CN118420571A - Furan-based polyester film composition, nucleating agent and preparation method thereof - Google Patents
Furan-based polyester film composition, nucleating agent and preparation method thereof Download PDFInfo
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- CN118420571A CN118420571A CN202410631365.8A CN202410631365A CN118420571A CN 118420571 A CN118420571 A CN 118420571A CN 202410631365 A CN202410631365 A CN 202410631365A CN 118420571 A CN118420571 A CN 118420571A
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- furan
- based polyester
- nucleating agent
- furandicarboxylate
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 47
- 229920006267 polyester film Polymers 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000004888 barrier function Effects 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000000465 moulding Methods 0.000 claims abstract description 15
- OFTKFKYVSBNYEC-UHFFFAOYSA-N 2-furoyl chloride Chemical compound ClC(=O)C1=CC=CO1 OFTKFKYVSBNYEC-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 polyethylene terephthalate-2, 5-furandicarboxylate Polymers 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 26
- 238000005266 casting Methods 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 229920001634 Copolyester Polymers 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- DGJKAGRTYAPHJB-UHFFFAOYSA-N O=C1OCCOC(=O)C2=C1C=CO2 Chemical compound O=C1OCCOC(=O)C2=C1C=CO2 DGJKAGRTYAPHJB-UHFFFAOYSA-N 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- ZOVSNXYOLUSCIN-UHFFFAOYSA-N 6-methyl-6,7-dihydrofuro[2,3-f][1,4]dioxocine-4,9-dione Chemical compound O1C2=C(C=C1)C(=O)OC(COC2=O)C ZOVSNXYOLUSCIN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- NTOGAFXYRHJEAO-UHFFFAOYSA-N 6,7,8,9-tetrahydrofuro[2,3-c][1,6]dioxecine-4,11-dione Chemical compound O=C1OCCCCOC(=O)C2=C1C=CO2 NTOGAFXYRHJEAO-UHFFFAOYSA-N 0.000 claims 1
- UXRYJOQTDQJUHV-UHFFFAOYSA-N C(CCCCC)OC(=O)C=1OC=CC=1C(=O)O Chemical compound C(CCCCC)OC(=O)C=1OC=CC=1C(=O)O UXRYJOQTDQJUHV-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FKDBCRVNYOLHRK-UHFFFAOYSA-N O1C(=C(C=C1)C(=O)O)C(=O)O.C(CO)O Chemical group O1C(=C(C=C1)C(=O)O)C(=O)O.C(CO)O FKDBCRVNYOLHRK-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- LNDGLWNBOWIGSN-UHFFFAOYSA-N ethane-1,2-diol;[1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCCO.OCC1(CO)CCCCC1 LNDGLWNBOWIGSN-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
In order to solve the problems of low stretching rate and low molding efficiency of furan-based polyester in the biaxial stretching molding process, the invention provides a furan-based polyester film composition with rapid molding and high barrier property, a nucleating agent and a preparation method. The novel nucleating agent N, N' -1, 4-phthaloyl amine is prepared by taking biological furoyl chloride as a raw material. Based on the parts by weight, 100 parts of furan-based polyester and 0.1-3 parts of nucleating agent are blended to prepare the fast-forming and high-barrier-property furan-based polyester film composition. The novel nucleating agent is used, the film of the polyester composition is formed rapidly, the barrier property of the furan-based polyester film and the crystallization efficiency in the biaxial stretching forming process are effectively improved, and the novel nucleating agent has good market prospect.
Description
Technical Field
The invention belongs to the technical field of biomass furan-based polyesters, and particularly relates to a furan-based polyester film composition with rapid forming and high barrier property, a nucleating agent and a preparation method thereof.
