CN115197549A - Rapid crystallization PET resin of nanometer attapulgite copolymerized PEG and preparation method thereof - Google Patents
Rapid crystallization PET resin of nanometer attapulgite copolymerized PEG and preparation method thereof Download PDFInfo
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- CN115197549A CN115197549A CN202210743454.2A CN202210743454A CN115197549A CN 115197549 A CN115197549 A CN 115197549A CN 202210743454 A CN202210743454 A CN 202210743454A CN 115197549 A CN115197549 A CN 115197549A
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 102
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 102
- 238000002425 crystallisation Methods 0.000 title claims abstract description 81
- 230000008025 crystallization Effects 0.000 title claims abstract description 80
- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 18
- 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 135
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 87
- 229920001223 polyethylene glycol Polymers 0.000 claims description 72
- 238000005886 esterification reaction Methods 0.000 claims description 54
- 230000032050 esterification Effects 0.000 claims description 50
- 239000002002 slurry Substances 0.000 claims description 30
- 239000003365 glass fiber Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000006068 polycondensation reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 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
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229920006351 engineering plastic Polymers 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 238000006243 chemical reaction 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
- 239000000203 mixture Substances 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
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 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
- 230000000379 polymerizing effect Effects 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
- 239000002994 raw material Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 23
- 239000002667 nucleating agent Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 3
- 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
- 239000006185 dispersion Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001125 extrusion Methods 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
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 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
- 238000005342 ion exchange Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- -1 bottles Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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
- 238000012827 research and development Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 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
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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 rapid crystallization PET resin of nanometer attapulgite copolymerized with PEG and a preparation method thereof, wherein the rapid crystallization PET resin is copolymerized and synthesized by a monomer containing a PET chain segment, a monomer containing a PEG chain segment and ionized modified nanometer attapulgite through 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 adding amount, and the fast crystallization nucleating agent is stably and uniformly dispersed in the polyester PET macromolecules through in-situ polymerization and flexible chain segment copolymerization, and the flexible chain segment is polymerized into the polyester chain segment, so that the crystallization property 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 rapid crystallization PET resin of nanometer attapulgite copolymerized PEG and a preparation method thereof.
Background
PET is a thermoplastic engineering plastic with excellent mechanical properties, heat resistance and chemical reagent resistance, and is widely applied to the fields of fibers, bottles, films and the like. At present, the application of PET in non-fiber polyester (bottle sheet, film, engineering plastic) is increasing, and the engineering plastic is one of the research and development hotspots in the PET non-fiber field. However, the main chain of PET has high rigidity and the chain segment moves slowly, so the crystallization speed is slow, further the injection molding temperature is high, the molding cycle is long, the product is easy to stick and warp, and the application of the PET in engineering plastics is severely restricted.
Publication No. CN1388177A provides a method for obtaining a rapidly crystallized polyethylene terephthalate composite by physical modification in a twin-screw extruder. Firstly, polyethylene terephthalate, a composite crystallization nucleating agent and other additives are stirred and mixed at a high speed, then the mixture is fed into a double-screw extruder by a precisely metered feeder, then the precisely metered feeder for filling reinforcing agent is added into the extruder, and the mixture is plasticized, melted and compounded, and then the mixture is extruded, pulled into strips, cooled, granulated, dried and packaged into a finished product. The technology still has the limitations of not fast enough crystallization, long processing period and easy warping. And the blending method requires a large amount of added crystallization nucleating agent, which causes the production cost to be too high and is not suitable for the actual production requirement.
Patent publication No. CN101899201A provides a kind of PET resin with fast crystallization prepared by introducing inorganic attapulgite powder into the PET polymerization process and reacting attapulgite with terephthalic acid (PTA) and Ethylene Glycol (EG). Because the inorganic attapulgite has incomplete intercalation separation and larger grain diameter, a large amount of inorganic-organic weak interface defects exist in the polymerization process, and the high-rigidity polyester chain segment is not improved, the mechanical property, especially the impact resistance, of the obtained high-crystallization polyester resin is still not good, and the crystallization process of the product still needs to be finished at a higher molding temperature.
