CN115197549B - Rapid crystallization PET resin of nano attapulgite copolymerized PEG and preparation method thereof - Google Patents
Rapid crystallization PET resin of nano attapulgite copolymerized PEG and preparation method thereof Download PDFInfo
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- CN115197549B CN115197549B CN202210743454.2A CN202210743454A CN115197549B CN 115197549 B CN115197549 B CN 115197549B CN 202210743454 A CN202210743454 A CN 202210743454A CN 115197549 B CN115197549 B CN 115197549B
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- attapulgite
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 104
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 104
- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- 238000002425 crystallisation Methods 0.000 title claims abstract description 66
- 230000008025 crystallization Effects 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 142
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 81
- 229920001223 polyethylene glycol Polymers 0.000 claims description 71
- 238000005886 esterification reaction Methods 0.000 claims description 51
- 230000032050 esterification Effects 0.000 claims description 47
- 239000003365 glass fiber Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000006068 polycondensation reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 17
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004246 zinc acetate Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 229920006351 engineering plastic Polymers 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 18
- 239000002667 nucleating agent Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 82
- 239000005020 polyethylene terephthalate Substances 0.000 description 82
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 bottles Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical group OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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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)
- Dispersion Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a fast crystallization PET resin of nano attapulgite copolymerized PEG and a preparation method thereof, wherein the fast crystallization PET resin is synthesized by copolymerizing a monomer containing a PET chain segment, a monomer containing a PEG chain segment and ionized modified nano attapulgite by an in-situ polymerization method; wherein, the mass percentage of the monomer containing the PEG chain segment is 3-25%; the mass percentage of the ionized modified nano attapulgite is 0.1-3%. The invention has simple process and small additive addition, and the quick crystallization nucleating agent is stably and uniformly dispersed in the polyester PET macromolecules by in-situ polymerization and flexible chain segment copolymerization, and the flexible chain segment is polymerized into the polyester chain segment, so that the crystallization performance and the shock resistance of the PET resin are greatly improved.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a fast crystallized PET resin of nano attapulgite copolymerized PEG and a preparation method thereof.
Background
PET is a thermoplastic engineering plastic with excellent mechanical property, heat resistance and chemical reagent resistance, so that the PET is widely applied to the fields of fibers, bottles, films and the like. At present, the application of PET in non-fiber polyester (bottle flakes, films and engineering plastics) is increasing, and the engineering plastics are one of development hot spots in the field of PET non-fiber. However, since the main chain of PET has high rigidity and slow chain movement, the crystallization speed is relatively slow, so that the injection molding temperature is high, the molding period is long, the product is easy to stick to the mold and warp, and the application in engineering plastics is severely restricted.
The publication CN1388177a provides a method for obtaining a fast crystallizing polyethylene terephthalate composite by physical modification with a twin screw extruder. Firstly, stirring and mixing polyethylene glycol terephthalate, a composite crystallization nucleating agent and other auxiliary agents at a high speed, then sending the mixture into a double-screw extruder through a precisely-metering feeder, then adding the precisely-metering feeder for filling the reinforcing agent into the extruder, plasticizing, melting, compounding, and finally extruding, bracing, cooling, granulating, drying and packaging to obtain the finished product. The technology still has the limitations of not being fast enough in crystallization, long in processing period, easy to warp and the like. And the blending method requires a relatively large amount of crystallization nucleating agent to be added, which results in excessive production costs and is not suitable for practical production.
Publication No. CN101899201A provides for the introduction of inorganic attapulgite powder into the PET polymerization process, and the reaction of the attapulgite with terephthalic acid (PTA) and Ethylene Glycol (EG) to produce a class of rapidly crystallizing PET resins. Because the inorganic attapulgite has incomplete intercalation separation and larger particle size, a large number of inorganic-organic weak interface defects exist in the polymerization process, the high-rigidity polyester chain segments are not improved, the mechanical properties, particularly the impact resistance, of the obtained high-crystallization polyester resin are still poor, and the crystallization process of the product still needs to be completed at a higher molding temperature.