Background
With the increasing scarcity of traditional petroleum resources and the serious environmental pollution problems, the development of biomass-derived bio-based materials has gained widespread attention. Pentahydroxy methyl furfural is a biomass feedstock that can be extracted from natural plants and further prepared to form furandicarboxylic acid (FDCA) monomers, and furanyl polyesters prepared from such monomers have been rapidly developed in recent years, with polyethylene furandicarboxylate (PEF) being a more typical example. Compared with petroleum-based raw material terephthalic acid (PTA), FDCA has the same functional group and similar aromaticity and reactivity, and can form a series of high-performance polymer materials through polycondensation reaction with glycol or diamine and the like. The derivative product has the advantages of no toxicity, reproducibility, controllable degradation and the like, and has the performances of glass transition temperature, melting point, young modulus, tensile strength and the like which are equivalent to those of PTA products. Therefore, the polyethylene terephthalate-2, 5-furandicarboxylic acid ethylene copolyester (PETF) prepared by introducing FDCA into the PTA system in a copolymerization mode can greatly improve the performance advantage compared with the traditional polyethylene terephthalate (PET). However, the crystallization rate of the PETF polyester is slow, the molding processing period is long, and the like, so that the application of the PETF in production and life is limited. The novel nucleating agent is developed to solve the problems of low stretching rate and low molding efficiency of the furan-based polyester film in the biaxial stretching molding process, and is a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems of low stretching rate and low molding efficiency of the furan-based polyester film in the biaxial stretching molding process, the invention provides a nucleating agent for furan-based polyester, a furan-based polyester film composition with rapid molding and high barrier property and a preparation method thereof. The novel nucleating agent is used, so that the film of the polyester composition is rapidly formed, and the barrier property of the furan-based polyester film and the efficiency in the biaxial stretching forming process are effectively improved.
In a first aspect, the present invention provides a class of nucleating agents for furan-based polyesters, said nucleating agents being N, N' -1, 4-benzenedicarboxamide having the structural formula:
in a second aspect, the invention provides a method for preparing a nucleating agent for improving the rapid forming and barrier properties of a furan-based polyester film composition, which comprises the following specific steps:
S1, adding p-phenylenediamine, an acid binding agent and a solvent into a reactor, controlling the temperature to-10-5, and stirring;
s2, slowly dripping furoyl chloride into the reactor after the furoyl chloride is dissolved in the same solvent, wherein the dripping time is not less than 20min;
S3, heating to the reflux temperature of the solvent, and reacting for not less than 3 hours;
S4, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain white powder, namely the nucleating agent N, N' -1, 4-phthalimide.
Further, the molar ratio of the p-phenylenediamine to the furoyl chloride is 1: 2.05 to 2.2; the molar ratio of the furoyl chloride to the acid binding agent is 1;1.
Further, the acid binding agent is at least one selected from triethylamine and pyridine.
Further, the solvent is selected from one of acetonitrile, toluene, chloroform, dioxane, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Further, in the step S1, the mass ratio of the p-phenylenediamine to the solvent is 0.02-0.045: 1.
Further, the mass ratio of the furoyl chloride to the solvent in the step S2 is 0.06-0.12: 1.
Further, in the step S1, the mixture is placed in an ice-water bath with the temperature of-10 to 5 and stirred by magnetic force.
Further, the step S4 is to adopt suction filtration under the condition of reduced pressure; absolute ethyl alcohol and distilled water are adopted for washing; the drying mode is vacuum drying under the condition of 80 temperature.
The raw materials of the nucleating agent prepared by the method are derived from straw biomass, and the nucleating agent has no peculiar smell, good compatibility, easy dispersion and no sedimentation.
In a third aspect, the invention provides a fast-forming and high-barrier-property furan-based polyester film composition, which comprises, by mass, 100 parts of furan-based polyester and 0.1-3 parts of nucleating agent;
The nucleating agent is N, N' -1, 4-benzene difuran formamide, and the structural formula is as follows:
The furyl polyester is ethylene glycol furandicarboxylate, propylene glycol furandicarboxylate, butylene glycol furandicarboxylate, pentylene glycol furandicarboxylate, hexylene glycol furandicarboxylate, octylene glycol furandicarboxylate, polyethylene terephthalate-2, 5-ethylene glycol furandicarboxylate, polyethylene terephthalate-2, 5-propylene glycol furandicarboxylate, polybutylene terephthalate-2, 5-butylene glycol furandicarboxylate, at least one of poly (ethylene adipate-2, 5-furandicarboxylic acid) glycol copolyester, poly (propylene adipate-2, 5-furandicarboxylic acid) glycol copolyester, poly (butylene adipate-2, 5-furandicarboxylic acid) cyclohexanedimethanol-ethylene glycol copolyester, poly (2, 5-furandicarboxylic acid) cyclohexanedimethanol-propylene glycol copolyester, and poly (2, 5-furandicarboxylic acid) cyclohexanedimethanol-butanediol copolyester.
Further, the mass ratio of the furan-based polyester to the nucleating agent is preferably 100:0.1-1.
Further, the mass ratio of the furan-based polyester to the nucleating agent is preferably 100:0.3-0.5.