Some reports about rapid crystallization nucleation of PET polyester are also reported at home and abroad, and the nucleation is mostly realized by adding a macromolecular crystallization promoter and an inorganic powder nucleating agent, and the problems of dispersibility of additives, slow local crystallization of polyester, unobvious improvement on other performances of polyester and the like exist.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above and/or the problems of insufficient crystallization, long processing period and poor mechanical properties of the prior art.
Therefore, one of the purposes of the invention is to overcome the defects of the traditional method of adding a composite crystallization nucleating agent of inorganic powder and a polymeric crystallization promoter in a blending manner to influence the performance of polyester PET, complicated process route, high production cost and the like, and to provide the rapid crystallization PET resin of the nano-attapulgite copolymerized PEG and the preparation method thereof, wherein the process is simple, the addition amount of the additive is small, the rapid crystallization nucleating agent is stably and uniformly dispersed in the polyester PET macromolecules in a copolymerization manner, and the product performance is greatly improved.
In order to solve the technical problems, the invention provides the following technical scheme: a rapid crystallization PET resin of nanometer attapulgite copolymerized with PEG is copolymerized and synthesized by a monomer containing a PET chain segment, a monomer containing a PEG chain segment and ionized modified nanometer attapulgite through an in-situ polymerization method;
wherein, the weight percentage of the monomer containing the PEG chain segment is 3-25%; the mass percentage content of the ionized modified nano-attapulgite is 0.1-3%.
As a preferred embodiment of the rapid crystallization PET resin of the nano-attapulgite copolymerized PEG of the invention, the resin comprises the following components: the monomer containing the PET chain segment is prepared 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 or titanium catalysts, and the content of the catalyst is 6-300 ppm of the mass of the terephthalic acid.
As a preferred embodiment of the rapid crystallization PET resin of the nano-attapulgite copolymerized PEG of the invention, the resin comprises the following components: the monomer containing PEG chain segment is polyethylene glycol prepolymer with molecular weight of 400-10000.
As a preferred embodiment of the rapid crystallization PET resin of the nano-attapulgite copolymerized PEG of the invention, the resin comprises the following components: the ionization modified nano-attapulgite comprises divalent/trivalent organic metal salts as ionization modifying components, 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 salts is 10.2-4.
As a preferred embodiment of the rapid crystallization PET resin of the nano-attapulgite copolymerized PEG of the invention, the resin comprises the following components: 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 rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG, which comprises the following steps,
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, performing polymerization reaction for 1-4 hours, and discharging to obtain the rapid crystallization PET resin of the nano-attapulgite copolymerized PEG;
wherein, the mass percentage of the polyethylene glycol in the rapid crystallization PET resin is 3-25%; the mass percentage of the ionized modified nano attapulgite in the rapid crystallization PET resin is 0.1-3%.
As a preferred scheme of the preparation method of the rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG, the method comprises the following steps: the molar ratio of terephthalic acid to ethylene glycol is 1.10-1.25.
As a preferred scheme of the preparation method of the rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG, the method comprises the following steps: in the esterification reaction, 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 lasts for 1-2 hours, and the esterification rate is up to more than 90-99 percent, thus finishing the esterification.
As a preferred scheme of the preparation method of the rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG, the method comprises the following steps: the polymerization reaction has a polycondensation kettle pressure of-50 to-105 kPa and a reaction temperature of 260 to 280 ℃.
The invention also discloses a preparation method of the PET engineering plastic particles of the nanometer attapulgite copolymerized PEG, which comprises the following steps,
the rapidly crystallized PET resin of nano-attapulgite copolymerized PEG according to any one of claims 1 to 5 and glass fiber are added into a twin-screw extruder at the same time, the content of the glass fiber is 10 to 40 percent of the total amount, and the rapidly crystallized PET engineering plastic particles are obtained after water cooling and dicing after extrusion.