There are reports about rapid crystallization and nucleation of PET polyesters at home and abroad, and the rapid crystallization and nucleation of PET polyesters are realized by adding a high molecular crystallization promoter and an inorganic powder nucleating agent, and the problems of dispersibility of additives, slow local crystallization of polyester, unobvious improvement on other properties of polyester and the like exist.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above-mentioned and/or problems of insufficient crystallization, long processing period, and poor mechanical properties in the prior art.
Therefore, one of the purposes of the invention is to overcome the defects of the traditional composite crystallization nucleating agent which is added with inorganic powder and a high molecular crystallization accelerator in a blending way and has influence on the performance of polyester PET, a complex process route, high production cost and the like, and provide the fast crystallization PET resin which has simple process, small addition amount of additives, ensures that the fast crystallization nucleating agent is stably and uniformly dispersed in polyester PET macromolecules in a copolymerization way, and greatly improves the product performance of nano attapulgite copolymerized PEG and the preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme: a fast crystallization PET resin of nano attapulgite copolymerized PEG is prepared by copolymerizing a monomer containing a PET chain segment, a monomer containing a PEG chain segment and ionized modified nano attapulgite by an in-situ polymerization method;
wherein, the mass percentage of the monomer containing the PEG chain segment is 3-25%; the mass percentage of the ionized modified nano attapulgite is 0.1-3%.
As a preferable scheme of the fast crystallization PET resin of the nano attapulgite copolymerized PEG, the following is adopted: the monomer containing the PET chain segment is polymerized by at least two monomers of terephthalic acid and ethylene glycol under a catalyst, wherein the catalyst comprises one or more of antimony catalysts, germanium catalysts and titanium catalysts, and the catalyst content is 6-300 ppm of the mass of terephthalic acid.
As a preferable scheme of the fast crystallization PET resin of the nano attapulgite copolymerized PEG, the following is adopted: the monomer containing PEG chain segment is polyethylene glycol prepolymer with molecular weight of 400-10000.
As a preferable scheme of the fast crystallization PET resin of the nano attapulgite copolymerized PEG, the following is adopted: the ionization modified nano attapulgite comprises divalent/trivalent organic metal salt as an ionization modification component, wherein the apparent particle diameter D50 of the nano attapulgite is 50-800 nm, and the mass ratio of the nano attapulgite to the organic metal salt is 10:0.2-4.
As a preferable scheme of the fast crystallization PET resin of the nano attapulgite copolymerized PEG, the following is adopted: the divalent/trivalent organic metal salt comprises one of zinc acetate, aluminum acetate, magnesium acetate and zinc citrate.
The invention also discloses a preparation method of the nano attapulgite copolymerized PEG rapid crystallization PET resin, which comprises the following steps of,
adding acid modified attapulgite and divalent/trivalent organic metal salt into ethylene glycol, pre-dispersing in a stirrer, and then dispersing and crushing in a ball mill for 1-12 hours to obtain modified attapulgite slurry;
adding terephthalic acid, modified attapulgite slurry, polyethylene glycol and ethylene glycol into an esterification kettle for esterification reaction;
adding a catalyst with the mass of 6-300 ppm of terephthalic acid, mixing and stirring for 10-20 minutes, introducing into a polycondensation kettle, and discharging after polymerization for 1-4 hours to obtain the fast crystallized PET resin of the nano attapulgite copolymerized PEG;
wherein, the mass percentage of the polyethylene glycol in the fast crystallization PET resin is 3-25%; the mass percentage of the ionized modified nano attapulgite in the fast crystallized PET resin is 0.1-3%.
As a preferable scheme of the preparation method of the fast crystallization PET resin of the nano attapulgite copolymerized PEG, the preparation method comprises the following steps: the mol ratio of terephthalic acid to ethylene glycol is 1:1.10-1.25.