In a fourth aspect, the invention provides a method for preparing a fast-forming and high-barrier-property furan-based polyester film composition, comprising the steps of pre-mixing furan-based polyester and a nucleating agent in proportion; and then sequentially carrying out melt blending, tape casting and two-way stretching processes to obtain the furan-based polyester film composition.
Further, the melt blending process is as follows: placing the pre-mixed furan-based polyester and nucleating agent in a double-screw extruder for melt blending to obtain a master batch; the processing temperature of the double-screw extruder is 190-250, and the screw rotating speed is 140-160rpm.
Further, the casting molding process comprises the following steps: placing the master batch into a single-screw extrusion casting machine for casting forming to obtain a sheet; the processing temperature of the single-screw extrusion casting machine is 190-250, and the screw rotating speed is 110-130rpm.
Further, the biaxial stretching process is as follows: placing the sheet material in a biaxial stretching machine for biaxial stretching to obtain the furan-based polyester film composition; the processing temperature of the biaxial stretching machine is 100-120, the stretching ratio is 2-5, the stretching speed is 50v/s-400v/s, and the shaping temperature is 130-150.
Further, in the casting molding process, the master batch is placed in a single-screw extrusion casting machine for casting molding, and the sheet of the furan-based polyester film composition with the thickness of 500-600 mu m is obtained.
Further, the sheet after casting is cut into sheets of not more than 20 x 20cm before biaxial stretching. The thickness of the biaxially stretched film is 25-55 μm.
Further, the processing temperatures of the conveying section, the melting section, the mixing section, the exhausting section and the homogenizing section of the twin-screw extruder are 190, 220, 230, 245 and 250, the temperature of the machine head 248 and the screw rotating speed are 150rpm.
Further, the processing temperatures of the conveying section, the melting section, the mixing section, the exhaust section and the homogenizing section of the single-screw extrusion casting machine are 190, 220, 230, 245 and 250, the temperature of the machine head is 260, and the rotating speed of the screw is 120rpm.
Further, the mass ratio of the furan-based polyester to the nucleating agent is 100:0.1-1.
Further, before pre-mixing, the furan-based polyester and the nucleating agent are firstly placed in a vacuum oven and dried for 12-24 hours under 80-100.
Further, the masterbatch is dried in an oven at 100-120 hours before preparing the sheet.
The invention discloses application of a nucleating agent N, N '-1, 4-phthalimide in polyester, in particular to application of the nucleating agent N, N' -1, 4-phthalimide in improving barrier property and stretch forming efficiency performance of furyl polyester.
The beneficial effects are that:
The furoyl chloride which is one of the raw materials of the nucleating agent is derived from straw biomass, is safe and environment-friendly, and is nontoxic and harmless to human bodies and the environment; n, N' -1, 4-benzene difuran formamide is used as a nucleating agent, is melt-blended with furan-based polyester to obtain a furan-based polyester composition, and is prepared into a furan-based polyester film composition through a biaxial stretching process, the preparation steps are simple and economical, the fast molding is realized through one-step reaction, the fast molding furan polyester composition film material with high barrier property is obtained, and the film material is suitable for industrial production;
Drawings
FIG. 1 is an NMR-H spectrum of N, N' -1, 4-benzenedicarboxamide nucleating agent in example 1.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be made. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein; it will be apparent that the embodiments in the specification are only some, but not all, embodiments of the invention.
Preferred embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention.
Test instrument model: the nuclear magnetic resonance spectrometer used was Vaian DLG400,400 (Varian, USA) and the gas permeameter used was VAC-V2 (blue, china).
Example 1 (preparation of nucleating agent, N, N' -1, 4-Benzodifuran carboxamide)
1.081G of p-phenylenediamine and 2.23g of triethylamine were weighed into a 100mL two-necked flask equipped with a magnet, and 30mL of acetonitrile was added thereto, and the flask was placed in a 0-ice bath stirring pot. 2.872g of furoyl chloride was weighed into a beaker, 15mL of acetonitrile was added thereto, after which, after it was sufficiently dissolved, it was transferred into a 25mL constant pressure funnel, and the residual liquid in the beaker was transferred three times with 5mL of acetonitrile. The furoyl chloride solution in the constant pressure funnel was slowly added dropwise to the flask under 0-atmosphere, and the total time of addition was controlled to be about half an hour. After the completion of the dropwise addition, the temperature was raised to 80, and the reaction was carried out for 3 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration, washing a filter cake with deionized water for 2 times, washing with absolute ethyl alcohol for 1 time, and vacuum drying for 12 hours under 80 ℃ to obtain white powder, wherein the yield is 91.4%, and the structure of the obtained product is identical to that of N, N' -1, 4-phthalamide through nuclear magnetic resonance hydrogen spectrum test analysis.
