CN115181319A - Preparation method of polyphenyl ether foamable particles - Google Patents

Preparation method of polyphenyl ether foamable particles Download PDF

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Publication number
CN115181319A
CN115181319A CN202210947368.3A CN202210947368A CN115181319A CN 115181319 A CN115181319 A CN 115181319A CN 202210947368 A CN202210947368 A CN 202210947368A CN 115181319 A CN115181319 A CN 115181319A
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polyphenyl ether
ether composition
polyphenylene ether
polyphenyl
parts
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CN115181319B (en
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信春玲
何亚东
任峰
乔世泽
郭梦浩
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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
    • 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
    • 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
    • C08J9/14—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 organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/14—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 organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of polyphenyl ether foamable particles, which comprises the following steps: s1, adding a polyphenyl ether composition into an extruder for melting and plasticizing to obtain a polyphenyl ether composition melt, wherein the polyphenyl ether composition comprises, by weight, 20-90 parts of polyphenyl ether, 10-80 parts of styrene-based polymer, 0-10 parts of flame retardant, 0.1-0.3 part of antioxidant, 0.5-3 parts of foam cell nucleating agent and 0.5-3 parts of lubricant; s2, injecting a physical foaming agent into the melt of the polyphenyl ether composition and uniformly mixing to form a homogeneous polyphenyl ether solution; s3, reducing the temperature of the homogeneous polyphenylene ether solution to a temperature 40-60 ℃ above the Tg of the polyphenylene ether composition; and S4, extruding the cooled polyphenyl ether composition melt, and quickly cooling/drawing, drying and granulating to obtain polyphenyl ether foamable particles with the diameter of less than or equal to 1mm. The method has the advantages of high production efficiency, low cost, small particle size, good heat resistance of molded products and high mechanical property, and the prepared polyphenyl ether foamable particles can be processed into products with various shapes by adopting a conventional foamable bead molding method.

Description

Preparation method of polyphenyl ether foamable particles
Technical Field
The invention relates to the field of material processing, in particular to a preparation method of polyphenyl ether foamable particles.
Background
Polyphenylene oxide has excellent heat resistance, flame retardance and dimensional stability, and is an engineering plastic with excellent performance. Through foaming processing, the light weight of the polyphenyl ether can be realized, and unique functionality such as heat insulation, sound insulation, buffering performance and low dielectric performance is endowed to the material. The expandable beads can be expanded and bonded together in the heating process, can be processed into expanded products with various shapes and structures, and can be widely applied to the fields of buffer packaging, building heat preservation, cold-chain logistics, toys and the like. The polyphenyl ether foamable bead has excellent heat resistance and dimensional stability, and has wide application fields in the fields of automobiles, new energy batteries, precision instruments and the like.
In the prior art, there are two processes for preparing expandable beads of polymers: 1) Melting and mixing a polymer and an additive, extruding and hot-cutting or water-cooling, drawing strips and cutting granules to prepare unfoamed particles, putting the unfoamed particles into an autoclave containing dispersion liquid, introducing a foaming agent, saturating for a certain time at a certain temperature and under a certain pressure, then decompressing and foaming, and washing and drying to obtain polymer foamable beads; 2) And mixing the polymer and the additive, adding the mixture into an extruder, injecting a foaming agent into a polymer melt in the extruder, uniformly mixing, cooling, extruding, and underwater pelletizing to obtain the foamable polymer beads. The polymer expandable bead can be expanded and welded for the second time to form a foamed product after being heated.
CN201711098090.2 discloses a functional expandable/expanded polystyrene bead and a preparation method thereof, wherein an extrusion method is adopted, a polymer melt and a foaming agent are uniformly mixed, and the mixture is extruded and expanded by a second-order cooling extruder, and is subjected to underwater granulation to prepare the expandable bead or the expanded bead. By adopting an underwater pelletizing method, too low water temperature can cause cooling of a machine head, and the pressure of the machine head rises rapidly, so that materials with lower viscosity can be processed usually, particularly, a polyphenyl ether resin system with extremely sensitive viscosity to temperature is not suitable for processing, and in addition, foamed beads with larger size are not suitable for molding products with high dimensional precision requirement.