As a preferable scheme of the preparation method of the fast crystallization PET resin of the nano attapulgite copolymerized PEG, the preparation method comprises the following steps: the esterification reaction is carried out, the temperature of the esterification kettle is raised to 230-250 ℃ by stirring, the internal pressure of the esterification kettle is controlled to be 200-400 kPa, the reaction is carried out for 1-2 hours, and the esterification is finished when the esterification rate reaches over 90-99 percent.
As a preferable scheme of the preparation method of the fast crystallization PET resin of the nano attapulgite copolymerized PEG, the preparation method comprises the following steps: the polymerization reaction is carried out, the pressure of a polycondensation kettle is between-50 and-105 kPa, and the reaction temperature is between 260 and 280 ℃.
The invention also discloses a preparation method of the nano attapulgite copolymerized PEG rapid crystallization PET engineering plastic particles, which comprises the following steps of,
the fast crystallization PET resin of the nano attapulgite copolymer PEG and glass fiber according to any one of claims 1 to 5 are simultaneously added into a double screw extruder, the content of the glass fiber is 10 to 40 percent of the total amount, and the fast crystallization PET engineering plastic particles are obtained after extrusion, water cooling and granulating.
Compared with the prior art, the invention has the following beneficial effects:
(1) The ionization modified nano attapulgite slurry can be directly participated in the PET polymerization process, can be uniformly dispersed in the PET polyester in a network structure, forms a nano microphase material structure with good compatibility with PET polyester molecular chains and good interface, can well improve the strength of the PET, promotes the rapid crystallization of the PET, avoids the traditional need of adding a high molecular crystallization promoter, and reduces the influence on other properties of the PET.
(2) The molecular weight of the polyethylene glycol prepolymer with the flexible long chain segment is 400-10000, the hydroxyl functional groups involved in the polyethylene glycol prepolymer can participate in the polymerization reaction of polyester in the PET polymerization process, and the block structure of the polyethylene glycol with the flexible chain segment and the rigid terephthalic acid-ethylene glycol chain segment is formed. The flexible polyethylene glycol chain segment greatly promotes the regular crystallization and folding of the PET chain segment in the crystallization process, and accelerates the crystallization speed of PET; meanwhile, the soft block PEG chain segment also reduces the crystallization defect and stress concentration effect of the PET rigid chain segment, and greatly improves the mechanical properties of PET, in particular the impact resistance and the elongation of the material.
(3) The invention has simple production process, less additive consumption and low production cost. The cold crystallization temperature of the fast crystallized PET resin of the nano attapulgite copolymerized PEG is reduced by 20 ℃ compared with that of the conventional PET resin, and the hot crystallization temperature is increased by more than 15 ℃ compared with that of the conventional PET resin; the impact strength of the fast crystallized PET engineering plastic particles of the nano attapulgite copolymerized PEG is improved by more than 50 percent. The cost is controllable, and meanwhile, other performances of the PET resin are greatly improved, so that the PET resin is well suitable for production requirements.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
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 in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) 100 g of phosphoric acid modified attapulgite (purchased from Xuyi attapulgite application technology research and development and industrialization center of the Chinese academy of sciences) is added with 50 g of 20% concentration zinc acetate aqueous solution, then added into 750 g of ethylene glycol, pre-dispersed in a stirrer, then dispersed and crushed in a zirconium dioxide ball mill for 5 hours, so that the attapulgite and the zinc acetate are fully ion-exchanged, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, thereby obtaining the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 150nm, and the effective concentration of the ionized modified nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-glycol slurry and glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to be 200-400 kPa, reacting for 1.5 hours, finishing esterification, removing the pressure, adding 200ppm of ethylene glycol antimony catalyst by mass of terephthalic acid, adding 10% of polyethylene glycol prepolymer by mass of terephthalic acid and the molecular weight of 1000, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to keep the pressure of the polycondensation kettle at-50 to-105 kPa, controlling the reaction temperature at 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of terephthalic acid to the glycol monomers is 1.0:1.20, and the content of ionized modified attapulgite in the resin is 0.1%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 30 percent, the rotating speed of the screw is 200r/min, the torque is 70 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Example 2