Example 2 (blending)
The nucleating agent prepared in example 1 and ethylene furandicarboxylate were dried in a vacuum oven for 12 hours under 60. 5kg of polyethylene furandicarboxylate and 3g of nucleating agent are taken and mixed in advance in a self-sealing bag, and then put into a SHJ20 twin-screw extruder for melt mixing. The extruder five temperature control zone temperatures and the die head temperatures were set at 190, 220, 230, 245, 250, and 248, respectively, with screw speeds of 150rpm. The ethylene furandicarboxylate sheet was prepared by a single screw casting machine, the temperatures of the five temperature control zones of the single screw casting machine and the temperature of the machine head were respectively set to 200, 220, 230, 245, 250 and 260, and the screw rotation speed was 120rpm.
Example 3 (blending)
The polyethylene furandicarboxylate was dried in a vacuum oven for 12 hours under 60. Then put into a SHJ 20 twin-screw extruder for melt mixing. The extruder five temperature control zone temperatures and the die head temperatures were set at 190, 220, 230, 245, 250, and 248, respectively, with screw speeds of 150rpm. The ethylene furandicarboxylate sheet was prepared by a single screw casting machine, the temperatures of the five temperature control zones of the single screw casting machine and the temperature of the machine head were respectively set to 200, 220, 230, 245, 250 and 260, and the screw rotation speed was 120rpm.
Example 4 (blending)
The nucleating agent prepared in example 1 and propylene glycol furandicarboxylate were dried in a vacuum oven for 12 hours under 60. 5kg of polypropylene furandicarboxylate and 3g of nucleating agent are taken and mixed in advance in a self-sealing bag, and then put into a SHJ 20 twin-screw extruder for melt mixing. The extruder five temperature control zone temperatures and the die head temperatures were set at 160, 170, 190, 210, 220, and 235, respectively, with screw speeds of 150rpm. The propylene glycol furandicarboxylate sheet was prepared by a single screw casting machine, the temperature of the five temperature control zones of the single screw casting machine and the temperature of the machine head were respectively set to 160, 170, 190, 210, 220 and 235, and the screw rotation speed was 120rpm.
Example 5 (blending)
The pure propylene furandicarboxylate was dried in a vacuum oven at 60 hours and then placed into an SHJ 20 twin screw extruder for melt mixing. The extruder five temperature control zone temperatures and the die head temperatures were set at 160, 170, 190, 210, 220, and 235, respectively, with screw speeds of 150rpm. The propylene glycol furandicarboxylate sheet was prepared by a single screw casting machine, the temperature of the five temperature control zones of the single screw casting machine and the temperature of the machine head were respectively set to 160, 170, 190, 210, 220 and 235, and the screw rotation speed was 120rpm.
Example 6 (double pull)
The ethylene furandicarboxylate sheet prepared in example 2 was cut into 13x13cm pieces, and a double drawing experiment was performed in a biaxial stretching apparatus at a drawing temperature of 105, a drawing rate of 50v/s, a drawing ratio of 3, and a setting temperature of 150.
Example 7 (double pull)
The draw ratio was changed to 4 in accordance with the conditions of example 6.
Example 8 (double pull)
The draw ratio was changed to 5 in accordance with the conditions of example 6.
Example 9 (double pull)
The stretching rate was changed to 100v/s in accordance with the conditions of example 6.
Example 10 (double pull)
The stretching rate was changed to 200v/s in accordance with the conditions of example 6.
Example 11 (comparative example)
The ethylene furandicarboxylate sheet prepared in example 3 was cut into 13x13cm pieces, and a double drawing experiment was performed in a biaxial stretching apparatus at a drawing temperature of 105, a drawing rate of 50v/s, a drawing ratio of 3, and a setting temperature of 150.
Example 12 (comparative example)
The draw ratio was changed to 4 in accordance with the conditions of example 11.
Example 13 (comparative example)
The draw ratio was changed to 5 in accordance with the conditions of example 11.
Example 14 (comparative example)
The stretching rate was changed to 100v/s in accordance with the conditions of example 11.
