CN113150507A - Petroleum resin modified bio-based polyester and preparation method thereof - Google Patents
Petroleum resin modified bio-based polyester and preparation method thereof Download PDFInfo
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- 239000003208 petroleum Substances 0.000 title claims abstract description 71
- 239000011347 resin Substances 0.000 title claims abstract description 68
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 229920000728 polyester Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 41
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000006068 polycondensation reaction Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 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 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims 3
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 15
- 230000008025 crystallization Effects 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000002035 prolonged effect Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000000155 melt Substances 0.000 abstract description 5
- 238000004383 yellowing Methods 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical group 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- -1 Polyethylene furandicarboxylate Polymers 0.000 description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from 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
- C08G63/66—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to petroleum resin modified bio-based polyester and a preparation method thereof. The invention relates to petroleum resin modified bio-based polyester, which comprises the following components in parts by weight: 30-80 parts of furan dicarboxylic acid and/or esterified product thereof, 20-70 parts of ethylene glycol and 5-20 parts of petroleum resin. The melt index of the polyester material is increased from 32.1g/10min to 46.1g/10min or above by adding the petroleum resin, which shows that the processing fluidity of the PEF is obviously improved, and the phenomena of yellowing, degradation and the like caused by too long heating time in the PEF processing can be avoided; meanwhile, the semi-crystallization time is prolonged from 30.9min to 38.7min or more, which shows that the crystallization rate of the PEF is obviously reduced, the crystallization time is prolonged, and the improvement of the transparency of the PEF product is facilitated.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to petroleum resin modified bio-based polyester and a preparation method thereof.
Background
Polyethylene furandicarboxylate (PEF) is a full-bio-based green polyester prepared by using bio-based furan dicarboxylic acid or an esterified product thereof and dihydric alcohol as raw materials, and has higher glass transition temperature (87 ℃), higher tensile modulus (2.8GPa) and more excellent gas barrier property compared with petroleum-based counterpart polyethylene terephthalate (PET). Based on the above properties, PEF has been regarded as a polyester material that can be used in the fields of food packaging, plastic bottles, films, and the like, instead of PET.
However, PEF suffers from yellowing, degradation and the like due to too long heating time, so that high fluidity is required in the high-temperature processing processes of injection molding, film blowing and the like of the PEF, so as to shorten the high-temperature contact time as much as possible and avoid the occurrence of the adverse phenomena of yellowing, degradation and the like; in addition, the existing PEF products are dark in color, and the application of the PEF products in packaging, plastics and film products is severely limited. The prior Chinese invention patent (CN107840948A) discloses a technical problem of improving the dark color of bio-based furan polyester by adding furan diformyl chloride into a bio-based composition, which mainly depends on the nucleophilic substitution reaction of furan diformyl chloride and dihydric alcohol in the composition to generate a white esterified substance, thereby undoubtedly increasing the complexity of the reaction process and increasing the possibility of generating byproducts, meanwhile, the furan diformyl chloride has stronger corrosion performance, and can be easily corroded by the furan diformyl chloride if the furan diformyl chloride is not used properly, the price of the furan diformyl chloride is expensive (about 990 yuan/g), and the production cost of the bio-based furan polyester is greatly increased.
Disclosure of Invention
The present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a petroleum resin-modified bio-based polyester having excellent processing flowability, high transparency, and low production cost.
The above object of the present invention can be achieved by the following technical solutions: a petroleum resin modified bio-based polyester comprises the following components in parts by weight: 30-80 parts of furan dicarboxylic acid and/or esterified product thereof, 20-70 parts of ethylene glycol and 5-20 parts of petroleum resin.