JP2013082865A discloses a method of preparing expandable polystyrene resin particles and a molded article prepared therefrom. Adding polystyrene resin, liquid paraffin, aromatic hydrocarbon and nucleating agent into an extruder, melting and mixing uniformly, then injecting a foaming agent into a polymer melt of the extruder, mixing uniformly, extruding through a machine head with multiple holes, quickly entering cooling water, and carrying out underwater granulation to prepare expandable polystyrene resin particles. The addition of low molecular weight liquid paraffin and aromatic hydrocarbon can increase the fluidity of polystyrene and improve the secondary expansion ratio, but the addition of small molecular weight lubricant can reduce the modulus and heat resistance of the foamed product.
CN202111674095.1 discloses a method for preparing a modified polyphenylene ether foamed bead molding, which comprises the following steps: granulating modified polyphenyl ether raw material resin by an extruder to obtain modified polyphenyl ether particles, filling the modified polyphenyl ether particles into a forming die, locking the die, putting the die into an autoclave for gas saturation, decompressing the autoclave, cooling the forming die, and opening the die to obtain a modified polyphenyl ether foaming bead forming body. The process method is an intermittent foaming process, and has the advantages of long production period, low efficiency and higher cost.
Therefore, the prior polymer expandable bead has the problems of long production period, low mechanical property of expandable bead molded products, low temperature resistance and the like.
Disclosure of Invention
The invention provides a preparation method of polyphenyl ether foamable particles, which solves the technical problems of long production cycle of polymer foamable beads, low mechanical property of foamable bead molding products and low temperature resistance.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the preparation method of the polyphenyl ether foamable particle comprises the following steps: s1, adding a polyphenyl ether composition into an extruder for melting and plasticizing to obtain a polyphenyl ether composition melt, wherein the polyphenyl ether composition comprises, by weight, 20-90 parts of polyphenyl ether, 10-80 parts of styrene-based polymer, 0-10 parts of flame retardant, 0.1-0.3 part of antioxidant, 0.5-3 parts of foam cell nucleating agent and 0.5-3 parts of lubricant; s2, injecting a physical foaming agent into the polyphenyl ether composition melt and uniformly mixing to form a polyphenyl ether composition melt containing the foaming agent; s3, reducing the temperature of the polyphenyl ether composition melt containing the foaming agent to a temperature 40-60 ℃ above the glass transition temperature of the polyphenyl ether composition to obtain a cooled polyphenyl ether composition melt containing the foaming agent; and S4, extruding the cooled polyphenyl ether composition melt containing the foaming agent through a plurality of round holes of an extrusion die on a machine head, rapidly cooling, and then drawing, drying and granulating to obtain polyphenyl ether foamable particles with the diameter of less than or equal to 1mm.
Preferably, in the method for preparing the polyphenylene ether expandable fine particles, the intrinsic viscosity of the polyphenylene ether is 35 to 50mL/g.
Preferably, in the above method for producing expandable fine particles of polyphenylene ether, the styrene-based polymer is at least one of polystyrene, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene-styrene block copolymer, and hydrogenated styrene-butadiene-styrene.
Preferably, in the above method for producing expandable fine particles of polyphenylene ether, the flame retardant is at least one of tricresyl phosphate, resorcinol-bis-diphenyl phosphate, liquid tetraphenyl bisphenol a diphosphate, and solid tetraphenyl bisphenol a diphosphate.
Preferably, in the preparation method of the polyphenyl ether foamable particles, the foam cell nucleating agent is talcum powder and SiO 2 At least one of calcium carbonate, wollastonite, sepiolite and nano calcium silicate.
Preferably, in the preparation method of the polyphenylene ether foamable particle, the lubricant is at least one of zinc stearate, calcium stearate, pentaerythritol stearate, stearic acid amide, glyceryl monostearate, erucamide, ethylene bis stearic acid amide, hyperbranched compound and polytetrafluoroethylene.
Preferably, in the above method for preparing the polyphenylene ether foamable fine particles, the physical blowing agent is n-butane, isobutane, n-pentane, isopentane, cyclopentane, cyclohexane, heptane, ethanol, 1, 2-tetrafluoroethane (HFC-134 a), 1-difluoroethane (HFC-152 a), trans 1-3, 3-tetrafluoropropene (HFO-1234 ze), trans 1-chloro-3, 3-trifluoropropene (HCFO), CO 2 、H 2 At least one of O.