Example 15 (comparative example)
The stretching rate was changed to 200v/s in accordance with the conditions of example 11.
Example 16 (double pull)
The propylene furandicarboxylate sheet prepared in example 4 was cut into 13x13cm pieces and subjected to a double drawing test in a biaxial stretching apparatus at a drawing temperature of 85, a drawing rate of 50v/s, a drawing ratio of 3, and a setting temperature of 150.
Example 17 (double pull)
The draw ratio was changed to 4 in accordance with the conditions of example 16.
Example 18 (double pull)
The draw ratio was changed to 5 in accordance with the conditions of example 16.
Example 19 (double pull)
The stretching rate was changed to 100v/s in accordance with the conditions of example 16.
Example 20 (double pull)
The stretching rate was changed to 200v/s in accordance with the conditions of example 16.
Example 21 (comparative example)
The propylene furandicarboxylate sheet prepared in example 5 was cut into 13x13cm pieces and subjected to a double drawing test in a biaxial stretching apparatus at a drawing temperature of 105, a drawing rate of 50v/s, a drawing ratio of 3, and a setting temperature of 150.
Example 22 (comparative example)
The draw ratio was changed to 4 in accordance with the conditions of example 21.
Example 23 (comparative example)
The draw ratio was changed to 5 in accordance with the conditions of example 21.
Example 24 (comparative example)
The stretching rate was changed to 100v/s in accordance with the conditions of example 21.
Example 25 (comparative example)
The stretching rate was changed to 200v/s in accordance with the conditions of example 21.
Example 26 (blending)
The nucleating agent prepared in example 1 and polyfurandicarboxylic acid-terephthalic acid-ethylene glycol ester (PETF-10) were dried in a vacuum oven for 12 hours under 60. 5kg of PETF-10 and 3g of nucleating agent are taken and mixed in advance in a self-sealing bag, and then put into a SHJ 20 twin-screw extruder for melt mixing. The extruder five temperature control zone temperatures and the die head temperatures were set at 190, 220, 230, 245, 250, and 248, respectively, with screw speeds of 150rpm. The ethylene furandicarboxylate sheet was prepared by a single screw casting machine, the temperatures of the five temperature control zones of the single screw casting machine and the temperature of the machine head were respectively set to 200, 220, 230, 245, 250 and 260, and the screw rotation speed was 120rpm.
Example 27 (blending)
The polyfurandicarboxylic acid-ethylene terephthalate (PETF-10) was dried in a vacuum oven for 12 hours under 60 hours. Then put into a SHJ20 twin-screw extruder for melt mixing. The extruder five temperature control zone temperatures and the die head temperatures were set at 190, 220, 230, 245, 250, and 248, respectively, with screw speeds of 150rpm. The ethylene furandicarboxylate sheet was prepared by a single screw casting machine, the temperatures of the five temperature control zones of the single screw casting machine and the temperature of the machine head were respectively set to 200, 220, 230, 245, 250 and 260, and the screw rotation speed was 120rpm.
Example 28 (blending)
The copolyester ratio was changed to PETF20 in accordance with the conditions of example 26.
Example 29 (blending)
The copolyester ratio was changed to PETF30 in accordance with the conditions of example 26.
Example 30 (blending)
The copolyester ratio was changed to PETF40 in accordance with the conditions of example 26.
Example 31 (blending)
The copolyester ratio was changed to PETF50 in accordance with the conditions of example 26.
Example 32 (double pull)
The PETF10 sheet prepared in example 26 was cut to 13X 13cm and subjected to a double drawing test in a biaxial stretching apparatus at a drawing temperature of 100, a drawing rate of 50v/s, a drawing ratio of 3 and a setting temperature of 140.
Example 33 (double pull)
The draw ratio was changed to 4 in accordance with the conditions of example 32.
Example 34 (double pull)
The draw ratio was changed to 5 in accordance with the conditions of example 32.
Example 35 (double pull)
The stretching rate was changed to 100v/s in accordance with the conditions of example 32.
Example 36 (double pull)
The stretching rate was changed to 200v/s in accordance with the conditions of example 32.
Example 37 (double pull)
The stretching temperature was changed to 110 in accordance with the conditions of example 32.
Example 38 (double pull)
The stretching temperature was changed to 120 in accordance with the conditions of example 32.
