CN113512228A - General polyester high-power expanded bead and preparation method thereof - Google Patents
General polyester high-power expanded bead and preparation method thereof Download PDFInfo
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- CN113512228A CN113512228A CN202110601805.1A CN202110601805A CN113512228A CN 113512228 A CN113512228 A CN 113512228A CN 202110601805 A CN202110601805 A CN 202110601805A CN 113512228 A CN113512228 A CN 113512228A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005187 foaming Methods 0.000 claims abstract description 65
- 239000012530 fluid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
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- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 6
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides polyester expanded beads, wherein the expansion ratio of the polyester expanded beads is 20-40 times; the diameter of the cells of the polyester expanded beads is 50-150 mu m. The high-magnification polyester expanded bead has a specific structure, particularly, the expanded bead has a uniform cell structure from the center to the edge, and is an ultra-light material with excellent performance. In addition, the invention only adopts the polyester with the general grade as the raw material, namely the polyester expanded beads with high magnification which can be obtained. The preparation method provided by the invention adopts the supercritical fluid, combines a specific foaming process, has the advantages of simple process, low foaming temperature, short reaction time, environmental protection, easy control and high production efficiency, the prepared foaming beads meet the technical requirements of a steam forming process, the preparation method is a typical additive manufacturing process, the material utilization rate is up to more than 99 percent, a workpiece can be used for a long time at the temperature of-50-160 ℃, the application range is wide, and the preparation method is favorable for realizing industrial mass production and application.
Description
Technical Field
The invention belongs to the technical field of polyester expanded beads, relates to a polyester expanded bead and a preparation method thereof, and particularly relates to a general polyester high-power expanded bead and a preparation method thereof.
Background
The polyester resin is a general term for a high molecular compound obtained by polycondensation of a diol or a diacid or a polyol and a polyacid. The polyester resins are classified into saturated polyester resins and unsaturated polyester resins. The unsaturated polyester adhesive is mainly composed of unsaturated polyester resin, pigment and filler, initiator and other auxiliary agents. The adhesive has the advantages of small viscosity, easy wetting, good manufacturability, large hardness of a cured adhesive layer, good transparency, high brightness, capability of being pressurized and quickly cured at room temperature, good heat resistance and excellent electrical property. The defects are large shrinkage, low adhesive toughness, poor chemical medium resistance and water resistance, and the product is used for non-structural adhesives. The adhesive is mainly used for gluing glass fiber reinforced plastic, hard plastic, concrete, electric can sealing and the like. The foam plastic is an aggregate formed by dispersing gas in a solid polymer, and has the advantages of light weight, heat insulation, buffering, insulation, corrosion prevention, low price and the like. Therefore, the composite material is widely applied to daily necessities, packaging, industry, agriculture, transportation industry, military industry and aerospace industry. Particularly, EPP (expanded polypropylene) and polypropylene resin foaming materials emerging in recent years are high-crystalline polymer/gas composite materials with excellent performance, become the fastest-growing environment-friendly novel compression-resistant cushioning and heat-insulating materials at present, and are widely applied to the fields of automobiles, turnover boxes, houses and the like at present.
Polyethylene terephthalate (PET) resin is a large amount of general materials, has large yield and low cost, is widely applied to various fields of daily life, but common polyester has high crystallinity and low viscosity, the melt strength is sharply reduced after melting, and the common polyester cannot be directly made into a foaming material.
Therefore, how to find a suitable method to solve the above problems in the general polyester resin foaming technology of polyethylene terephthalate resins and to widen the application depth and width of polyester foamed materials has become one of the focuses of great concern of many research and development manufacturers and researchers at the same time.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyester expanded bead and a preparation method thereof, and particularly to a general polyester high-power expanded bead, wherein the polyester expanded bead provided by the present invention only uses general-grade polyester as a raw material, i.e. an available high-power, uniformly expanded polyester expanded bead; and the process is simple and easy to control, and is favorable for realizing industrial scale production and application.
The invention provides polyester expanded beads, wherein the expansion ratio of the polyester expanded beads is 20-40 times;
the diameter of the cells of the polyester expanded beads is 50-150 mu m.