The petroleum resin contains hydroxyl groups and other groups, and the hydroxyl groups and other groups are added as raw materials, so that the petroleum resin can interact with other material components, the compatibility among the components is improved, the processing fluidity of the PEF is improved, and the phenomena of yellowing, degradation and the like caused by overlong heating time during PEF processing are avoided; meanwhile, the crystallization rate of the PEF can be reduced, the crystallization time is prolonged, and the improvement of the transparency of the PEF product is facilitated. However, in the present application, when the amount of petroleum resin added is less than 5 parts, the fluidity of the obtained bio-based polyester is not significantly improved, and the fluidity of the bio-based polyester material is more significantly improved with the increase of the amount of petroleum resin added, but the tensile strength is gradually reduced, and when the amount of petroleum resin added is more than 20 parts, the tensile strength of the bio-based polyester material is greatly reduced, and the amount of petroleum resin added is strictly controlled within the above range.
More preferably, the weight portion of the petroleum resin is 5-15.
Preferably, the petroleum resin is at least one of C5 petroleum resin, C9 petroleum resin, hydrogenated C5 petroleum resin and hydrogenated C9 petroleum resin.
More preferably, the petroleum resin has a relative number average molecular weight of 300-3000.
Preferably, the petroleum resin modified bio-based polyester further comprises an esterification or ester exchange catalyst and a polycondensation catalyst, and the amount of the esterification or ester exchange catalyst and the polycondensation catalyst is 0.2 to 0.5mol percent of the furan dicarboxylic acid and/or the esterified product thereof. For the reaction of the invention, the catalyst amount is too small, the activity is low, and the reaction can not be stimulated; when the amount is too large, the reaction will generate sudden aggregation, and the product performance is affected, so the addition is required to be strictly carried out according to the proportion range.
Further preferably, the esterification or transesterification catalyst is at least one of anhydrous zinc acetate and anhydrous manganese acetate.
More preferably, the polycondensation catalyst is at least one of antimony acetate, ethylene glycol antimony, tetrabutyl titanate and tetraisopropyl titanate.
Another object of the present invention is to provide a method for preparing the petroleum resin modified bio-based polyester, the method comprising the steps of:
(1) weighing raw material components of furan dicarboxylic acid and/or esterified substances thereof, ethylene glycol, petroleum resin, an esterification or ester exchange catalyst and a polycondensation catalyst for later use;
(2) uniformly mixing furan dicarboxylic acid and/or an esterified product thereof, ethylene glycol and petroleum resin, and then adding an esterification or ester exchange catalyst to carry out esterification or ester exchange reaction to obtain a first intermediate product;
(3) and adding a polycondensation catalyst into the first intermediate product, and carrying out a reduced pressure polycondensation reaction to obtain the petroleum resin modified bio-based polyester.
Preferably, the step (2) is carried out for 1-3h under a nitrogen atmosphere at the temperature of 200-220 ℃. By controlling the reaction conditions within the above range, the occurrence of side reactions such as oxidation can be avoided.
Preferably, the step (3) is carried out for 2-4h under the conditions of 250-270 ℃ and high vacuum with the pressure less than 300 Pa. The reaction conditions are controlled in the range, so that the generation of byproducts can be reduced, and the micromolecule byproducts generated in the reaction can be pumped away under the vacuum condition, so that the reaction is ensured to be carried out in the positive direction.
The bio-based polyester prepared by the raw material components and the preparation method can be widely applied to the fields of packaging, films, electric appliance elements and the like.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the petroleum resin contains hydroxyl groups and other groups, and is added as a raw material, so that the petroleum resin can interact with other material components, the compatibility among the components is improved, and the addition of the petroleum resin enables the melt index of the polyester material to be improved from 32.1g/10min to 46.1g/10min or more, which shows that the processing fluidity of PEF is obviously improved, and the phenomena of yellowing, degradation and the like caused by overlong heating time during PEF processing can be avoided; meanwhile, the semi-crystallization time is prolonged from 30.9min to 38.7min or more, which shows that the crystallization rate of the PEF is obviously reduced, the crystallization time is prolonged, and the improvement of the transparency of the PEF product is facilitated.
(2) The petroleum resin is an ethylene engineering byproduct, is low in price, not only reduces the cost of the PEF product, but also widens the application range of the petroleum resin, enriches the action of the ethylene engineering byproduct, reduces the accumulation and waste of the byproduct, changes waste into valuable and realizes the full utilization of petroleum resources.
