CN116284704A - Synthesis method of novel bio-based cardanol modified PET material - Google Patents
Synthesis method of novel bio-based cardanol modified PET material Download PDFInfo
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- CN116284704A CN116284704A CN202310460919.8A CN202310460919A CN116284704A CN 116284704 A CN116284704 A CN 116284704A CN 202310460919 A CN202310460919 A CN 202310460919A CN 116284704 A CN116284704 A CN 116284704A
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- cardanol
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- glycidyl ether
- glycol terephthalate
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 150
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 150
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 150
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 115
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 73
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 55
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 55
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 54
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 43
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 17
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 238000006703 hydration reaction Methods 0.000 claims abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 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 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000004224 protection Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 244000226021 Anacardium occidentale Species 0.000 abstract description 9
- 235000020226 cashew nut Nutrition 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920006025 bioresin Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses synthesis of a novel cardanol modified PET (polyethylene terephthalate) new material. The invention adopts cardanol and epichlorohydrin to stir and mix at room temperature to react to generate cardanol glycidyl ether, then the cardanol glycidyl ether and excessive water are subjected to hydration reaction to generate cardanol glycerol diol, and then the cardanol glycerol diol and terephthalic acid are subjected to esterification reaction to obtain terephthalic acid cardanol glycol ester, and the cardanol modified PET is generated through further polycondensation reaction: polyethylene terephthalate cardanol glycol ester. The production process adopts the bio-based cardanol modified PET to endow the PET cardanol polymer with the properties of high temperature resistance, oil resistance, chemical resistance and antibacterial property, so that the added value of the biological inedible cashew nut shell is improved.
Description
Technical Field
The invention relates to a synthesis method of a modified material, in particular to a synthesis method of a novel bio-based cardanol modified PET material.
Background
With the development of global economy and science and technology, plastic products are increasingly widely applied to daily life of people. PET is a widely used plastic material with good transparency, heat resistance and mechanical strength, and is widely applied to the fields of bottled beverages, food packaging and the like. However, the problems of low heat resistance, low weather resistance, low chemical resistance, etc. of PET limit its application in some special application fields. In order to improve the performance of PET, many researchers have tried various methods such as adding fillers, modifiers, etc.
The PET engineering plastic has excellent mechanical property, heat resistance, electrical insulation and chemical reagent resistance, and has low price, wide application market and good development prospect compared with other engineering plastics. The monomers terephthalic acid and ethylene glycol used in PET polymerization are derived from fossil resources, and the consumption of fossil resources is gradually increased as the consumption of the monomers terephthalic acid and ethylene glycol is increased. Therefore, bio-based monomers useful for PET and bio-based resins that can replace PET have become the current research focus. Cashew nut shell oil is taken as renewable biological mixed fat extracted from cashew nut shell waste, and a mixture mainly containing cardanol can be generated after simple heating treatment. And the cardanol polymer derivative has good toughness, hydrophobicity, low permeability, self-drying property, viscoelasticity and the like.
Disclosure of Invention
The purpose is as follows: according to the invention, the biological-based cardanol modified PET is adopted, so that an effective strategy is provided for improving the properties of high temperature resistance, oil resistance, chemical resistance, antibacterial property and the like of PET materials. The invention discloses synthesis of a novel cardanol modified PET (polyethylene terephthalate) new material.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme:
the synthesis method of the novel bio-based cardanol modified PET material is characterized by comprising the following steps:
(1) Synthesis of cardanol glycidyl ether
Adding cardanol, potassium hydroxide and dimethyl sulfoxide (DMSO) into a container, dropwise adding epichlorohydrin under the protection of ice bath, and stirring at room temperature; after the reaction is finished, the cardanol glycidyl ether is obtained through treatment;
(2) Synthesis of cardanol glycerol diol
Adding p-cardanol glycidyl ether and excessive water into a hydrothermal reaction kettle, and heating to 120-180 deg.C o Stirring and reacting for 3-8 hours, and extracting to obtain a product cardanol glycerol diol;
(3) Synthesis of polyethylene glycol terephthalate
Adding terephthalic acid, cardanol glycerol diol and p-toluenesulfonic acid into a container, stirring and reacting for about 8-12 hours at 230-260 ℃ to obtain cardanol glycol terephthalate; then gradually heating up and decompressing the reaction system, performing polycondensation reaction at the temperature of 250-300 ℃ and the pressure of 80-120Pa, ending the polymerization reaction after 1.5-2.5 hours, and then taking out the product of the cardanol polyethylene terephthalate.