Preferably, the polyester comprises a general purpose polyester resin;
the particle size of the polyester expanded beads is 2-8 mm;
the polyester expanded beads have a uniform cell distribution.
Preferably, the cells are of closed cell structure;
the polyester expanded beads are high-power expanded polyester beads;
the polyester expanded beads have a uniform cell structure from the center to the edge.
Preferably, the polyester comprises a polyethylene terephthalate resin;
the IV value of the polyethylene terephthalate resin is 0.8-1.2 dL/g;
the density of the polyester expanded beads is 30-60 kg/m3。
The invention provides a preparation method of polyester expanded beads, which comprises the following steps:
1) carrying out extrusion granulation and rapid cooling on polyester resin to obtain non-crystalline polyester particles;
2) placing the non-crystalline polyester particles obtained in the step into a die cavity at a certain temperature, filling a supercritical fluid, and obtaining a polymer-supercritical fluid homogeneous phase system after balancing;
3) and (3) decompressing and foaming the polymer-supercritical fluid homogeneous system obtained in the step to obtain the polyester foaming bead.
Preferably, the melt index of the polyester resin is 0.5-10 g/10 min;
the melt strength of the polyester resin is 1-10 cN;
the particle size of the polyester resin is 0.5-2.5 mm;
the polyester resin is dried polyester resin.
Preferably, a chain extender is also added into the polyester resin;
the mass ratio of the chain extender to the polyester resin is 0.15-0.4%;
the chain extender comprises polyfunctional acid anhydride or polyfunctional epoxy resin;
the water content of the polyester resin is less than or equal to 100 ppm;
the extrusion temperature is 250-270 ℃.
Preferably, the rapid cooling means includes water cooling;
the cooling temperature of the rapid cooling is less than or equal to 5 ℃;
the rapid cooling mode of the extrusion granulation comprises double-screw extrusion water-cooling brace granulation;
the certain temperature is 80-230 ℃;
the certain temperature is greater than the glass transition temperature of the polyester and less than the maximum crystallization temperature of the polyester.
Preferably, the total volume of the polyester resin accounts for 90-99% of the volume of the die cavity;
the supercritical fluid comprises supercritical N2And/or supercritical CO2；
The pressure of the supercritical fluid is 7.2-20 MPa;
the equilibrium includes the swelling penetration of the amorphous polyester particles to saturation by the supercritical fluid.
Preferably, the time for reaching the equilibrium is 15-30 min;
the pressure after the pressure relief foaming is normal pressure;
the pressure relief foaming is rapid pressure relief;
the pressure relief rate of the pressure relief foaming is 50-200 MPa/s.
The invention provides polyester expanded beads, wherein the expansion ratio of the polyester expanded beads is 20-40 times; the diameter of the cells of the polyester expanded beads is 50-150 mu m. Compared with the prior art, the invention is based on the research that the supercritical fluid (SCF, which refers to a fluid above the critical temperature and above the critical pressure) can be used for preparing the polymer foaming material by utilizing the advantages of high diffusion rate, high solubility and the like of the supercritical fluid in the polymer because the viscosity and the diffusion coefficient are close to gases, and the density and the solvation capacity are close to liquids, and the supercritical fluid foaming technology is clean in the whole foaming process and can not pollute the environment and foaming products.
The high-magnification polyester foaming bead prepared by the invention has a specific structure, the foaming magnification can reach 20-40 times, the pore diameter of the foaming bead is 50-150 mu m, and particularly, the foaming bead has a uniform cell structure from the center to the edge and is an ultra-light material with excellent performance. The polyester expanded bead provided by the invention only adopts general-grade polyester as a raw material, namely, the available high-magnification polyester expanded bead has the expansion magnification of 20-40 times, and is a structural material with excellent performance.