Compared with the prior art, the invention has the following beneficial effects:
(1) The ionized modified nano-attapulgite slurry utilized by the invention can directly participate in the PET polymerization process, can be uniformly dispersed in PET in a network structure to form a nano-micro-phase material structure with good compatibility with PET polyester molecular chains and good interface, can well improve the strength of the polyester PET, promotes the rapid crystallization of the polyester PET, avoids the traditional need of adding a high-molecular crystallization accelerator, and reduces the influence on other properties of the PET.
(2) The molecular weight of the polyethylene glycol prepolymer of the flexible long chain segment is 400-10000, and the participated hydroxyl functional group can participate in the polymerization reaction of polyester in the polymerization process of PET to form a block structure of the flexible chain segment polyethylene glycol and the rigid terephthalic acid-ethylene glycol chain segment. The flexible polyethylene glycol chain segment greatly promotes the regular crystallization and folding of the PET chain segment in the crystallization process, and the crystallization speed of PET is accelerated; meanwhile, the flexible 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, particularly 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 rapid crystallization PET resin of the nanometer 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; the impact strength of the rapidly crystallized PET engineering plastic particles of the nanometer attapulgite copolymerized PEG is improved by more than 50 percent. The cost is controllable, and other properties of the PET resin are greatly improved, so that the PET resin is well suitable for production requirements.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
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 than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is 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 Zhongkoyao), 50 g of 20% zinc acetate aqueous solution and 750 g of ethylene glycol are added, pre-dispersion is carried out in a stirrer, then dispersion and crushing are carried out in a zirconium dioxide ball mill for 5 hours, so that the attapulgite and the zinc acetate are subjected to sufficient ion exchange and are uniformly dispersed in the ethylene glycol, and the water is removed by vacuumizing to obtain the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite by a laser ion diameter measuring instrument is 150nm, and the effective concentration of the ionized modified nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-glycol slurry and ethylene glycol monomer 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 1.5 hours to ensure that the esterification rate is more than 94 percent, ending the esterification, relieving the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding polyethylene glycol prepolymer with the mass of 10 percent and the molecular weight of 1000 percent of terephthalic acid, mixing and stirring for 15 minutes, introducing 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 ℃, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG fast crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomer is 1.0;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 30 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 70 percent, the temperature of each section of the screw to be 275-285 ℃ of melt temperature, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, cooling by water after extrusion and then dicing.
Example 2
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% magnesium acetate aqueous solution, then 750 g of ethylene glycol is added, pre-dispersion is carried out in a stirrer, then dispersion and crushing are carried out in a zirconium dioxide ball mill for 10 hours, the attapulgite and zinc acetate are subjected to sufficient ion exchange and are uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, so as to obtain the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the attapulgite is 130nm by a laser ion diameter measuring instrument, and the effective concentration of the ionized modified nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-ethylene glycol slurry and ethylene glycol monomer 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 esterification, relieving pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding polyethylene glycol prepolymer with the mass of 10% of terephthalic acid and the molecular weight of 6000, mixing and stirring for 15 minutes, introducing into a polycondensation kettle, starting a vacuum pump to ensure that the pressure of the polycondensation kettle is kept between-50 and-105 kPa, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG rapid crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomer is 1.0;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 20 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 65 percent, the temperature of each section of the screw to be 275-285 ℃ of melt, 275-285 ℃ of the front section, 270-280 ℃ of the middle section and 250-280 ℃ of the rear section, cooling by water after extrusion and then dicing.
Example 3
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% aluminum acetate aqueous solution, then 750 g of ethylene glycol is added, pre-dispersion is carried out in a stirrer, then dispersion and crushing are carried out in a zirconium dioxide ball mill for 10 hours, the attapulgite and zinc acetate are subjected to sufficient ion exchange and are uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, so as to obtain the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the attapulgite is 130nm by a laser ion diameter measuring instrument, and the effective concentration of the ionized modified nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-glycol slurry and ethylene glycol monomer 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 esterification, relieving the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding polyethylene glycol prepolymer with the mass of 10% of terephthalic acid and the molecular weight of 6000, mixing and stirring for 15 minutes, introducing into a polycondensation kettle, starting a vacuum pump to ensure that the pressure of the polycondensation kettle is kept between-50 and-105 kPa, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG rapid crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomer is 1.0, and the content of the ionized modified attapulgite in the resin is 0.5%;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 30 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 65 percent, the temperature of each section of the screw to be 275-285 ℃ of melt, 275-285 ℃ of the front section, 270-280 ℃ of the middle section and 250-280 ℃ of the rear section, cooling by water after extrusion and then dicing.