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% magnesium acetate aqueous solution, then added into 750 g of ethylene glycol, pre-dispersed in a stirrer, then dispersed and crushed in a zirconium dioxide ball mill for 10 hours, so that the attapulgite and zinc acetate are fully ion-exchanged, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, thus obtaining the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 130nm, and the effective concentration of the ionized modified nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-ethylene glycol slurry and ethylene glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to 200-400 kPa, reacting for 2 hours to ensure that the esterification rate reaches 96%, ending the esterification, releasing the pressure, adding 200ppm of ethylene glycol antimony catalyst, adding 10% of polyethylene glycol prepolymer with the mass of terephthalic acid and the molecular weight of 6000, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to ensure that the pressure of the polycondensation kettle is kept between-50 and-105 kPa, controlling the reaction temperature to 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomers is 1.0:1.12, and the content of the ionized modified attapulgite in the resin is 0.3%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 20 percent, the rotating speed of the screw is 200r/min, the torque is 65 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 275-285 ℃ of the front section, 270-280 ℃ of the middle section, 250-280 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Example 3
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% concentration aluminum acetate aqueous solution, then added into 750 g of ethylene glycol, pre-dispersed in a stirrer, then dispersed and crushed in a zirconium dioxide ball mill for 10 hours, so that the attapulgite and zinc acetate are fully ion-exchanged, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, thus obtaining the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 130nm, and the effective concentration of the ionized modified nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-ethylene glycol slurry and ethylene glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to 200-400 kPa, reacting for 2 hours to ensure that the esterification rate reaches 96%, ending the esterification, releasing the pressure, adding 200ppm of ethylene glycol antimony catalyst, adding 10% of polyethylene glycol prepolymer with the mass of terephthalic acid and the molecular weight of 6000, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to ensure that the pressure of the polycondensation kettle is kept between-50 and-105 kPa, controlling the reaction temperature to 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomers is 1.0:1.12, and the content of the ionized modified attapulgite in the resin is 0.5%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 30 percent, the rotating speed of the screw is 200r/min, the torque is 65 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 275-285 ℃ of the front section, 270-280 ℃ of the middle section, 250-280 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Example 4
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then added into 750 g of ethylene glycol, pre-dispersed in a stirrer, then dispersed and crushed in a zirconium dioxide ball mill for 5 hours, so that the attapulgite and the zinc acetate are fully ion-exchanged, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, thus obtaining the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 150nm, and the effective concentration of the ionized modified nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-glycol slurry and glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to be 200-400 kPa, reacting for 1.5 hours to ensure that the esterification is finished with the esterification rate being more than 94%, releasing the pressure, then adding 200ppm of glycol antimony catalyst by mass of terephthalic acid, adding 10% of polyethylene glycol prepolymer by mass of terephthalic acid and the molecular weight of 1000, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to ensure that the pressure of the polycondensation kettle is kept between-50 and-105 kPa, controlling the reaction temperature to be 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of terephthalic acid to the glycol monomers is 1.0:1.20, and the content of the ionized modified attapulgite in the resin is 1.5%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 30 percent, the rotating speed of the screw is 200r/min, the torque is 70 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Example 5
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then added into 750 g of ethylene glycol, pre-dispersed in a stirrer, then dispersed and crushed in a zirconium dioxide ball mill for 5 hours, so that the attapulgite and the zinc acetate are fully ion-exchanged, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, thus obtaining the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 150nm, and the effective concentration of the ionized modified nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-glycol slurry and glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to be 200-400 kPa, reacting for 1.5 hours to ensure that the esterification is finished with the esterification rate being more than 94%, releasing the pressure, then adding 200ppm of glycol antimony catalyst by mass of terephthalic acid, adding 30% of polyethylene glycol prepolymer by mass of terephthalic acid and the molecular weight of 1000, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to ensure that the pressure of the polycondensation kettle is kept between-50 and-105 kPa, controlling the reaction temperature to be 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of terephthalic acid to the glycol monomers is 1.0:1.20, and the content of the ionized modified attapulgite in the resin is 1.5%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 20 percent, the rotating speed of the screw is 200r/min, the torque is 70 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Comparative example 1