According to the polyester expanded bead and the preparation method thereof provided by the invention, the used polyester resin raw material is a general brand, a supercritical fluid is adopted, a specific foaming process is combined, the process is simple, the foaming temperature is low, the reaction time is short, the environment is protected, the control is easy, the production efficiency is high, the prepared expanded bead meets the technical requirements of a steam forming process, the process is a typical additive manufacturing process, the material utilization rate is up to more than 99%, a workpiece can be used for a long time at the temperature of-50-160 ℃, and the invention can be used for preparing high-power expanded polyester beads, is wide in application range and is beneficial to realizing industrial scale production and application. The polyester expanded beads prepared by the method have similar appearance and use as EPP, have more excellent performance, have the compression strength 2-4 times of that of EPP, and have a prospect of replacing EPP in the future.
Experimental results show that by adopting the preparation method provided by the invention and combining the production process of amorphous modification-direct pressure relief foaming, the foaming of the general polyester resin with the melt index of 0.5-5 g/10min and the melt strength of 1-10 cN can be realized; the whole reaction time is short for 15-30 min, and the production efficiency is high. The diameter of the foam hole of the prepared foaming particle is 50-150 mu m smaller; the foaming multiplying power is high and reaches 20-40 times; the mechanical property is high, and the compressive strength is as high as 0.8 MPa; is a structural foam material with ultra-light weight and excellent performance.
Drawings
FIG. 1 is a scanning electron micrograph of a cut surface of polyester expanded beads prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a cut surface of the polyester expanded beads prepared in example 1 of the present invention;
FIG. 3 is a SEM photograph of a cut surface of the polyester expanded beads prepared in example 2 of the present invention;
FIG. 4 is a SEM photograph of a cut surface of the polyester expanded beads prepared in example 2 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the field of analytical purification or preparation of polyester foamed materials.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides polyester expanded beads, wherein the expansion ratio of the polyester expanded beads is 20-40 times;
the diameter of the cells of the polyester expanded beads is 50-150 mu m.
In the present invention, the polyester expanded beads are high-expansion polyester beads. The foaming ratio of the polyester expanded beads is 20 to 40 times, preferably 22 to 38 times, more preferably 25 to 35 times, and still more preferably 28 to 32 times.
In the invention, the diameter of the foam hole of the polyester expanded bead is 50-150 μm, preferably 70-130 μm, and more preferably 90-110 μm.
In the present invention, the polyester expanded beads have a porous structure. In particular, the cells are preferably of closed cell structure.
In the present invention, the polyester expanded beads are preferably high-expansion polyester beads.
In the present invention, the polyester expanded beads preferably have a uniform cell distribution. In particular, the polyester expanded beads preferably have a uniform cell structure from the center of the beads to the edge of the beads. I.e., the polyester expanded beads have a uniform cell distribution throughout.
In the invention, the particle size of the polyester expanded bead is preferably 2-8 mm, more preferably 3-7 mm, and more preferably 4-6 mm.
In the present invention, the density of the polyester expanded beads is preferably 30 to 60kg/m3More preferably 35 to 55kg/m3More preferably 40 to 50kg/m3。
In the present invention, the polyester preferably includes general-purpose polyester resins. Specifically, a polyethylene terephthalate resin may be used.
In the present invention, the IV value of the polyethylene terephthalate resin is preferably 0.8 to 1.2dL/g, more preferably 0.85 to 1.15dL/g, more preferably 0.9 to 1.1dL/g, and more preferably 0.95 to 1.05 dL/g. Specifically, the IV value is preferably measured with a 6:4 mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at 30 ℃ using an Ubbelohde viscometer.
In the present invention, in order to increase the IV value of the polyethylene terephthalate resin, it is preferable that a chain extender is further included in the polyester resin.
The invention provides a preparation method of polyester expanded beads, which comprises the following steps:
1) carrying out extrusion granulation and rapid cooling on polyester resin to obtain non-crystalline polyester particles;
2) placing the non-crystalline polyester particles obtained in the step into a die cavity at a certain temperature, filling a supercritical fluid, and obtaining a polymer-supercritical fluid homogeneous phase system after balancing;
3) and (3) decompressing and foaming the polymer-supercritical fluid homogeneous system obtained in the step to obtain the polyester foaming bead.
The invention firstly extrudes and granulizes polyester resin and rapidly cools the polyester resin to obtain non-crystalline polyester particles.
In the invention, the melt index of the polyester resin is preferably 0.5-5 g/10min, more preferably 1.5-4 g/10min, and more preferably 2.5-3 g/10 min. Wherein the melt index MI is measured with a 2.16kg weight at 190 ℃.