(3) The preparation method is simple, the process is green and environment-friendly, and industrialization is easy to realize.
Drawings
FIG. 1: method for preparing modified biobased polyester of example 31An H-NMR spectrum;
FIG. 2: the crystallinity versus crystallization time curve for the modified bio-based polyester of example 3;
Detailed Description
The following are specific examples of the present invention and illustrate the technical solutions of the present invention for further description, but the present invention is not limited to these examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The test means adopted in the implementation process of the invention are as follows:
1. nuclear magnetic resonance Hydrogen Spectroscopy 1H-NMR was measured with a Bruker400AVANCE III Spectrometer type instrument, 400MHz, CF3COOD；
2. The melt index is tested according to GB/T3682-2000;
3. the tensile strength is tested according to GB/T1040-;
4. isothermal crystallization was determined using Differential Scanning Calorimetry (DSC) at 40ml/min N2Atmosphere protection, test temperature program as follows: (a) heating from 25 ℃ to 250 ℃ at a heating rate of 10 ℃/min, and eliminating heat history; (b) keeping the temperature constant at 250 ℃ for 5 min; (c) rapidly cooling to 25 deg.C at a speed of 200 deg.C/min; (d) heating from 25 ℃ to 150 ℃ at a heating rate of 100 ℃/min; (e) keeping the temperature constant for 2-4h at 150 ℃.
Example 1
Weighing 30 parts of 2, 5-furandicarboxylic acid, 20 parts of ethylene glycol and 5 parts of petroleum resin according to parts by weight, uniformly mixing, adding anhydrous zinc acetate with the amount of 0.2 mol% of 2, 5-furandicarboxylic acid, and carrying out esterification reaction for 1h at 200 ℃ in a nitrogen atmosphere to obtain a first intermediate product;
and adding antimony acetate with the dosage of 0.2 mol% of 2, 5-furandicarboxylic acid into the first intermediate product, and performing reduced pressure polycondensation reaction for 2 hours at the temperature of 250 ℃ and under the high vacuum condition with the pressure of less than 300Pa to obtain the petroleum resin modified bio-based polyester.
Example 2
Weighing 40 parts of dimethyl 2, 5-furandicarboxylate, 30 parts of ethylene glycol and 7 parts of petroleum resin according to parts by weight, uniformly mixing, adding anhydrous manganese acetate with the use amount of 0.3 mol% of the dimethyl 2, 5-furandicarboxylate, and carrying out ester exchange reaction for 2 hours at 205 ℃ in a nitrogen atmosphere to obtain a first intermediate product;
adding ethylene glycol antimony with the dosage of 0.3 mol% of dimethyl 2, 5-furandicarboxylate into the first intermediate product, and carrying out a reduced pressure polycondensation reaction for 3h under the conditions of 255 ℃ and a high vacuum with the pressure of less than 300Pa to obtain the petroleum resin modified bio-based polyester.
Example 3
Weighing 50 parts of dimethyl 2, 5-furandicarboxylate, 40 parts of ethylene glycol and 10 parts of petroleum resin according to parts by weight, uniformly mixing, adding anhydrous zinc acetate with the use amount of 0.4 mol% of the dimethyl 2, 5-furandicarboxylate, and carrying out ester exchange reaction for 2 hours at 210 ℃ in a nitrogen atmosphere to obtain a first intermediate product;
adding tetrabutyl titanate with the dosage of 0.4 mol% of dimethyl 2, 5-furandicarboxylate into the first intermediate product, and carrying out a reduced pressure polycondensation reaction for 3h under the conditions of 260 ℃ and a high vacuum with the pressure of less than 300Pa to obtain the petroleum resin modified bio-based polyester.