(1) 100 g of phosphoric acid modified attapulgite is added into 750 g of ethylene glycol, pre-dispersed in a stirrer, dispersed and crushed in a zirconium dioxide ball mill for 5 hours, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, so that nano attapulgite-ethylene glycol slurry is obtained. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 150nm, and the effective concentration of the nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-glycol slurry and glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to be 200-400 kPa, reacting for 1.5 hours, finishing esterification, removing the pressure, adding 200ppm of ethylene glycol antimony catalyst by mass of terephthalic acid, adding 10% of polyethylene glycol prepolymer by mass of terephthalic acid and the molecular weight of 1000, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to keep the pressure of the polycondensation kettle at-50 to-105 kPa, controlling the reaction temperature at 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of terephthalic acid to the glycol monomers is 1.0:1.20, and the content of ionized modified attapulgite in the resin is 0.1%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 30 percent, the rotating speed of the screw is 200r/min, the torque is 70 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Comparative example 2
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then added into 750 g of ethylene glycol, pre-dispersed in a stirrer, then dispersed and crushed in a zirconium dioxide ball mill for 5 hours, so that the attapulgite and the zinc acetate are fully ion-exchanged, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, thus obtaining the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 150nm, and the effective concentration of the ionized modified nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-ethylene glycol slurry and ethylene glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to be 200-400 kPa, reacting for 1.5 hours, ending esterification with the esterification rate being more than 94%, releasing the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding diethylene glycol (DEG) with the mass of 10% and the molecular weight of 106, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to keep the pressure of the polycondensation kettle at-50 to-105 kPa, controlling the reaction temperature at 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of terephthalic acid to the ethylene glycol monomers is 1.0:1.20, and the content of ionized modified attapulgite in the resin is 0.1%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 30 percent, the rotating speed of the screw is 200r/min, the torque is 70 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Comparative example 3
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then added into 750 g of ethylene glycol, pre-dispersed in a stirrer, then dispersed and crushed in a zirconium dioxide ball mill for 5 hours, so that the attapulgite and the zinc acetate are fully ion-exchanged, uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, thus obtaining the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite passing through a laser ion calliper is 150nm, and the effective concentration of the ionized modified nano attapulgite-ethylene glycol slurry is 13%;
(2) Adding terephthalic acid, ionized modified nano attapulgite-ethylene glycol slurry and ethylene glycol monomers into an esterification kettle, stirring and heating the esterification kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to be 200-400 kPa, reacting for 1.5 hours, ending esterification with the esterification rate being more than 94%, releasing the pressure, then adding 200ppm of ethylene glycol antimony catalyst by mass of terephthalic acid, adding 10% of polyethylene glycol prepolymer by mass of terephthalic acid and the molecular weight of 20000, mixing and stirring for 15 minutes, introducing the mixture into a polycondensation kettle, starting a vacuum pump to keep the pressure of the polycondensation kettle at-50 to-105 kPa, controlling the reaction temperature at 250-280 ℃, and discharging the reaction kettle for 3 hours to obtain the in-situ polymerized nano attapulgite copolymerized PEG fast crystallized PET resin, wherein the molar ratio of terephthalic acid to the ethylene glycol monomers is 1.0:1.20, and the content of ionized modified attapulgite in the resin is 0.1%;
(3) The prepared fast crystallized PET resin of the nano attapulgite copolymerized PEG is added into a hopper of a double-screw extruder, glass fiber is added into the double-screw extruder, the content of the glass fiber is controlled to be 30 percent, the rotating speed of the screw is 200r/min, the torque is 70 percent, the temperatures of all sections of the screw are respectively 275-285 ℃ of melt, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and the extruded glass fiber is cooled by water and then pelletized.