In the invention, the melt strength of the polyester resin is preferably 1 to 10cN, more preferably 3 to 8cN, and more preferably 5 to 6 cN.
In the present invention, the particle size of the polyester resin is preferably 0.5 to 2.5mm, more preferably 0.8 to 2.3mm, more preferably 1.0 to 2.0mm, and more preferably 1.2 to 1.8 mm.
In the present invention, the polyester resin is preferably a dried polyester resin.
In the present invention, the moisture content of the polyester resin is preferably 100ppm or less.
In the present invention, a chain extender is preferably further added to the polyester resin. Specifically, the chain extender preferably includes a polyfunctional acid anhydride or a polyfunctional epoxy resin.
In the present invention, the mass ratio of the chain extender to the polyester resin is preferably 0.15% to 0.4%, more preferably 0.2% to 0.35%, and still more preferably 0.25% to 0.3%.
The invention selects general polyester, polyethylene glycol terephthalate resin, and IV value is 0.8-1.2 dL/g (detected by using 6:4 mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at 30 ℃ by using Ubbelohde viscometer). In the invention, the IV value is lower than 0.8dL/g, the melt strength is low, and the bubbles are easy to collapse and merge and cannot be foamed smoothly; IV value is higher than 1.2dL/g, bubble growth is difficult, and high-rate foaming can not be realized. The IV value of common polyester is between 0.6 and 0.8dL/g, and the common polyester cannot be directly used for foaming and needs further tackifying modification. In the extrusion melting process, 0.15-0.4% of chain extender is added, the chain extender is polyfunctional acid anhydride or polyfunctional epoxy, and the IV value of the general polyester is adjusted to be 0.8-1.2 dL/g. And (3) granulating by water bracing, controlling the water temperature in a cooling water tank to be 5 ℃, and quickly cooling to inhibit crystallization of polyester to prepare the non-crystalline to-be-foamed particles with the particle size of 1-2 mm.
In the invention, the extrusion temperature is preferably 250-270 ℃, more preferably 254-266 ℃, and more preferably 258-262 ℃.
In the present invention, the rapid cooling means preferably includes water cooling.
In the present invention, the cooling temperature of the rapid cooling is preferably 5 ℃ or less.
In the present invention, the extrusion granulation rapid cooling mode preferably comprises twin-screw extrusion water-cooling strand granulation.
The invention adopts the polyester resin with the water content of less than 100ppm after vacuum drying, and the polyester resin is extruded and granulated by a double-screw extruder, and 0.15 to 0.4 percent of chain extender is added in the extrusion and melting process. The temperature of the feeding section of the extruder is preferably 250-260 ℃ (more preferably 252-258 ℃, more preferably 254-256 ℃), the temperature of the melting section is preferably 260-265 ℃ (more preferably 261-264 ℃, more preferably 262-263 ℃), the temperature of the homogenizing section is preferably 265-270 ℃ (more preferably 266-279 ℃, more preferably 267-268 ℃), and the temperature of the die is preferably 270 ℃. The method comprises the steps of granulating by water bracing, controlling the temperature of cooling water by a refrigerator, wherein the temperature of the cooling water is less than 5 ℃, and inhibiting crystallization of polyester by a rapid cooling process, thereby preparing amorphous polyester granules with the grain diameter of preferably 1-2 mm (more preferably 1.2-1.8 mm, and more preferably 1.4-1.6 mm).
Placing the non-crystalline polyester particles obtained in the above-mentioned step into a mould cavity at a certain temp., filling supercritical fluid, after equilibrium is reached, obtaining polymer-supercritical fluid homogeneous phase system
In the invention, the certain temperature is preferably 80-230 ℃, more preferably 100-210 ℃, more preferably 120-190 ℃, and more preferably 140-170 ℃. Specifically, the temperature can be 120-160 ℃. In particular, the certain temperature is preferably greater than the glass transition temperature of the polyester and less than the maximum crystallization temperature of the polyester.