The cardanol glycidyl ether is generated by adopting the stirring and mixing reaction of cardanol and epichlorohydrin at room temperature. And then carrying out hydration reaction on the cardanol glycidyl ether and excessive water to generate cardanol glycerol diol. Then, carrying out esterification reaction on cardanol glycerol diol and terephthalic acid to obtain cardanol glycol terephthalate, and carrying out further polycondensation reaction to obtain cardanol modified PET: polyethylene terephthalate cardanol glycol ester.
Aiming at the limitation of PET, the invention develops a novel cardanol modified PET new material by utilizing a main component cardanol (shown as a formula 2) modified PET material in cashew nut shell oil (Cashew nut shell liquid, CNSL) with good oxidation resistance, ultraviolet resistance and biodegradability, so as to improve the performance of PET and expand the application field of cashew nut shell oil.
A PET structure of formula 1;
a cardanol structure of formula 2;
the cardanol glycidyl ether (2) is generated by adopting the stirring and mixing reaction of the cardanol (1) and the epichlorohydrin at room temperature. And then carrying out hydration reaction on the cardanol glycidyl ether and excessive water to generate cardanol glycerol diol (3). Then, cardanol glycol and terephthalic acid are subjected to esterification reaction to obtain cardanol glycol terephthalate (4), and cardanol modified PET can be generated through further polycondensation reaction: and (5) polyethylene glycol terephthalate (cardanol terephthalate). The reaction formula is shown in the formula 3.
A synthesis reaction equation of cardanol modified PET of formula 3;
the production process adopts the bio-based cardanol modified PET to endow the PET cardanol polymer with the properties of high temperature resistance, oil resistance, chemical resistance and antibacterial property. The process reduces the use of ethylene glycol from fossil resources, expands the use range of cashew nut shell oil, and improves the added value of the biologically inedible cashew nut shells.
Preferably, the synthesis of the novel bio-based cardanol modified PET material comprises the following synthesis steps:
(1) Synthesis of cardanol glycidyl ether
Cardanol, potassium hydroxide and dimethyl sulfoxide (DMSO) were added to a round bottom flask, epichlorohydrin was slowly added dropwise under ice bath protection, and then stirred at room temperature for 24 hours. After the reaction is finished, the cardanol glycidyl ether is obtained through treatment.
(2) Synthesis of cardanol glycerol diol
Adding p-cardanol glycidyl ether and excessive water into a hydrothermal reaction kettle, and heating to 150 o Stirring and reacting the C for 5 hours, and extracting to obtain the product cardanol glycerol diol.
(3) Synthesis of polyethylene glycol terephthalate
Adding terephthalic acid, cardanol glycerol diol and p-toluenesulfonic acid into a round bottom flask, and carrying out stirring reaction at 250 ℃ for about 10 hours to carry out esterification to obtain cardanol glycol terephthalate; then the reaction system is gradually heated and decompressed, and then the polycondensation reaction is carried out at 280 ℃ and under the pressure of 100Pa, the polymerization reaction is finished after 2 hours, and then the product of the cardanol glycol terephthalate is taken out.
Preferably, the feeding range in the synthesis of the cardanol glycerol diol in the step (2) is as follows: the molar feed ratio of cardanol glycidyl ether to water is 1: 15-25; based on the reaction economy and the difficulty of the post-refining operation, the final selected feeding mole ratio is 1:20 for feeding.
Preferably, the feeding range in the synthesis of the cardanol glycol terephthalate in the step (3) is as follows: the molar feed ratio of terephthalic acid to cardanol glycerol diol is 1:0.8 to 1.25; based on the reaction economy and the difficulty of the post-refining operation, the final selected feeding mole ratio is 1:1 for feeding.