Comparative example 4
And performing performance evaluation by using super-bright SB500 polyester chips produced by instrumentation chemical fibers.
Comparative example 5
Adding SB500 polyester chips into a hopper of a double-screw extruder, adding glass fibers into the double-screw extruder, controlling the content of the glass fibers to be 30% of the total amount, controlling the rotating speed of the screws to be 200r/min and the torque to be 65%, wherein the temperatures of all sections of the screws are respectively 275-285 ℃ of melt temperature, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and cooling by water after extrusion and granulating.
Comparative example 6
Adding SB500 polyester chips into a hopper of a double-screw extruder, adding glass fibers into the double-screw extruder, controlling the content of the glass fibers to be 20 percent of the total amount, controlling the rotating speed of the screws to be 200r/min and the torque to be 65 percent, wherein the temperatures of all sections of the screws are respectively 275-285 ℃ of melt temperature, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, and cooling by water after extrusion and granulating.
The performance test was performed on the above examples 1 to 5 and comparative examples 1 to 6, and the results are shown in table 1.
TABLE 1
As can be seen from the comparison of the data in example 1 and example 4, the content of the ionized modified attapulgite in the resin is increased from 0.1% to 1.5%, the characteristic viscosity of the resin and the notch impact strength of the resin are not obviously changed, but the peak value of the cold crystallization temperature of the resin is reduced from 97 ℃ to 88 ℃, the peak value of the hot crystallization temperature of the resin is increased from 208 ℃ to 216 ℃, and the notch impact performance of the modified PET is reduced from 95J/m to 90J/m.
As can be seen from the comparison of the data in the examples 4 and 5, the content of the polyethylene glycol prepolymer is increased from 10% to 30%, and each performance index is greatly reduced.
As can be seen from the comparison of the data of the embodiment 1 and the comparative example 1, the nano attapulgite added in the comparative example 1 is not subjected to ionization modification, the final resin notch impact strength and the modified PET notch impact performance are reduced, meanwhile, the resin cold crystallization temperature peak value is increased from 97 ℃ to 110 ℃, and the resin hot crystallization temperature peak value is increased from 208 ℃ to 210 ℃, which is attributed to the ionization modification of the nano attapulgite slurry, can directly participate in the PET polymerization process, can be uniformly dispersed in PET polyester in a network structure, forms a nano microphase material structure with good compatibility with PET polyester molecular chains and good interface, can well improve the strength of PET, promote PET rapid crystallization, avoid the traditional need of adding a high molecular crystallization accelerator, and reduce the influence on other PET performances.
As can be seen from a comparison of the data in example 1 and comparative examples 2 and 3, the use of polyethylene glycol with too high or too low a molecular weight negatively affects PET properties. By adopting low molecular weight DEG, the notch impact strength of the resin and the notch impact performance of the modified PET are greatly reduced, and meanwhile, the peak value of the cold crystallization temperature of the resin is increased from 97 ℃ to 140 ℃, and the peak value of the hot crystallization temperature of the resin is reduced from 208 ℃ to 189 ℃. The high molecular weight PEG is adopted, the notch impact strength of the resin and the notch impact performance of the modified PET are obviously reduced, and meanwhile, the peak value of the cold crystallization temperature of the resin is increased from 97 ℃ to 142 ℃, and the peak value of the hot crystallization temperature of the resin is increased from 208 ℃ to 216 ℃.