In the invention, the selection principle of a certain temperature (T1) is that the glass transition temperature Tg of the polyester is higher than, and the maximum crystallization temperature of the polyester is lower than, so that on one hand, the rapid permeation of the supercritical fluid can be ensured, and on the other hand, the crystallinity of the polyester is low, the dissolution amount of the supercritical fluid is large, and further, the high foaming is realized.
In the present invention, the ratio of the total volume of the polyester resin to the volume of the cavity is preferably 90% to 99%, more preferably 92% to 97%, and still more preferably 94% to 95%.
In the present invention, the supercritical fluid preferably includes supercritical N2And/or supercritical CO2More preferably supercritical N2Or supercritical CO2。
In the invention, the pressure of the supercritical fluid is preferably 7.2-20 MPa, more preferably 10-17 MPa, and more preferably 13-16 MPa.
In the present invention, the equilibrium preferably includes the penetration of the amorphous polyester particles into saturation by swelling with the supercritical fluid.
In the invention, the time for reaching the equilibrium is preferably 15-30 min, more preferably 18-27 min, and more preferably 21-24 min.
Finally, decompressing and foaming the polymer-supercritical fluid homogeneous system obtained in the step to obtain the polyester foaming bead.
In the present invention, the pressure after the pressure-releasing foaming is preferably normal pressure.
In the present invention, the pressure relief foaming is preferably rapid pressure relief.
In the invention, the pressure relief rate of the pressure relief foaming is preferably 50-200 MPa/s, more preferably 80-170 MPa/s, and more preferably 110-140 MPa/s.
The invention selects rapid pressure relief to normal pressure, when the pressure relief rate is lower than 50MPa/s, especially lower than 20MPa/s, the quantity of gas nuclei formed by breaking a homogeneous equilibrium state is small, the quantity of foam pores of the obtained foaming material is small, and the foam pores are easy to grow and form defects. When the pressure relief rate is higher than 200MPa/s, the number of gas nuclei is large, the diameter of bubbles is small, the diameter of cells is small, and the foaming ratio is low.
The invention is a complete and refined integral preparation scheme, better ensures the foaming rate and the appearance of the polyester beads, and improves the performance of the polyester beads, and the preparation method of the polyester expanded beads can specifically comprise the following steps:
1) extruding and granulating general polyester resin, and rapidly cooling to prepare non-crystalline particles;
2) placing amorphous polyester particles in a container with a constant temperature T1 (a certain temperature), filling supercritical fluid for permeation and swelling to reach an equilibrium state, and forming a polymer-supercritical fluid homogeneous phase system;
3) after the balance is achieved, the pressure is quickly released to 0 (normal pressure), and the polyester particles are foamed and expanded to obtain polyester foamed beads with the diameter of 50-150 mu m of cells and the foaming ratio of 20-40 times.
The high-magnification polyester expanded bead has a specific structure, the expansion ratio can reach 20-40 times, the pore diameter of the expanded bead is 50-150 mu m, particularly the expanded bead has a uniform cell structure from the center to the edge, and the expanded bead is an ultra-light material with excellent performance. The polyester expanded bead provided by the invention only adopts general-grade polyester as a raw material, namely, the available high-magnification polyester expanded bead has the expansion magnification of 20-40 times, and is a structural material with excellent performance.
According to the polyester expanded bead and the preparation method thereof provided by the invention, the used polyester resin raw material is a general brand, a supercritical fluid is adopted, a specific foaming process is combined, the process is simple, the foaming temperature is low, the reaction time is short, the environment is protected, the control is easy, the production efficiency is high, the prepared expanded bead meets the technical requirements of a steam forming process, the process is a typical additive manufacturing process, the material utilization rate is up to more than 99%, a workpiece can be used for a long time at the temperature of-50-160 ℃, and the invention can be used for preparing high-power expanded polyester beads, is wide in application range and is beneficial to realizing industrial scale production and application. The polyester expanded beads prepared by the method have similar appearance and use as EPP, have more excellent performance, have the compression strength 2-4 times of that of EPP, and have a prospect of replacing EPP in the future.