Preferably, in the preparation method of the polyphenylene ether foamable particle, in step S4, the cooled polyphenylene ether composition melt is extruded through a plurality of circular holes of an extrusion die on a machine head, immediately enters a cooling water tank for rapid cooling, is pulled by a tractor and dried by an air-cooled drying device, and enters a granulator for granulation, wherein the diameter of the circular hole is less than or equal to 2mm, and the melt pressure at the extrusion die on the machine head is greater than or equal to 5Mpa.
Preferably, in the above method for producing expandable fine particles of polyphenylene ether, T g The temperature of cooling water is more than or equal to minus 130 ℃ and less than or equal to T g _ At 100 ℃ wherein T g Is the glass transition temperature of the polyphenylene ether composition.
Preferably, in the above method for producing expandable fine particles of polyphenylene ether, in step S4, the take-off line speed is 1.5 to 20 times the extrusion line speed.
The beneficial effects of the invention are as follows:
the preparation method of the polyphenyl ether foamable particle adopts polyphenyl ether resin as a main raw material, utilizes the rule that the viscoelasticity of the polyphenyl ether resin is changed rapidly along with the temperature, has the advantages of high production efficiency, low cost, small size of the foamable particle, good heat resistance of a molded product, high mechanical property and the like, and has wide application prospect in precision instruments, thin-wall products and new energy power battery heat management systems; the polyphenyl ether foamable particle prepared by the method can be processed into products with various shapes by adopting a conventional foamable bead molding method.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below.
FIG. 1 is a flow chart of a method for preparing expandable fine particles of polyphenylene ether according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
As shown in FIG. 1, the method for preparing expandable fine particles of polyphenylene ether of the present invention comprises the steps of:
s1, adding the polyphenyl ether composition into an extruder for melting and plasticizing to obtain a polyphenyl ether composition melt, wherein the polyphenyl ether composition comprises, by weight, 20-90 parts of polyphenyl ether, 10-80 parts of styrene-based polymer, 0-10 parts of flame retardant, 0.1-0.3 part of antioxidant, 0.5-3 parts of foam cell nucleating agent and 0.5-3 parts of lubricant.
Wherein, poly 2, 6-dimethyl-1, 4-phenyl ether, called polyphenylene oxide (PPO) for short, the characteristic viscosity is 35-50 mL/g, and one or more polyphenylene oxide resins with intrinsic viscosity can be selected; the styrene-based polymer is at least one of polystyrene, high Impact Polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), and hydrogenated styrene-butadiene-styrene (SEBS), and is preferably polystyrene or high impact polystyrene.
The flame retardant is microcapsule-coated red phosphorus or organic phosphate flame retardant, and is at least one of tricresyl phosphate, resorcinol-bis-diphenyl phosphate (RDP), liquid tetraphenyl bisphenol A diphosphate or solid tetraphenyl bisphenol A diphosphate. Magnesium hydroxide, mica, antimony trioxide, nano montmorillonite or organic silicon resin, expandable graphite and the like can also be added as auxiliary flame retardants, and the addition amount of the auxiliary flame retardants is 0-20wt% of the polyphenylene oxide resin composition. The addition of the flame retardant improves the flame retardance of the polyphenyl ether.
The antioxidant is at least one of hindered phenol antioxidant, phosphite antioxidant and thioester antioxidant. The hindered phenol antioxidant is tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010), the phosphite ester antioxidant is phosphite ester (2, 4-di-tert-butylphenyl) ester (antioxidant 168), the sulfate antioxidant is dilauryl thiodipropionate (antioxidant DLTP), and the antioxidant can be added with a high-efficiency carbon free radical trapping agent (antioxidant 136).
The foam cell nucleating agent is talcum powder and SiO 2 At least one of calcium carbonate, wollastonite, sepiolite and nano calcium silicate, and the foam cell nucleating agent is preferably nano SiO surface treated by silane coupling agent 2 Or nano silicic acid.
The lubricant is at least one of zinc stearate, calcium stearate, pentaerythritol stearate, stearic acid amide, glyceryl monostearate, erucamide, ethylene bis stearic acid amide, hyperbranched compound and polytetrafluoroethylene. The addition of the lubricant can reduce the adhesion of the polyphenylene ether on the metal wall surface in the extruder, reduce the shear heat generation, reduce the modulus of the polyphenylene ether composition and increase the foaming ratio during molding foaming. The addition amount of the lubricant is less than 0.5wt% of the polyphenylene ether resin composition and does not exert the above-mentioned effects, and the addition amount of more than 3wt% may greatly reduce the melt viscosity, fail to build the head pressure, or may cause a large number of cells to be broken and merged at the time of secondary foaming.