As can be seen from the comparison of the data of example 1 and comparative example 4, the cold crystallization temperature of the fast crystallizing PET resin of nano attapulgite copolymerized PEG is reduced by 20 ℃ compared with the conventional PET resin, and the hot crystallization temperature is increased by more than 15 ℃ compared with the conventional PET resin; as can be seen from the comparison of the data of example 1 and comparative examples 5 and 6, the impact strength of the fast crystallization PET engineering plastic particles of the nano attapulgite copolymerized PEG is improved by more than 50%; the performance of the PET resin prepared by the invention is greatly improved, and the PET resin is well suitable for production requirements.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (6)
1. A fast crystallization PET resin of nano attapulgite copolymerized PEG is characterized in that: the method is characterized in that the polymer is synthesized by copolymerizing a monomer containing a PET chain segment, a monomer containing a PEG chain segment and ionized modified nano attapulgite by an in-situ polymerization method;
wherein the mass percentage of the monomer containing the PEG chain segment is 3-25%; the mass percentage of the ionized modified nano attapulgite is 0.1-3%;
the monomer containing the PEG chain segment is a polyethylene glycol prepolymer, and the molecular weight is 400-10000;
the ionization modified nano attapulgite comprises divalent/trivalent organic metal salt as an ionization modification component, wherein the apparent particle diameter D50 of the nano attapulgite is 50-800 nm, and the mass ratio of the nano attapulgite to the organic metal salt is 10:0.2-4; the divalent/trivalent organic metal salt comprises one of zinc acetate, aluminum acetate, magnesium acetate and zinc citrate;
the monomer containing the PET chain segment is formed by polymerizing at least two monomers of terephthalic acid and ethylene glycol under a catalyst, wherein the catalyst comprises one or more of antimony catalysts, germanium catalysts and titanium catalysts, and the catalyst content is 6-300 ppm of the mass of terephthalic acid.
2. The method for preparing the nano attapulgite copolymerized PEG fast crystallization PET resin according to claim 1, which is characterized in that: comprising the steps of (a) a step of,
adding acid modified attapulgite and divalent/trivalent organic metal salt into ethylene glycol, pre-dispersing in a stirrer, and then dispersing and crushing in a ball mill for 1-12 hours to obtain ionized modified nano attapulgite slurry;
adding terephthalic acid, ionized modified nano attapulgite slurry and ethylene glycol into an esterification kettle for esterification reaction;
adding a catalyst with the mass of 6-300 ppm of terephthalic acid, adding a polyethylene glycol prepolymer, mixing and stirring for 10-20 minutes, introducing into a polycondensation kettle, and discharging after polymerization for 1-4 hours to obtain the fast crystallization PET resin of the nano attapulgite copolymerized PEG;
wherein the mass percentage of the polyethylene glycol in the fast crystallization PET resin is 3-25%; the mass percentage of the ionized modified nano attapulgite in the fast crystallization PET resin is 0.1-3%.
3. The method for preparing the nano attapulgite copolymerized PEG fast crystallization PET resin according to claim 2, which is characterized in that: the molar ratio of terephthalic acid to ethylene glycol is 1:1.10-1.25.
4. The method for preparing the nano attapulgite copolymerized PEG fast crystallization PET resin according to claim 2, which is characterized in that: and (3) stirring and heating the esterification reaction kettle to 230-250 ℃, controlling the internal pressure of the esterification kettle to be 200-400 kPa, and reacting for 1-2 hours to ensure that the esterification rate reaches more than 90-99% and ending the esterification.
5. The method for preparing the nano attapulgite copolymerized PEG fast crystallization PET resin according to claim 2, which is characterized in that: the polymerization reaction is carried out, the pressure of the polycondensation kettle is minus 50 to minus 105kPa, and the reaction temperature is 260-280 ℃.
6. A preparation method of a nano attapulgite copolymerized PEG rapid crystallization PET engineering plastic particle is characterized by comprising the following steps: comprising the steps of (a) a step of,
the fast crystallization PET resin of the nano attapulgite copolymerized PEG and glass fiber are simultaneously added into a double screw extruder, the content of the glass fiber is 10-40% of the total amount, and the fast crystallization PET engineering plastic particles are obtained after water cooling and granulating after extrusion.
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