Preferably, the monomer of the cardanol glycol terephthalate is cardanol glycol terephthalate, and the cardanol glycol terephthalate can be obtained by esterifying cardanol glycol and terephthalic acid, and the scope of the right also includes the situation that the mixture of cardanol glycol terephthalate and glycol terephthalate with different proportions is partially adopted as the monomer.
Preferably, the batch feeding range in the synthesis of the cardanol glycidyl ether in the step (1) is as follows: the molar feed ratio of cardanol to epichlorohydrin is 1:1-5, and according to the reaction effect and economy, the invention preferably selects 1:3.2.
the invention has the beneficial effects that:
(1) The cardanol glycidyl ether is generated by adopting the stirring and mixing reaction of cardanol and epichlorohydrin at room temperature. And then carrying out hydration reaction on the cardanol glycidyl ether and excessive water to generate cardanol glycerol diol. Then, carrying out esterification reaction on cardanol glycerol diol and terephthalic acid to obtain cardanol glycol terephthalate, and carrying out further polycondensation reaction to obtain cardanol modified PET: polyethylene terephthalate cardanol glycol ester. According to the process, cardanol glycerol diol from cashew nut shell oil is used as a raw material to replace ethylene glycol for reaction, and cardanol groups are introduced into the obtained PET product, so that the high temperature resistance, oil resistance, chemical resistance and antibacterial property of cardanol are introduced into the PET product, the application range of the PET product is further widened, and the added value of the PET product is improved.
(2) The cardanol in the biologically inedible part is nontoxic, environment-friendly, low in price and stable in property, and even if trace residues exist in the product, the cardanol does not have adverse effect on the use of the prepared material, so that the method is suitable for the implementation of industrial production of environment-friendly and economic PET materials.
Detailed Description
The invention is illustrated by the following examples:
example 1 (molar feed ratio of cardanol glycidyl ether to distilled water was 1:15, molar feed ratio of terephthalic acid to cardanol glycerol diol was 1:0.8).
(1) Synthesis of cardanol glycidyl ether
Cardanol (90.0 g, 0.30 mol), potassium hydroxide (44.0 g, 0.78 mol) and DMSO (200 mL) were added to a 500mL round bottom flask, and epichlorohydrin (89.0 g, 0.96 mol) was slowly added dropwise under ice bath protection, followed by stirring at room temperature for 24 hours. After the completion of the reaction, the reaction mixture was extracted with diethyl ether, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation, followed by separation by chromatography (ethyl acetate: n-hexane=1:9 v/v as developing solvent) to give cardanol glycidyl ether (85.0 g, yield 79.7%).
(2) Synthesis of cardanol glycerol diol
Adding p-cardanol glycidyl ether (18.0 g, 0.05 mol) and excessive distilled water (13.5 g, 0.75 mol) into a hydrothermal reaction kettle, heating to 150 o C is stirred and reacted for 5 hours, the product is taken out of a hydrothermal reaction kettle after being cooled, the solvent is removed by diethyl ether extraction, anhydrous magnesium sulfate drying, filtration and rotary evaporation, and then the product cardanol glycerol diol (13.9 g, yield 77.1%) is obtained by separating through a chromatographic column (the developing agent is ethyl acetate: n-hexane=1:2 v/v).
(3) Synthesis of polyethylene glycol terephthalate
Terephthalic acid (6.6 g,0.04 mol), cardanol glycerol diol (11.5 g,0.032 mol) and p-toluenesulfonic acid (0.17 g,0.001 mol) were added to a round bottom flask equipped with a water separator, replaced with nitrogen gas twice, and the mixture was stirred at 250℃for about 10 hours to carry out esterification (the end of the reaction was determined based on the amount of water produced) to obtain cardanol glycol terephthalate; then the reaction system is gradually heated up and decompressed, and then the polycondensation reaction is carried out under the reaction condition that the temperature is 280 ℃ and the pressure is less than 100Pa, the polymerization reaction is finished after 2 hours, then the product of the cardanol polyethylene terephthalate is taken out, and the cardanol polyethylene terephthalate is washed by ethanol, dried and weighed (14.1 g, yield 88.1%) after cooling.
