuring;cthe storage modulus is measured by dynamic mechanical thermal analysis (DMA).
As can be seen from table 1, the plasticizer prepared according to the present invention can significantly improve the ductility of polylactic acid (PLA). Compared with the traditional petroleum-based DOTP, the plasticizer has better plasticizing performance and better thermal stability. It is particularly noted that even with 5% addition of WFOPA-3, the plasticization efficiency is higher than with 20% addition of DOTP, and the mechanical (storage modulus) and thermal stability are higher.
Further, as is clear from FIG. 5, the addition amount and glass transition temperature (T) of the plasticizer WFOPA-3gMeasured by DSC) can be scattered evenly around the Fox equation curve, which indicates that WFOPA-3 has good compatibility with polylactic acid.
Example 12
PVC powder (100 parts) and WFOPA-1(40 parts), heat stabilizer: premixing calcium stearate (1.5 parts) and zinc stearate (0.5 part); the mixed batch was then compounded for 5min at 175 ℃ using a Haake extruder and then 5 parallel PVC/WFOPA-1 samples were prepared as required for the test using a Haake MiniJet II, Karlsruhe, Germany injection molding machine at 165 ℃ and 600 bars.
PVC powder (100 parts) and WFOPA-2(40 parts), heat stabilizer: premixing calcium stearate (1.5 parts) and zinc stearate (0.5 part); the mixed batch was then compounded for 5min at 175 ℃ using a Haake extruder and then 5 parallel PVC/WFOPA-2 samples were prepared as required for the test using a Haake injection molding machine (Haake MiniJet II, Karlsruhe, Germany) at 165 ℃ under 600 bars.
PVC powder (100 parts) and WFOPA-3(40 parts), heat stabilizer: premixing calcium stearate (1.5 parts) and zinc stearate (0.5 part); the mixed batch was then compounded for 5min at 175 ℃ using a Haake extruder and then 5 parallel PVC/WFOPA-3 samples were prepared as required for the test using a Haake injection molding machine (Haake MiniJet II, Karlsruhe, Germany) at 165 ℃ under 600 bars.
Mixing PVC powder (100 parts) with DOTP (40 parts), and a heat stabilizer: premixing calcium stearate (1.5 parts) and zinc stearate (0.5 part); the mixed material was then compounded for 5min at 175 ℃ using a Haake extruder and then 5 parallel PVC/DOTP samples were prepared as required for the test using a Haake MiniJet II, Karlsruhe, Germany at 165 ℃ under 600 bars.
TABLE 2 evaluation of application Properties
In the table, the number of the first and second,aglass transition temperature (T)g) Obtained from dynamic mechanical thermal analysis (DMA) curves;bT5％，T10％temperature, representing 5% and 10% weight loss, respectively, of the sample, as measured by Thermogravimetry (TGA);cmobility: and (3) soaking the plasticized PVC sample in n-hexane for 24 hours at the temperature of 23 +/-2 ℃ and the relative humidity of 50 +/-10%, and calculating according to the mass reduction percentage.
As can be seen from Table 2, the ductility of PVC can be remarkably improved by the plasticizer prepared by the invention, and with the increase of the polymerization degree n, the elongation at break and the thermal stability of the plasticizer are better, even better than those of the traditional petroleum-based DOTP, which indicates that the waste edible vegetable oil-based polyacid alcohol ether ester plasticizer has excellent plasticizing performance and thermal stability. The special indication that the migration resistance of the waste edible vegetable oil-based polyalcohol ether ester is better than that of DOTP indicates that the waste edible vegetable oil-based polyalcohol ether ester is safer.
The plasticized PVC specimens described above were analyzed by testing on a UV-vis spectrometer (Perkin-Elmer, Model Lambda 25) and the results are shown in FIG. 6. In addition, as can be seen from FIG. 6, the transmittances of WFOPA-1, WFOPA-2, WFOPA-3, WFOPAM and the like in the UV wavelength range of 200-.
Claims (10)
1. A method for preparing vegetable oil-based polyacid alcohol ether ester by using waste edible vegetable oil is characterized in that the waste edible vegetable oil is used as a raw material, firstly, hydrolysis and isomerization reaction are carried out, then, Diels-Alder addition reaction is carried out on the waste edible vegetable oil and maleic anhydride to obtain vegetable oil-based polyacid, and the vegetable oil-based polyacid ether ester is synthesized by esterification reaction of the vegetable oil-based polyacid and dihydric alcohol monoalkyl ether; wherein, the molar ratio of the vegetable oil-based polyacid to the dihydric alcohol monoalkyl ether is as follows: 1: 1-5; the structural general formula of the dihydric alcohol monoalkyl ether is as follows:
in the formula, n is: 1 to 5, R1Is H or CH3，R2Is C1-6An alkyl group.