Experimental results show that by adopting the preparation method provided by the invention and combining the production process of amorphous modification-direct pressure relief foaming, the foaming of the general polyester resin with the melt index of 0.5-5 g/10min and the melt strength of 1-10 cN can be realized; the whole reaction time is short for 15-30 min, and the production efficiency is high. The diameter of the foam hole of the prepared foaming particle is 50-150 mu m smaller; the foaming multiplying power is high and reaches 20-40 times; the mechanical property is high, and the compressive strength is as high as 0.8 MPa; is a structural foam material with ultra-light weight and excellent performance.
In order to further illustrate the present invention, the following will describe a polyester expanded bead and a method for preparing the same in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
The examples select general polyester, polyethylene glycol terephthalate resin, fiber grade polyester chip initial IV value 0.6 ~ 0.7dL/g, bottle grade resin chip initial IV value 0.7 ~ 0.8dL/g, use Ubbelohde viscometer at 30 ℃ with phenol and 1,1,2, 2-tetrachloroethane 6:4 mixed solvent to detect, chain extender adopts pyromellitic dianhydride (PMDA) or isocyanuric acid triglycidyl ester (TGIC), in the twin screw extruder direct melt reaction extrusion.
Example 1
Firstly, fiber grade polyester chips and a chain extender are dried for more than 4 hours at 80 ℃ in vacuum, and the water content is controlled to be less than 100 ppm.
Then, extruding and granulating through a double-screw extruder, wherein the feeding section of the extruder is 250-260 ℃, the melting section is 260-265 ℃, the homogenizing section is 265-270 ℃ and the neck mold is 270 ℃. In the extrusion melting process, 0.35-0.4% of pyromellitic dianhydride (PMDA) is added, and the IV value of the polyester is controlled to be 1.0-1.2 dL/g. Granulating by water drawing to obtain non-crystalline foaming granule with particle diameter of 1mm, wherein the cooling water temperature is lower than 5 deg.C, and rapid cooling is used to inhibit crystallization.
Then, placing the particles to be foamed in a high-pressure container with constant temperature of T1, replacing air, charging supercritical carbon dioxide, and swelling and permeating for 30min to saturation at the supercritical pressure of 16MPa and the temperature of T1 of 160 ℃.
Then, quickly relieving the pressure in the high-pressure container from 16MPa to 0 at the pressure relief rate of 200MPa/s, foaming and expanding the polyester particles to obtain the polyester resin with the bulk density of 30kg/m3The expanded beads of (2) were expanded 40 times with respect to the original beads, and scanning electron micrographs of the sections of the expanded beads are shown in FIGS. 1 and 2.
Referring to FIG. 1, FIG. 1 is a scanning electron micrograph of a cut surface of the polyester expanded beads prepared in example 1 of the present invention.
Referring to FIG. 2, FIG. 2 is a scanning electron micrograph of a cut surface of the polyester expanded beads prepared in example 1 of the present invention.
As can be seen from FIGS. 1 and 2, the cell diameter is 50 to 100 μm.
Example 2
First, the bottle grade polyester chip and the chain extender were dried for use by the drying method of example 1.
Then, the mixture is extruded and granulated by a double-screw extruder, the extrusion process of the example 1 is adopted, and 0.15 to 0.18 percent of triglycidyl isocyanurate (TGIC) is added in the melting process, so that the IV value of the polyester is controlled to be 0.8 to 1.0 dL/g. Granulating by water drawing to obtain non-crystalline foaming granule with particle size of 2mm, wherein the cooling water temperature is lower than 5 deg.C, and rapid cooling is used to inhibit crystallization.
Then, placing the particles to be foamed in a high-pressure container with constant temperature of T1, replacing air, charging supercritical carbon dioxide, and swelling and permeating for 45min to saturation at the supercritical fluid pressure of 13MPa and the temperature of T1 of 120 ℃.
Then, quickly relieving the pressure in the high-pressure container from 13MPa to 0 at the pressure relief rate of 50MPa/s, foaming and expanding the polyester particles to obtain the polyester resin with the bulk density of 60kg/m3Foaming ofThe beads, which are 20 times expanded relative to the original particles, are shown in FIG. 3 and FIG. 4 as scanning electron micrographs of the sections of the expanded beads.