Example 2 (molar feed ratio of cardanol glycidyl ether to distilled water was 1:20, molar feed ratio of terephthalic acid to cardanol glycerol diol was 1:1).
(1) Synthesis of cardanol glycidyl ether
As in example 1.
(2) Synthesis of cardanol glycerol diol
Adding p-cardanol glycidyl ether (18.0 g, 0.05 mol) and excessive distilled water (18.0 g, 1.00 mol) into a hydrothermal reaction kettle, heating to 150 o C is stirred and reacted for 5 hours, the product is taken out of a hydrothermal reaction kettle after being cooled, the solvent is removed by diethyl ether extraction, anhydrous magnesium sulfate drying, filtration and rotary evaporation, and then the product cardanol glycerol diol (15.0 g, yield 83.2%) is obtained by separating the product by a chromatographic column (the developing agent is ethyl acetate: n-hexane=1:2 v/v).
(3) Synthesis of polyethylene glycol terephthalate
Terephthalic acid (6.6 g,0.04 mol), cardanol glycol (14.4 g,0.04 mol) and p-toluenesulfonic acid (0.17 g,0.001 mol) were added to a round bottom flask equipped with a water separator, replaced with nitrogen twice, and the mixture was stirred at 250℃for about 10 hours to carry out esterification (the end of the reaction was determined based on the amount of water produced) to obtain cardanol glycol terephthalate; then the reaction system is gradually heated up and decompressed, and then the polycondensation reaction is carried out under the reaction condition that the temperature is 280 ℃ and the pressure is less than 100Pa, the polymerization reaction is finished after 2 hours, then the product of the cardanol polyethylene terephthalate is taken out, and the cardanol polyethylene terephthalate is washed by ethanol, dried and weighed (18.1 g, yield 89.1%) after cooling.
Example 3 (molar feed ratio of cardanol glycidyl ether to distilled water was 1:25, molar feed ratio of terephthalic acid to cardanol glycerol diol was 1:1.25).
(1) Synthesis of cardanol glycidyl ether
As in example 1.
(2) Synthesis of cardanol glycerol diol
Adding p-cardanol glycidyl ether (18.0 g, 0.05 mol) and excessive distilled water (22.5 g, 1.25 mol) into a hydrothermal reaction kettle, heating to 150 o C is stirred and reacted for 5 hours, the product is taken out of a hydrothermal reaction kettle after being cooled, the solvent is removed by diethyl ether extraction, anhydrous magnesium sulfate drying, filtration and rotary evaporation, and then the product cardanol glycerol diol (15.2 g, yield 83.2%) is obtained by separating the product by a chromatographic column (the developing agent is ethyl acetate: n-hexane=1:2 v/v).
(3) Synthesis of polyethylene glycol terephthalate
Terephthalic acid (5.3 g, 0.32 mol), cardanol glycol (14.4 g,0.04 mol) and p-toluenesulfonic acid (0.17 g,0.001 mol) were added to a round bottom flask equipped with a water separator, replaced with nitrogen twice, and the mixture was stirred at 250℃for about 10 hours to carry out esterification (the end of the reaction was determined based on the amount of water produced) to obtain cardanol glycol terephthalate; then the reaction system is gradually heated up and depressurized, and then the polycondensation reaction is carried out under the reaction condition that the temperature is 280 ℃ and the pressure is less than 100Pa, the polymerization reaction is ended after 2 hours, and then the product of the cardanol polyethylene terephthalate (14.3 g, yield 89.4%) is taken out.
The present invention has been described in terms of the preferred embodiments, but the invention is not limited thereto, and the equivalent substitution or equivalent transformation can be adopted to achieve the technical solution within the scope of the present invention.