2. The method for preparing vegetable oil-based polyalcohol ether ester by using waste edible vegetable oil according to claim 1, which is characterized by comprising the following steps:
1) adding sodium hydroxide and an ethanol-water solution into a reactor, stirring and heating to 60-70 ℃, then dropwise adding waste edible vegetable oil into a reaction system, reacting for 2-5h, adjusting the pH of the system to 2-3, and continuing to react for 1-5h until the reaction is finished; extracting the mixture with a solvent to obtain an organic phase, and washing with deionized water; finally, removing the solvent and water by a reduced pressure distillation mode to obtain viscous dark liquid;
2) taking viscous dark liquid, potassium hydroxide and ethylene glycol, controlling the temperature at 165 ℃ and 190 ℃, and stirring for reaction for 10-12 h; then adding deionized water, controlling the temperature to be 90-110 ℃, continuing to react for 0.5-1h, and cooling the reaction temperature to room temperature; adjusting the pH value to 2-3; extracting the organic phase by using a solvent and washing by using deionized water; finally, removing the solvent and water by reduced pressure distillation to obtain conjugated vegetable oil acid;
3) taking conjugated vegetable oil-based acid, maleic anhydride, hydroquinone and acetic acid, controlling the temperature at 105 ℃ and 130 ℃ and carrying out nitrogen protection reaction for 5-7 h; then adding deionized water to continue reacting for 0.5-1h under the reflux condition, and cooling the system temperature to room temperature; extracting the organic phase with a solvent and washing with deionized water; finally, removing the solvent and water by using a reduced pressure distillation mode to obtain the vegetable oil-based polyacid;
4) reacting vegetable oil-based polyacid, dihydric alcohol monoalkyl ether, a catalyst and a dehydrating agent at the temperature of 120 ℃ and 150 ℃ for 5-8 h; removing excessive diol monoalkyl ether and dehydrating agent by refining treatment, and then washing the residual liquid until the pH value of the system is neutral; finally, carrying out reduced pressure distillation and dehydration to obtain vegetable oil-based polyolester ester; wherein the catalyst is one of p-toluenesulfonic acid, sulfuric acid, tetrabutyl titanate, stannous chloride and cation exchange resin, and the using amount is 0.5-5 wt%; the dehydrating agent is one of methylbenzene or cyclohexane, and the using amount is 40-70 wt%.
3. The method for preparing the vegetable oil-based polyol ether ester by using the waste edible vegetable oil as claimed in claim 2, wherein in the step 1), the waste edible vegetable oil is stirred and heated to 60-70 ℃, then the waste edible vegetable oil is dropped into the reaction system, after the reaction is carried out for 2 hours, the pH value of the system is adjusted to 2-3 by using 0.5-1mol/L hydrochloric acid, and the reaction is finished after the reaction is continued for 1 hour.
4. The method for preparing vegetable oil-based poly (acid alcohol ether ester) using waste edible vegetable oil as claimed in claim 2, wherein in the step 2), the reaction is performed for 10h under stirring at 180-190 ℃, then deionized water is added to react for 0.5h at 90-100 ℃, and then the reaction temperature is reduced to room temperature.
5. The method for preparing vegetable oil-based poly (acid alcohol ether ester) from waste edible vegetable oil as claimed in claim 2, wherein in step 3), the reaction is carried out at 105-120 ℃ for 5-6h under the protection of nitrogen, then deionized water is added to continue the reaction for 0.5h under the reflux condition, and then the temperature of the system is reduced to room temperature.
6. The vegetable oil-based poly (acid-based alcohol ether ester) obtained by the method for preparing the vegetable oil-based poly (acid-based alcohol ether ester) according to any one of claims 1 to 5, using waste edible vegetable oil.
7. The vegetable oil poly-acid alcohol ether ester of claim 6, wherein the components comprise:
wherein R is1H or CH3，R2＝C1-C6An alkyl group, n is 1 to 5.
8. Use of the vegetable oil-based polyalcohol ether esters according to claim 6 or 7 as plasticizers.
9. Use according to claim 8, characterized in that: mixing and extruding polylactic acid and vegetable oil-based polyol ether ester in an extruding machine; then preparing a polylactic acid sample mixed with the vegetable oil-based polyol ether ester on an injection molding machine according to the requirement to prepare a required product; wherein the mass ratio of the vegetable oil-based alcohol ether ester to the polylactic acid is as follows: 5-20: 100.
10. Use according to claim 9, characterized in that: adding PVC powder and a heat stabilizer into vegetable oil polyol ether ester serving as a plasticizer, mechanically premixing, and then mixing and extruding the mixture to prepare the PVC material with the uvioresistant performance.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829458A (en) * | 2015-04-01 | 2015-08-12 | 南京林业大学 | Synthetic method of di(glycol monoalkyl ether)terephthalate |
| CN105481690A (en) * | 2015-12-01 | 2016-04-13 | 江苏怡达化学股份有限公司 | Benzoyl ricinoleic acid binary alcohol ether ester and synthetic method thereof |
| EP3287484A1 (en) * | 2015-09-28 | 2018-02-28 | Evonik Degussa GmbH | Cyclohexane-1,2,4-tricarboxylic acid tripentylester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070207939A1 (en) * | 2006-02-10 | 2007-09-06 | Gyorgyi Fenyvesi | Compositions comprising mono and di esters of biologically-based 1,3-propanediol |
-
2019
- 2019-02-21 CN CN201910136307.7A patent/CN109970556B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829458A (en) * | 2015-04-01 | 2015-08-12 | 南京林业大学 | Synthetic method of di(glycol monoalkyl ether)terephthalate |
| EP3287484A1 (en) * | 2015-09-28 | 2018-02-28 | Evonik Degussa GmbH | Cyclohexane-1,2,4-tricarboxylic acid tripentylester |
| CN105481690A (en) * | 2015-12-01 | 2016-04-13 | 江苏怡达化学股份有限公司 | Benzoyl ricinoleic acid binary alcohol ether ester and synthetic method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Esters of maleinized fatty compounds as plasticizers;Ursula Biermann et al.;《Eur. J. Lipid Sci. Technol.》;20120131;第144卷(第1期);第49-54页 * |
| Use of Hempseed-Oil-Derived Polyacid and Rosin-Derived Anhydride Acid as Cocuring Agents for Epoxy Materials;Ran Li et al.;《ACS Sustainable Chemistry & Engineering》;20180207;第6卷(第3期);第4016-4025页 * |
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