Referring to FIG. 3, FIG. 3 is a scanning electron micrograph of a cut surface of the polyester expanded beads prepared in example 2 of the present invention.
Referring to FIG. 4, FIG. 4 is a scanning electron micrograph of a cut surface of the polyester expanded beads prepared in example 2 of the present invention.
As can be seen from FIGS. 3 and 4, the cell diameter is between 100 and 150 μm.
Example 3
First, the fiber grade polyester chip and the chain extender were dried for use by the drying method of example 1.
Then, the mixture was extruded and pelletized by a twin-screw extruder, and 0.2 to 0.25% of pyromellitic dianhydride (PMDA) was added during the melting by the extrusion process of example 1 to control the IV value of the polyester to 0.9 to 1.1 dL/g. Granulating by water drawing to obtain non-crystalline foaming granule with particle diameter of 1.5mm, wherein the cooling water temperature is lower than 5 deg.C, and rapid cooling is used to inhibit crystallization.
Then, the particles to be foamed are placed in a high-pressure container with constant temperature of T1, air is replaced, and then 1:5 supercritical N is filled2And CO2The supercritical fluid pressure is 15MPa, the temperature T1 is 150 ℃, and the swelling and infiltration are carried out for 40min to saturation.
Then, quickly relieving the pressure in the high-pressure container from 15MPa to 0 at the pressure relief rate of 100MPa/s, foaming and expanding the polyester particles to obtain the polyester granules with the bulk density of 35kg/m3Expanded beads, expanded 36 times with respect to the original particles.
The foaming beads are put under the steam pressure of 4.5kg to prepare a formed foaming plate with the density of 40kg/m3And the compression strength under 50% deformation is measured to be 0.5MPa, which is far higher than that of EPP under the same density.
Example 4
First, bottle grade polyester chips and a chain extender were dried for use by the drying method of example 1.
Then, the mixture is extruded and granulated by a double-screw extruder, the extrusion process of the example 1 is adopted, and 0.25 to 0.3 percent of triglycidyl isocyanurate (TGIC) is added in the melting process, so that the IV value of the polyester is controlled to be 1.1 to 1.2 dL/g. Granulating by water drawing to obtain non-crystalline foaming granule with particle size of 2mm, wherein the cooling water temperature is lower than 5 deg.C, and rapid cooling is used to inhibit crystallization.
Then, the particles to be foamed are placed in a high-pressure container with constant temperature of T1, air is replaced, and then 5:1 supercritical N is filled2And CO2Supercritical carbon dioxide with supercritical fluid pressure of 14MPa and temperature T1 selected at 145 deg.C, and swelling and permeating for 30min to saturation.
Then, quickly relieving the pressure in the high-pressure container from 14MPa to 0 at the pressure relief rate of 150MPa/s, foaming and expanding the polyester particles to obtain the polyester resin with the bulk density of 50kg/m3Expanded beads, expanded by a factor of 25 with respect to the original particles.
The foaming beads are molded in hot air at 180 ℃ to prepare a foaming plate with the density of 55kg/m3And the compression strength under 50% deformation is measured to be 0.8MPa, which is far higher than that of EPP under the same density.
Comparative example 1
Comparative example 1 is a comparative example to example 1, and the foaming effect was observed by increasing the crystallinity of the polyester.
Firstly, fiber grade polyester chips and a chain extender are dried for more than 4 hours at 80 ℃ in vacuum, and the water content is controlled to be less than 100 ppm.
Then, extruding and granulating through a double-screw extruder, wherein the feeding section of the extruder is 250-260 ℃, the melting section is 260-265 ℃, the homogenizing section is 265-270 ℃ and the neck mold is 270 ℃. In the extrusion melting process, 0.35-0.4% of pyromellitic dianhydride (PMDA) is added, and the IV value of the polyester is controlled to be 1.0-1.2 dL/g. Granulating by water drawing to obtain non-crystalline foaming granule with particle diameter of 1mm, wherein the cooling water temperature is lower than 5 deg.C, and rapid cooling is used to inhibit crystallization.
Then, the amorphous polyester particles are placed in an electrothermal blowing dry box at 120 ℃, fully crystallized for 4 hours and taken out for standby.