Example 4
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then 750 g of ethylene glycol is added, pre-dispersion is carried out in a stirrer, then dispersion and crushing are carried out in a zirconium dioxide ball mill for 5 hours, the attapulgite and the zinc acetate are subjected to sufficient ion exchange and are uniformly dispersed in the ethylene glycol, and water involved is removed by vacuumizing, so that the ionized modified nano attapulgite-ethylene glycol slurry is obtained. Wherein, the D50 of the attapulgite by a laser ion diameter measuring instrument is 150nm, and the effective concentration of the ionized and modified nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-glycol slurry and ethylene glycol monomer 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 1.5 hours to ensure that the esterification rate is more than 94 percent, ending the esterification, relieving the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding polyethylene glycol prepolymer with the mass of 10 percent and the molecular weight of 1000 percent of terephthalic acid, mixing and stirring for 15 minutes, introducing 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 ℃, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG fast crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomer is 1.0;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 30 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 70 percent, the temperature of each section of the screw to be 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, cooling by water after extrusion, and then pelletizing.
Example 5
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then 750 g of ethylene glycol is added, pre-dispersion is carried out in a stirrer, then dispersion and crushing are carried out in a zirconium dioxide ball mill for 5 hours, the attapulgite and the zinc acetate are subjected to sufficient ion exchange and are uniformly dispersed in the ethylene glycol, and the water involved is removed by vacuumizing, so as to obtain the ionized modified nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite by a laser ion diameter measuring instrument is 150nm, and the effective concentration of the ionized modified nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-glycol slurry and ethylene glycol monomer 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 1.5 hours to ensure that the esterification rate is more than 94 percent, ending the esterification, relieving the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding polyethylene glycol prepolymer with the mass of 30 percent and the molecular weight of 1000 percent of terephthalic acid, mixing and stirring for 15 minutes, introducing 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 ℃, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG fast crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomer is 1.0;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 20 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 70 percent, the temperature of each section of the screw to be 275-285 ℃ of melt temperature, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, cooling by water after extrusion and then dicing.
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 vacuumized to remove the participating water, so as to obtain nano attapulgite-ethylene glycol slurry. Wherein, the D50 of the particle size of the attapulgite by a laser ion diameter measuring instrument is 150nm, and the effective concentration of the nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-glycol slurry and ethylene glycol monomer 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 1.5 hours to ensure that the esterification rate is more than 94 percent, ending the esterification, relieving the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding polyethylene glycol prepolymer with the mass of 10 percent and the molecular weight of 1000 percent of terephthalic acid, mixing and stirring for 15 minutes, introducing 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 ℃, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG fast crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomer is 1.0;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 30 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 70 percent, the temperature of each section of the screw to be 275-285 ℃ of melt temperature, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, cooling by water after extrusion and then dicing.
Comparative example 2
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then 750 g of ethylene glycol is added, pre-dispersion is carried out in a stirrer, then dispersion and crushing are carried out in a zirconium dioxide ball mill for 5 hours, the attapulgite and the zinc acetate are subjected to sufficient ion exchange and are uniformly dispersed in the ethylene glycol, and water involved is removed by vacuumizing, so that the ionized modified nano attapulgite-ethylene glycol slurry is obtained. Wherein, the D50 of the particle size of the attapulgite by a laser ion diameter measuring instrument is 150nm, and the effective concentration of the ionized modified nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-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 1.5 hours to ensure that the esterification rate is more than 94 percent, ending the esterification, relieving the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of the terephthalic acid, adding diethylene glycol (DEG) with the mass of 10 percent of the terephthalic acid and the molecular weight of 106, mixing and stirring for 15 minutes, introducing 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 ℃, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG fast crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomers is 1.0;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 30 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 70 percent, the temperature of each section of the screw to be 275-285 ℃ of melt temperature, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, cooling by water after extrusion and then dicing.