S2, injecting a physical foaming agent into the polyphenyl ether composition melt, and uniformly mixing the physical foaming agent with the polyphenyl ether composition melt under the action of a screw rod to form the polyphenyl ether composition melt containing the foaming agent.
Physical blowing agents are n-butane, isobutane, n-pentane, isopentane, cyclopentane, cyclohexane, heptane, ethanol, 1, 2-tetrafluoroethane (HFC-134 a), 1-difluoroethane (HFC-152 a), trans 1-3, 3-tetrafluoropropene (HFO-1234 ze), trans 1-chloro-3, 3-trifluoropropene (HCFO), CO 2 、H 2 At least one of O. The addition amount of the physical foaming agent is 1-20wt% of the polyphenylene ether composition, preferablyPreferably 1 to 15wt%, more preferably 3 to 15wt%, most preferably 3 to 10wt%.
S3, reducing the temperature of the polyphenylene ether homogeneous solution containing the foaming agent to the glass transition temperature (T) of the polyphenylene ether composition g ) Above 40-60 ℃ temperature, i.e. T g +40 ℃ to T g +60 ℃ to obtain a cooled melt of the polyphenylene ether composition containing the blowing agent.
The glass transition temperature test method of the polyphenyl ether composition comprises the following steps: weighing the components in proportion, extruding and granulating by a double-screw extruder or melting and mixing by an internal mixer to obtain the polyphenyl ether composition, and testing the glass transition temperature Tg of the polyphenyl ether composition by adopting differential scanning calorimetry according to GB/T19466.2-2004, wherein the concrete operations are as follows: taking 5-10mg of sample, and placing in Differential Scanning Calorimeter (DSC), under N 2 Under the atmosphere, the nitrogen flow rate is 50mL/min, the temperature is increased to 300 ℃ at the rate of 20 ℃/min, the temperature is kept for 5min to eliminate the thermal history of the sample, then the temperature is quickly reduced to 0 ℃ and kept for 5min, then the temperature is increased to 300 ℃ at the rate of 20 ℃/min, the temperature is increased for the second time, a test heat break-along-temperature change curve is recorded, and the intersection point of the middle line between two extrapolation baselines and the curve is taken as the glass transition temperature Tg.
And S4, extruding the cooled polyphenyl ether composition melt containing the foaming agent through a plurality of round holes of an extrusion die on a machine head, rapidly cooling, and then drawing, drying and granulating to obtain polyphenyl ether foamable particles, wherein the diameter of the polyphenyl ether foamable particles is less than or equal to 1mm, preferably less than or equal to 0.5mm.
And extruding the cooled polyphenyl ether composition melt containing the physical foaming agent through a plurality of round holes of an extrusion die on a machine head, and immediately entering a cooling water tank for rapid cooling to avoid the expansion of bubbles. Wherein 100 to 200 round holes are uniformly distributed on the extrusion die on the machine head, and the diameter of the round holes is less than or equal to 2mm, preferably less than or equal to 1.5mm, and more preferably less than or equal to 1mm. The melt pressure at the extrusion die on the machine head is more than or equal to 5MPa, preferably more than or equal to 10MPa by adjusting the extrusion output and the temperature in the extrusion process. The temperature of the cooling water in the cooling water tank is T g -130 ℃ to T g Between-100 ℃ and Tg is that of the polyphenylene ether groupThe compound has a glass transition temperature of, i.e., T g The temperature of cooling water is more than or equal to minus 130 ℃ and less than or equal to T g -100 ℃ so that the polyphenylene ether composition containing the blowing agent is rapidly cooled after melt extrusion.
And (3) drying the cooled polyphenyl ether strips by a traction machine and a blow-drying device (air cooling drying device), and then, feeding the dried polyphenyl ether strips into a granulator for granulation to obtain polyphenyl ether foamable particles. Wherein the drawing line speed is 1.5 to 20 times, preferably 1.5 to 10 times, more preferably 2 to 5 times the extrusion line speed of the head, and the extrusion line speed is set at 100 to 200m/min so that the extruded polyphenylene ether strand is drawn to give a polyphenylene ether expandable fine particle having a diameter of 1mm or less, preferably 0.5mm or less.