Detected, the bio-based polyester1The H-NMR spectrum is shown in figure 1, wherein the H atomic peak of CH on a furan ring is at 7.13ppm, the H atomic peak of CH2 on ethylene glycol is at 4.55ppm, the solvent peak is at 11.31ppm, and the position of the characteristic peak is completely consistent with that of PEF, so that the petroleum resin does not participate in chemical reaction, but the processing fluidity and the crystallization rate of the bio-based polyester are improved by a physical modification mode, and the negative influence caused by the modification of the bio-based polyester through the chemical reaction in the prior art is avoided;
the crystallinity of the modified bio-based polyester in this example is plotted against the crystallization time as shown in FIG. 2.
Example 4
Weighing 70 parts of dimethyl 2, 5-furandicarboxylate, 60 parts of ethylene glycol and 15 parts of petroleum resin according to parts by weight, uniformly mixing, adding anhydrous manganese acetate with the use amount of 0.3 mol% of dimethyl 2, 5-furandicarboxylate, and carrying out ester exchange reaction for 3 hours at 215 ℃ in a nitrogen atmosphere to obtain a first intermediate product;
adding tetraisopropyl titanate with the dosage of 0.3mol percent of dimethyl 2, 5-furandicarboxylate into the first intermediate product, and carrying out 2h reduced pressure polycondensation reaction at 265 ℃ under the high vacuum condition with the pressure of less than 300Pa to obtain petroleum resin modified bio-based polyester.
Example 5
Weighing 80 parts of dimethyl 2, 5-furandicarboxylate, 70 parts of ethylene glycol and 20 parts of petroleum resin according to parts by weight, uniformly mixing, adding anhydrous zinc acetate with the use amount of 0.5 mol% of the dimethyl 2, 5-furandicarboxylate, and carrying out ester exchange reaction for 1h at 220 ℃ in a nitrogen atmosphere to obtain a first intermediate product;
and adding a polycondensation catalyst with the dosage of 0.5 mol% of 2, 5-furandicarboxylic acid dimethyl ester into the first intermediate product, and carrying out a reduced pressure polycondensation reaction for 4 hours under the conditions of 270 ℃ and a high vacuum with the pressure of less than 300Pa to obtain the petroleum resin modified bio-based polyester.
Example 6
The only difference from example 3 is that the amount of petroleum resin added in the raw material components was 5 parts.
Example 7
The only difference from example 3 is that the amount of petroleum resin added in the raw material components was 8 parts.
Example 8
The only difference from example 3 is that the amount of petroleum resin added in the raw material components was 15 parts.
Example 9
The only difference from example 3 is that the amount of petroleum resin added in the raw material components was 20 parts.
Comparative example 1
The only difference from example 3 is that no petroleum resin was added to the raw material components.
Comparative example 2
The only difference from example 3 is that the amount of petroleum resin added was 3 parts.
Comparative example 3
The only difference from example 3 is that the amount of petroleum resin added was 25 parts.
Comparative example 4
The only difference from example 3 is that the amount of the esterification or transesterification catalyst and the polycondensation catalyst used is 0.1 mol% based on the furan dicarboxylic acid and/or the esterified product thereof.
Comparative example 5
The only difference from example 3 is that the amount of the esterification or transesterification catalyst and the polycondensation catalyst used is 0.6 mol% based on the furan dicarboxylic acid and/or the esterified product thereof.
The results of the performance test of the bio-based polyesters prepared in examples 1 to 9 and comparative examples 1 to 5 are shown in table 1.
Table 1: performance test results of bio-based polyesters prepared in examples 1 to 9 and comparative examples 1 to 5
As can be seen from the comparison between example 3 and examples 6-9 and comparative examples 1-3 in Table 1, when the weight portion of the petroleum resin is controlled between 5-15, the tensile strength of the prepared bio-based polyester is not changed obviously, the melt index is increased obviously, and the semi-crystallization time is prolonged obviously with the increase of the addition amount of the petroleum resin. When the content of the petroleum resin is less than 5 parts, the melt index is obviously reduced, and the semi-crystallization time is obviously shortened, which shows that the prepared bio-based polyester has poor fluidity and transparency, namely the addition amount of the petroleum resin is too small, and the improvement effect on the fluidity and the semi-crystallization time of the bio-based polyester is extremely small; when the content of the petroleum resin is higher than 15 parts, the tensile strength of the prepared bio-based polyester is in a descending trend, when the adding amount reaches 20 parts, the tensile strength is obviously reduced, when the adding amount exceeds 20 parts, the tensile strength is rapidly reduced, the petroleum resin possibly has certain viscosity, and the petroleum resin is coated on the surface of a reactant to form a viscous group along with the increase of the content, so that the reaction substance is prevented from fully contacting and reacting, and the generation of the bio-based polyester is influenced.