Comparative example 3
(1) 100 g of phosphoric acid modified attapulgite is added with 50 g of 20% zinc acetate aqueous solution, then 750 g of ethylene glycol is added, pre-dispersion is carried out in a stirrer, then dispersion and crushing are carried out in a zirconium dioxide ball mill for 5 hours, the attapulgite and the zinc acetate are subjected to sufficient ion exchange and are uniformly dispersed in the ethylene glycol, and water involved is removed by vacuumizing, so that the ionized modified nano attapulgite-ethylene glycol slurry is obtained. Wherein, the D50 of the attapulgite by a laser ion diameter measuring instrument is 150nm, and the effective concentration of the ionized and modified nano attapulgite-glycol slurry is 13 percent;
(2) Adding terephthalic acid, ionized modified nano-attapulgite-glycol slurry and ethylene glycol monomer 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 1.5 hours to ensure that the esterification rate is more than 94 percent, ending the esterification, relieving the pressure, then adding ethylene glycol antimony catalyst with the mass of 200ppm of terephthalic acid, adding polyethylene glycol prepolymer with the mass of 10 percent of terephthalic acid and the molecular weight of 20000, mixing and stirring for 15 minutes, introducing 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 ℃, reacting for 3 hours, and discharging to obtain the in-situ polymerized nano-attapulgite copolymerized PEG fast crystallization PET resin, wherein the molar ratio of the terephthalic acid to the ethylene glycol monomer is 1.0;
(3) Adding the prepared rapid crystallization PET resin of the nanometer attapulgite copolymerized PEG into a hopper of a double-screw extruder, simultaneously adding glass fiber into the double-screw extruder, controlling the content of the glass fiber to be 30 percent of the total amount, the rotating speed of the screw to be 200r/min, the torque to be 70 percent, the temperature of each section of the screw to be 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, cooling by water after extrusion, and then pelletizing.
Comparative example 4
And (3) performing performance evaluation on super-bright SB500 polyester chips produced by the characterization chemical fibers.
Comparative example 5
The preparation method comprises the steps of adding SB500 polyester chips into a hopper of a double-screw extruder, simultaneously adding glass fibers into the double-screw extruder, controlling the content of the glass fibers to be 30% of the total amount, controlling the rotation speed of the screw to be 200r/min and the torque to be 65%, controlling the temperatures of all sections of the screw to be 275-285 ℃ of melt, 270-280 ℃ of a front section, 250-280 ℃ of a middle section and 240-260 ℃ of a rear section, cooling the extruded polyester chips by water, and then pelletizing the polyester chips.
Comparative example 6
The method comprises the steps of adding SB500 polyester chips into a hopper of a double-screw extruder, simultaneously adding glass fibers into the double-screw extruder, controlling the content of the glass fibers to be 20% of the total amount, controlling the rotating speed of the screw to be 200r/min and the torque to be 65%, controlling the temperatures of all sections of the screw to be 275-285 ℃ of melt, 270-280 ℃ of the front section, 250-280 ℃ of the middle section and 240-260 ℃ of the rear section, cooling the extruded polyester chips by water and then dicing the polyester chips.
The results of the performance tests conducted on examples 1 to 5 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1
As can be seen by comparing the data of 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 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 example 4 and example 5, the content of the polyethylene glycol prepolymer is increased from 10% to 30%, and all performance indexes are 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, and finally the notch impact strength of the resin and the notch impact performance of the modified PET are reduced, meanwhile, the peak value of the cold crystallization temperature of the resin is increased from 97 ℃ to 110 ℃, and the peak value of the hot crystallization temperature of the resin is increased from 208 ℃ to 210 ℃, which is attributed to the fact that the ionized modified nano attapulgite slurry can directly participate in the polymerization process of the PET, can be uniformly dispersed in the PET in a network structure, forms a nano microphase material structure with good compatibility with a PET polyester molecular chain and a good interface, can well improve the strength of the polyester PET, promotes the rapid crystallization of the polyester PET, avoids the traditional need of adding a high-molecular crystallization accelerator, and reduces the influence on other performances of the PET.