The extruder adopted in the preparation method is one of a single-screw extruder, a double-screw extruder or a single-screw serial melt pump extrusion system, a single-screw extruder serial single-screw extruder system, a double-screw serial single-screw extrusion system and a double-screw serial melt pump extrusion system.
Preferably a twin screw in-line single screw extrusion system wherein: the first-order double-screw extruder is a co-rotating double-screw extruder or a heterogeneous rotating double-screw extruder, a foaming agent injection port is formed in the first-order extruder and is in fluid connection with a foaming agent pressurization metering system, the temperature of each section of the first-order extruder is set to be 220-280 ℃, and the polyphenyl ether composition is melted and plasticized in the first-order extruder and is uniformly mixed with the foaming agent; the second order extruder temperature is set at a temperature 40-60 ℃ above the glass transition temperature (Tg) of the polyphenylene ether composition and the polyphenylene ether temperature is reduced to increase melt viscoelasticity.
In the case where the extruder is a single-screw tandem melt pump extrusion system or a twin-screw tandem melt pump extrusion system, the melt pump temperature is set at a temperature 40 to 60 ℃ above the glass transition temperature (Tg) of the polyphenylene ether composition, and the polyphenylene ether temperature is lowered to increase the melt viscoelasticity.
In the embodiment where the extruder is a single-screw extruder or a twin-screw extruder, the polyphenylene ether composition is melt-plasticized in the single-screw extruder or the twin-screw extruder and uniformly mixed with the blowing agent, and then the temperature of the screw extruder or the twin-screw extruder is set to a temperature of 40 to 60 ℃ above the glass transition temperature (Tg) of the polyphenylene ether composition.
The method adopts the modes of extrusion, cooling, traction and grain cutting instead of underwater grain cutting, thereby solving the problems of overhigh pressure and difficult control of the machine head on one hand; on the other hand, the method can be used for extruding the polyphenyl ether resin with higher viscosity and higher molecular weight, and is beneficial to improving the heat resistance and the mechanical property of a final product. Specifically, by adding a proper lubricant, the extrusion stability of the polyphenylene ether resin composition is improved, and the foaming rate of the foamable polyphenylene ether particles during molding is improved; after the polyphenylene oxide composition is taken out of the machine head, a rapid cooling method is adopted, the temperature of cooling water is controlled to be lower than Tg-100 ℃, so that the melt viscosity of the polyphenylene oxide composition is increased rapidly, the growth of bubbles and the expansion of extruded strips can be inhibited, the diameter of the extruded strips is further reduced through high-speed traction, the yield is improved, the size of foamable particles is reduced, and the molding product with higher molding precision or thin wall is facilitated.
Examples
Experiment raw materials:
poly 2, 6-dimethyl-1, 4-phenylene oxide (PPO), LXR045, intrinsic viscosity 45 ± 5ml/g (test standard GB/T1632.1), south china star synthetic materials ltd;
polystyrene (GPPS), green ampere 525, melt flow rate 6.7g/10min (measured according to national standard GB/T3682-2000, test temperature 200 ℃, weight 5 kg)
Polystyrene GPPS PG-33, zhenjiangqimei melt flow rate 8.5g/10min
Flame retardant, resorcinol-diphenyl diphosphate (RDP), jones Yake science and technology, inc
Tetraphenyl (bisphenol a) diphosphate (BDP): yake science and technology Co Ltd of Jiangsu
Triphenyl phosphate (TPP): zhang hong Rui ya chemical Co Ltd
High Impact Polystyrene (HIPS), 476L, melt flow rate 5g/10min, zhenjiang Qimei Yangzi Basff, 514 Shanghai Seisaceae petrochemical
Hydrogenated styrene-butadiene-styrene (SEBS), YH602, petrochemical company of Balng, china
Antioxidant 1010, south Beijing Hua Li Ming Ke Kong
Talcum powder, 1250 mesh, beijing Liguo Weiye ultra-fine division Co Ltd
Gas phase nano SiO 2 Aerosil R202 surface hydrophobic treatment Evonik
Pentaerythritol stearate, shandong Ruije New Material Co Ltd
CO 2 Purity 99.9%, beijing Shunqanqite gas Co., ltd
Cyclopentane, purity 99.9%, cijing Shunqingqite gas Co., ltd
Trans-1-3,3, 3-tetrafluoropropene (HFO-1234 ze) with a purity of 99.9%, honivier China Co., ltd