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (9)
1. The petroleum resin modified bio-based polyester is characterized by comprising the following components in parts by weight: 30-80 parts of furan dicarboxylic acid and/or esterified product thereof, 20-70 parts of ethylene glycol and 5-20 parts of petroleum resin.
2. The bio-based polyester according to claim 1, wherein said petroleum resin is at least one of C5 petroleum resin, C9 petroleum resin, hydrogenated C5 petroleum resin, hydrogenated C9 petroleum resin.
3. The bio-based polyester according to claim 1, wherein the petroleum resin has a relative number average molecular weight of 300-3000.
4. The bio-based polyester according to claim 1, wherein said bio-based polyester further comprises an esterification or transesterification catalyst, a polycondensation catalyst, and the amount thereof is 0.2 to 0.5 mol% of furan dicarboxylic acid and/or its esterified product.
5. The bio-based polyester according to claim 4, wherein said esterification or transesterification catalyst is at least one of anhydrous zinc acetate, anhydrous manganese acetate.
6. The bio-based polyester according to claim 4, wherein the polycondensation catalyst is at least one of antimony acetate, antimony glycol, tetrabutyl titanate, and tetraisopropyl titanate.
7. A method of preparing the bio-based polyester according to claim 1, comprising the steps of:
(1) weighing raw material components of furan dicarboxylic acid and/or esterified substances thereof, ethylene glycol, petroleum resin, an esterification or ester exchange catalyst and a polycondensation catalyst for later use;
(2) furan dicarboxylic acid and/or an esterified product thereof, ethylene glycol, petroleum resin and an esterification or ester exchange catalyst are uniformly mixed, and esterification or ester exchange reaction is carried out to obtain a first intermediate product.
(3) And adding a polycondensation catalyst into the first intermediate product, and performing a reduced pressure polycondensation reaction to obtain the petroleum resin modified bio-based polyester.
8. The method for preparing bio-based polyester according to claim 7, wherein the step (2) is performed under nitrogen atmosphere at 200-220 ℃ for 1-3 h.
9. The method for preparing bio-based polyester according to claim 7, wherein the step (3) is performed under high vacuum conditions of 250-270 ℃ and less than 300Pa for 2-4 h.
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Citations (3)
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|---|---|---|---|---|
| JPH09227766A (en) * | 1995-12-20 | 1997-09-02 | Kuraray Co Ltd | Vibration damping polyester resin composition and its use |
| JP2003238670A (en) * | 2002-02-22 | 2003-08-27 | Arakawa Chem Ind Co Ltd | Polyester resin and coating material composition |
| CN111748190A (en) * | 2019-03-26 | 2020-10-09 | 荒川化学工业株式会社 | Resin composition and molded article |
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- 2021-03-29 CN CN202110334228.4A patent/CN113150507A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09227766A (en) * | 1995-12-20 | 1997-09-02 | Kuraray Co Ltd | Vibration damping polyester resin composition and its use |
| JP2003238670A (en) * | 2002-02-22 | 2003-08-27 | Arakawa Chem Ind Co Ltd | Polyester resin and coating material composition |
| CN111748190A (en) * | 2019-03-26 | 2020-10-09 | 荒川化学工业株式会社 | Resin composition and molded article |
Non-Patent Citations (1)
| Title |
|---|
| 李爱元等: "生物基呋喃聚酯及其与石油树脂共混物的制备及性能研究", 《化学推进剂与高分子材料》 * |
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