As can be seen from the comparison of the data in example 1 and comparative examples 2 and 3, the PET performance is negatively affected by the molecular weight of the polyethylene glycol used being too high or too low. By adopting the DEG with low molecular weight, the notch impact strength of the resin and the notch impact performance of the modified PET are both greatly reduced, 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 ℃. By adopting the high molecular weight PEG, the notch impact strength of the resin and the notch impact performance of the modified PET are both obviously reduced, meanwhile, the peak value of the cold crystallization temperature of the resin is increased from 97 ℃ to 142 ℃, and the peak value of the thermal 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 rapid crystallization PET resin of the 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 the example 1 and the comparative examples 5 and 6, the impact strength of the rapid crystallization PET engineering plastic particles of the nanometer attapulgite copolymerized PEG is improved by more than 50 percent; 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-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A rapid crystallization PET resin of nanometer attapulgite copolymerized PEG is characterized in that: the modified PET/attapulgite polymer is synthesized by copolymerizing a monomer containing a PET chain segment, a monomer containing a PEG chain segment and ionized modified nano attapulgite through 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%.
2. The rapidly crystallizing PET resin of nano-attapulgite copolymerized PEG according to claim 1, wherein: the monomer containing the PET chain segment is prepared 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 or titanium catalysts, and the content of the catalyst is 6-300 ppm of the mass of the terephthalic acid.
3. The rapidly crystallizing PET resin of nano-attapulgite copolpeg as claimed in claim 1 or 2, wherein: the monomer containing PEG chain segment is polyethylene glycol prepolymer with molecular weight of 400-10000.
4. The rapidly crystallized PET resin of nano-attapulgite copolymerized PEG according to claim 3, characterized in that: the ionization modified nano-attapulgite comprises a divalent/trivalent organic metal salt as an ionization modified 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 10.2-4.
5. The rapidly crystallized PET resin of nano-attapulgite copolymerized PEG according to any one of claims 1, 2, and 4, wherein: the divalent/trivalent organic metal salt comprises one of zinc acetate, aluminum acetate, magnesium acetate and zinc citrate.
6. A preparation method of a rapid crystallization PET resin of nanometer attapulgite copolymerized PEG is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
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, performing polymerization reaction for 1-4 hours, and discharging to obtain the rapid crystallization PET resin of the nano-attapulgite copolymerized PEG;
wherein, the mass percentage of the polyethylene glycol in the rapid crystallization PET resin is 3-25%; the mass percentage of the ionized modified nano attapulgite in the rapid crystallization PET resin is 0.1-3%.
7. The method for preparing the rapid crystallization PET resin of nano-attapulgite copolymerized PEG according to claim 6, characterized in that: the molar ratio of terephthalic acid to ethylene glycol is 1.10-1.25.
8. The method for preparing the rapid crystallization PET resin of nano-attapulgite copolymerized PEG according to claim 6, characterized in that: in the esterification reaction, the temperature of the esterification kettle is raised to 230-250 ℃ by stirring, the internal pressure of the esterification kettle is controlled to 200-400 kPa, and the esterification is finished after 1-2 hours until the esterification rate reaches more than 90-99%.
9. The method for preparing a rapidly crystallized PET resin of nano-attapulgite copolymerized PEG according to claim 6, characterized in that: the pressure of the polycondensation kettle is-50 to-105 kPa, and the reaction temperature is 260 to 280 ℃ in the polymerization reaction.
10. A preparation method of rapid crystallization PET engineering plastic particles of nanometer attapulgite copolymerized PEG is characterized in that: comprises the steps of (a) preparing a substrate,
the rapidly crystallized PET resin of the nano-attapulgite copolymerized PEG according to any one of claims 1 to 5 and the glass fiber 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 rapidly crystallized PET engineering plastic particles are obtained after water cooling and dicing.
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