Example 39 (double pull)
The PETF20 sheet prepared in example 28 was cut to 13X 13cm and subjected to a double drawing test in a biaxial stretching apparatus at a drawing temperature of 100, a drawing rate of 50v/s, a drawing ratio of 3 and a setting temperature of 140.
Example 40 (double pull)
The draw ratio was changed to 4 in accordance with the conditions of example 39.
Example 41 (double pull)
The draw ratio was changed to 5 in accordance with the conditions of example 39.
Example 42 (double pull)
The stretching rate was changed to 100v/s in accordance with the conditions of example 39.
Example 43 (double pull)
The stretching rate was changed to 200v/s in accordance with the conditions of example 39.
Example 44 (double pull)
The stretching temperature was changed to 110 in accordance with the conditions of example 39.
Example 45 (double pull)
The stretching temperature was changed to 120 in accordance with the conditions of example 39.
Example 46 (double pull)
The PETF30 sheet prepared in example 29 was cut to 13X 13cm and subjected to a double drawing test in a biaxial stretching apparatus at a drawing temperature of 100, a drawing rate of 50v/s, a drawing ratio of 3 and a setting temperature of 140.
Example 47 (double pull)
The draw ratio was changed to 4 in accordance with the conditions of example 46.
Example 48 (double pull)
The draw ratio was varied to 5 in accordance with the conditions of example 46.
Example 49 (double pull)
The stretching rate was changed to 100v/s in accordance with the conditions of example 46.
Example 50 (double pull)
The stretching rate was changed to 200v/s in accordance with the conditions of example 46.
Example 51 (double pull)
The stretching temperature was changed to 110 in accordance with the conditions of example 46.
Example 52 (double pull)
The stretching temperature was changed to 120 in accordance with the conditions of example 46.
Example 53 (double pull)
The PETF40 sheet prepared in example 30 was cut to 13X 13cm and subjected to a double drawing test in a biaxial stretching apparatus at a drawing temperature of 100, a drawing rate of 50v/s, a drawing ratio of 3 and a setting temperature of 140.
Example 54 (double pull)
The draw ratio was changed to 4 in accordance with the conditions of example 53.
Example 55 (double pull)
The draw ratio was changed to 5 in accordance with the conditions of example 53.
Example 56 (double pull)
The stretching rate was changed to 100v/s in accordance with the conditions of example 53.
Example 57 (double pull)
The stretching rate was changed to 200v/s in accordance with the conditions of example 53.
Example 58 (double pull)
The stretching temperature was changed to 110 in accordance with the conditions of example 53.
Example 59 (double pull)
The stretching temperature was changed to 120 in accordance with the conditions of example 53.
Example 60 (double pull)
The PETF50 sheet prepared in example 31 was cut to 13X 13cm and subjected to a double drawing test in a biaxial stretching apparatus at a drawing temperature of 100, a drawing rate of 50v/s, a drawing ratio of 3 and a setting temperature of 140.
Example 61 (double pull)
The draw ratio was changed to 4 in accordance with the conditions of example 60.
Example 62 (double pull)
The draw ratio was changed to 5 in accordance with the conditions of example 60.
Example 63 (double pull)
The stretching rate was changed to 100v/s in accordance with the conditions of example 60.
Example 64 (double pull)
The stretching rate was changed to 200v/s in accordance with the conditions of example 60.
Example 65 (double pull)
The stretching temperature was changed to 110 in accordance with the conditions of example 60.
Example 66 (double pull)
The stretching temperature was changed to 120 in accordance with the conditions of example 60.
Gas barrier property test: the prepared furan-based polyester film is cut into a circular sheet with the diameter of 5cm for gas barrier performance test, the test standard is GB/T1038-2000, the test temperature is 23, and the test humidity is 0% RH. The test results are shown in tables 1 and 2.
Mechanical property test: cutting the prepared furan-based polyester film into rectangular sheets with the length of 1cm multiplied by 5cm, and carrying out mechanical property test, wherein the test standard is GB/T1040.3-2006, and the stretching speed is 100mm/min. The results of testing the biaxially oriented films of PEF and PTF are shown in Table 1, and the results of testing the biaxially oriented films of PETF are shown in tables 1 and 2.