Claims (7)
1. The synthesis method of the novel bio-based cardanol modified PET material is characterized by comprising the following steps:
(1) Synthesis of cardanol glycidyl ether
Adding cardanol, potassium hydroxide and dimethyl sulfoxide (DMSO) into a container, dropwise adding epichlorohydrin under the protection of ice bath, and stirring at room temperature; after the reaction is finished, the cardanol glycidyl ether is obtained through treatment;
(2) Synthesis of cardanol glycerol diol
The p-cardanol glycidyl ether and the p-cardanol glycidyl ether are subjected to the reactionAdding water into a hydrothermal reaction kettle, heating to 120-180 deg.C o Stirring and reacting for 3-8 hours, and extracting to obtain a product cardanol glycerol diol;
(3) Synthesis of polyethylene glycol terephthalate
Adding terephthalic acid, cardanol glycerol diol and p-toluenesulfonic acid into a container, stirring and reacting for about 8-12 hours at 230-260 ℃ to obtain cardanol glycol terephthalate; then gradually heating up and decompressing the reaction system, performing polycondensation reaction at the temperature of 250-300 ℃ and the pressure of 80-120Pa, ending the polymerization reaction after 1.5-2.5 hours, and then taking out the product of the cardanol polyethylene terephthalate.
2. The synthesis method of the novel bio-based cardanol modified PET material according to claim 1, which is characterized by comprising the following steps:
(1) Synthesis of cardanol glycidyl ether
Adding cardanol, potassium hydroxide and dimethyl sulfoxide (DMSO) into a round bottom flask, slowly dropwise adding epichlorohydrin under the protection of an ice bath, and stirring at room temperature for 24 hours; after the reaction is finished, the cardanol glycidyl ether is obtained through treatment;
(2) Synthesis of cardanol glycerol diol
Adding p-cardanol glycidyl ether and excessive water into a hydrothermal reaction kettle, and heating to 150 o Stirring and reacting for 5 hours, and extracting to obtain a product cardanol glycerol diol;
(3) Synthesis of polyethylene glycol terephthalate
Adding terephthalic acid, cardanol glycerol diol and p-toluenesulfonic acid into a round bottom flask, stirring at 250 ℃ for reaction for about 10 hours, and esterifying to obtain cardanol glycol terephthalate; then the reaction system is gradually heated and decompressed, and then the polycondensation reaction is carried out at 280 ℃ and under the pressure of 100Pa, the polymerization reaction is finished after 2 hours, and then the product of the cardanol glycol terephthalate is taken out.
3. The synthesis method of the novel bio-based cardanol modified PET material according to claim 1, which is characterized in that: the feeding range in the synthesis of the cardanol glycerol diol in the step (2) is as follows: the molar feed ratio of cardanol glycidyl ether to water is 1: 15-25; based on the reaction economy and the difficulty of the post-refining operation, the final selected feeding mole ratio is 1:20 for feeding.
4. The synthesis method of the novel bio-based cardanol modified PET material according to claim 1, which is characterized in that: the feeding range in the synthesis of the cardanol glycol terephthalate in the step (3) is as follows: the molar feed ratio of terephthalic acid to cardanol glycerol diol is 1:0.8 to 1.25; based on the reaction economy and the difficulty of the post-refining operation, the final selected feeding mole ratio is 1:1 for feeding.
5. The synthesis method of the novel bio-based cardanol modified PET material according to claim 1, which is characterized in that: the monomer of the cardanol glycol terephthalate is cardanol glycol terephthalate, the cardanol glycol terephthalate can be obtained by esterifying cardanol glycerol diol and terephthalic acid, and the scope of the right also includes the situation that the mixture of the cardanol glycol terephthalate and the glycol terephthalate with different proportions is partially adopted as the monomer.
6. The synthesis method of the novel bio-based cardanol modified PET material according to claim 1, which is characterized in that: the feeding range in the synthesis of the cardanol glycidyl ether in the step (1) is as follows: the molar feed ratio of cardanol to epichlorohydrin is 1:1-5, and according to the reaction effect and economy, the invention preferably selects 1:3.2.
7. the method for synthesizing the novel bio-based cardanol modified PET material according to any one of claims 1 to 6, wherein the method is characterized in that: stirring and mixing cardanol (1) and epichlorohydrin at room temperature to react and generate cardanol glycidyl ether (2); then carrying out hydration reaction on the cardanol glycidyl ether and excessive water to generate cardanol glycerol diol (3); then, cardanol glycol and terephthalic acid are subjected to esterification reaction to obtain cardanol glycol terephthalate (4), and the cardanol modified PET is generated through further polycondensation reaction: a cardanol polyethylene terephthalate (5); the reaction formula is:
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