Then, the crystallized polyester particles are placed in a high-pressure container with a constant temperature of T1, supercritical carbon dioxide is filled after air is replaced, the supercritical fluid pressure is 16MPa, the temperature T1 is selected to be 160 ℃, and swelling and infiltration are carried out for 30 min.
And then, quickly relieving the pressure in the high-pressure container from 16MPa to 0 at the pressure relief rate of 200MPa/s, wherein the polyester particles are not foamed and the foamed beads cannot be prepared.
The above tests are repeated, and the swelling and permeation time is prolonged to be more than 24h, so that the foaming beads cannot be prepared.
The general polyester high power expanded beads provided by the present invention and the preparation method thereof are described in detail above, and the principle and embodiments of the present invention are explained herein by using specific examples, which are only used to help understand the method of the present invention and the core idea thereof, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any method in combination. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A polyester expanded bead is characterized in that the expansion ratio of the polyester expanded bead is 20-40 times;
the diameter of the cells of the polyester expanded beads is 50-150 mu m.
2. The polyester expanded beads according to claim 1, wherein the polyester comprises a general-purpose polyester resin;
the particle size of the polyester expanded beads is 2-8 mm;
the polyester expanded beads have a uniform cell distribution.
3. The polyester expanded bead according to claim 1, wherein the cells have a closed cell structure;
the polyester expanded beads are high-power expanded polyester beads;
the polyester expanded beads have a uniform cell structure from the center to the edge.
4. The polyester expanded bead according to claim 1, wherein the polyester comprises a polyethylene terephthalate resin;
the IV value of the polyethylene terephthalate resin is 0.8-1.2 dL/g;
the density of the polyester expanded beads is 30-60 kg/m3。
5. A preparation method of polyester expanded beads is characterized by comprising the following steps:
1) carrying out extrusion granulation and rapid cooling on polyester resin to obtain non-crystalline polyester particles;
2) placing the non-crystalline polyester particles obtained in the step into a die cavity at a certain temperature, filling a supercritical fluid, and obtaining a polymer-supercritical fluid homogeneous phase system after balancing;
3) and (3) decompressing and foaming the polymer-supercritical fluid homogeneous system obtained in the step to obtain the polyester foaming bead.
6. The method according to claim 5, wherein the polyester resin has a melt index of 0.5 to 10g/10 min;
the melt strength of the polyester resin is 1-10 cN;
the particle size of the polyester resin is 0.5-2.5 mm;
the polyester resin is dried polyester resin.
7. The production method according to claim 4, wherein a chain extender is further added to the polyester resin;
the mass ratio of the chain extender to the polyester resin is 0.15-0.4%;
the chain extender comprises polyfunctional acid anhydride or polyfunctional epoxy resin;
the water content of the polyester resin is less than or equal to 100 ppm;
the extrusion temperature is 250-270 ℃.
8. The method of claim 4, wherein the rapid cooling means comprises water cooling;
the cooling temperature of the rapid cooling is less than or equal to 5 ℃;
the rapid cooling mode of the extrusion granulation comprises double-screw extrusion water-cooling brace granulation;
the certain temperature is 80-230 ℃;
the certain temperature is greater than the glass transition temperature of the polyester and less than the maximum crystallization temperature of the polyester.
9. The preparation method according to claim 4, wherein the proportion of the total volume of the polyester resin to the volume of the cavity is 90-99%;
the supercritical fluid comprises supercritical N2And/or supercritical CO2；
The pressure of the supercritical fluid is 7.2-20 MPa;
the equilibrium includes the swelling penetration of the amorphous polyester particles to saturation by the supercritical fluid.
10. The method according to claim 4, wherein the time to reach equilibrium is 15 to 30 min;
the pressure after the pressure relief foaming is normal pressure;
the pressure relief foaming is rapid pressure relief;
the pressure relief rate of the pressure relief foaming is 50-200 MPa/s.
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| CN114374038A (en) * | 2022-03-22 | 2022-04-19 | 浙江阿莱西澳智能装备科技有限公司 | Carbon fiber composite material for new energy automobile chassis structure and battery pack tray |
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