TABLE 1 results of testing biaxially oriented PEF and PTF films
TABLE 2 results of testing biaxially oriented PEF and PTF films
According to the barrier property of the furan-based polyester film, the barrier property of the furan-based polyester film added with the nucleation is obviously improved along with the gradual increase of the stretching ratio, and then the furan-based polyester film added with the nucleating agent can reach lower barrier property on the premise of stretching to the same stretching ratio, and more nucleation sites can be generated in the stretching process due to the addition of the nucleating agent on the premise of rapid stretching rate, so that the degree of oriented crystallization of the furan-based polyester film in the stretching process is further promoted, the barrier property of the film is further improved, and the forming efficiency of the biaxially-oriented film is further improved due to the addition of the nucleating agent, so that the furan-based polyester film with high barrier property is further obtained.
While the foregoing embodiments of the present invention have been described in conjunction with the accompanying drawings, it is not intended to limit the scope of the present invention, and it will be apparent to those skilled in the art that various modifications or variations can be made without the need for inventive effort by those skilled in the art on the basis of the technical solutions of the present invention.
Claims (10)
1. The nucleating agent for furan-based polyester is characterized by being N, N' -1, 4-phthalfurancarboxamide, and has a structural formula:
2. a process for the preparation of a class of nucleating agents for furan-based polyesters as claimed in claim 1, comprising the steps of:
t1, adding p-phenylenediamine, an acid binding agent and a solvent into a reactor, controlling the temperature to-10-5, and stirring;
T2, dripping the furoyl chloride solution into the reactor for at least 20min; the solvent of the furoyl chloride solution and the step T1 use the same solvent;
t3, heating to the reflux temperature of the solvent, and reacting for not less than 3 hours;
t4, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain white powder, namely the nucleating agent N, N' -1, 4-phthalimide;
the molar ratio of the p-phenylenediamine to the furoyl chloride is 1:2.05 to 2.2; the molar ratio of the furoyl chloride to the acid binding agent is 1:1.
3. The preparation method according to claim 2, wherein the acid-binding agent is at least one selected from triethylamine and pyridine; the solvent is selected from one of acetonitrile, toluene, chloroform, dioxane, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
4. The preparation method according to claim 2, wherein the mass ratio of p-phenylenediamine to solvent in the step T1 is 0.02-0.045: 1, a step of; the mass ratio of the furoyl chloride to the solvent in the step T2 is 0.06-0.12: 1.
5. The furan-based polyester film composition with rapid forming and high barrier property is characterized by comprising, by mass, 100 parts of furan-based polyester and 0.1-3 parts of nucleating agent;
The nucleating agent is N, N' -1, 4-benzene difuran formamide.
6. The furan-based polyester film composition of claim 5, wherein the furan-based polyester is at least one selected from the group consisting of ethylene furandicarboxylate, propylene furandicarboxylate, butylene furandicarboxylate, pentyfurandicarboxylate, hexylfurandicarboxylate, octylfurandicarboxylate, polyethylene terephthalate-2, 5-furandicarboxylate, polypropylene terephthalate-2, 5-furandicarboxylate, polybutylene terephthalate-2, 5-furandicarboxylate, polyethylene adipate-2, 5-furandicarboxylate, polypropylene adipate-2, 5-furandicarboxylate, polybutylene adipate-2, 5-furandicarboxylate, poly 2, 5-furandimethanol-ethylene cyclohexanedicarboxylate, poly 2, 5-furandimethanol-propylene glycol copolyester, poly 2, 5-furandimethanol-cyclohexanedimethanol-butylene glycol copolyester.
7. A process for preparing the furan-based polyester film composition of any one of claims 5-6, characterized in that the furan-based polyester and the nucleating agent are pre-mixed in proportions; and then sequentially carrying out melt blending, tape casting and two-way stretching processes to obtain the furan-based polyester film composition.
8. The method of claim 7, wherein the melt blending process is: placing the pre-mixed furan-based polyester and nucleating agent in a double-screw extruder for melt blending to obtain a master batch; the processing temperature of the double-screw extruder is 190-250, and the screw rotating speed is 140-160rpm.
9. The method of claim 8, wherein the casting process is: placing the master batch into a single-screw extrusion casting machine for casting forming to obtain a sheet; the processing temperature of the single-screw extrusion casting machine is 190-250, and the screw rotating speed is 110-130rpm.
10. The method according to claim 9, wherein the biaxial stretching process is: placing the sheet in a biaxial stretching machine for biaxial stretching to obtain the furan-based polyester film composition with rapid molding and high barrier property; the processing temperature of the biaxial stretching machine is 100-120, the stretching ratio is 2-5, the stretching speed is 50v/s-400v/s, and the shaping temperature is 130-150.
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