Trans-1-chloro-3, 3-trifluoropropene (HCFO) of 99.9% purity, example 1 of Honeywell, china, inc
Extrusion equipment: the co-rotating double-screw extruder is connected in series with a single-screw extruder, the diameter of the double-screw extruder is 50mm, the length-diameter ratio of the double-screw extruder is 40, the diameter of the single screw is 150mm, and the length-diameter ratio of the single screw is 20
Foaming agent: cyclopentane
100 round holes with the diameter of 2mm are uniformly distributed on a die of the single-screw extruder
According to parts by weight, 87.9 parts of PPO LXR045, 10 parts of GPPS-33, 0.1 part of antioxidant 1010,2 parts of lubricant pentaerythritol stearate and 1 part of foam cell nucleating agent are weighed according to a proportion and then added into a double-screw extruder, and the temperature of each section of the double-screw extruder is as follows: injecting cyclopentane into a fourth zone of a double-screw extruder at 220 ℃, 280 ℃ and 280 ℃, melting and plasticizing various raw materials in the double-screw extruder to obtain a polyphenyl ether composition melt, uniformly mixing the polyphenyl ether composition melt with the cyclopentane, wherein the injection amount of the cyclopentane is 5wt% of the total weight of the polyphenyl ether composition melt, then inputting the mixture into a single-screw extruder through a closed pipeline system, slowly reducing the temperature of each section of the single-screw extruder from the initial 280 ℃ to 220-240 ℃, adjusting the feeding amount to ensure that the head pressure is 10MPa, extruding the polyphenyl ether composition melt containing foaming agent through a plurality of round holes on a die, the extrusion linear speed is 120m/min, then rapidly entering cooling water, the cooling water temperature is 80 ℃, rapidly drawing through a tractor at the drawing speed of 480m/min, drying through a blow-drying device, and then pelletizing to obtain foamable polyphenyl ether particles, wherein the particle diameter is 1.0mm.
The constituents of the material (i.e., polyphenylene ether composition) were sampled from the outlet of the head before injecting the blowing agent, and the glass transition temperature T of the polyphenylene ether composition was measured according to GB/T19466.2-2004 using a differential scanning calorimeter g The result was 180 ℃.
Placing the obtained polyphenyl ether foamable particles into a mould, rapidly heating to 200 ℃ by using microwave, rapidly expanding the polyphenyl ether foamable particles and mutually bonding the polyphenyl ether foamable particles together, and molding to obtain a foamed polyphenyl ether product with the product density of 200kg/m 3 。
Example 2
Extrusion equipment: the single screw extruder is connected in series with the single screw extruder: the diameter of the first-order single screw extruder is 65mm, and the length-diameter ratio is 40; the diameter of the second-order single-screw extruder is 150mm, and the length-diameter ratio is 20
200 round holes with the diameter of 1mm are uniformly distributed on a die of the second-order single-screw extruder
According to parts by weight, 70 parts of PPO LXR045, 30 parts of GPPS PS-33,0.1 part of antioxidant 1010,1 part of lubricant zinc stearate, 1 part of foam cell nucleating agent nano-silica and 5 parts of flame retardant are weighed in proportion and then added into a first-order single-screw extruder, and the temperatures of all sections of the first-order single-screw extruder are respectively as follows: injecting trans-1-3, 3-tetrafluoropropene (HFO-1234 ze) as a physical foaming agent into a fourth zone of a first-order single-screw extruder at 220 ℃, 280 ℃ and 280 ℃, melting and plasticizing various raw materials in the first-order single-screw extruder to obtain a polyphenyl ether composition melt, uniformly mixing the polyphenyl ether composition melt with the HFO-1234ze as the physical foaming agent, wherein the injection amount of the physical foaming agent is 10wt% of the total weight of the polyphenyl ether composition melt, then inputting the polyphenyl ether composition melt into a second-order single-screw extruder through a closed pipeline system, slowly reducing the temperature of each section of the second-order single-screw extruder from the initial 280 ℃ to 200-220 ℃, adjusting the feeding amount to ensure that the head pressure is 15MPa, extruding the polyphenyl ether composition melt containing the foaming agent through a plurality of round holes on a die, rapidly feeding the polyphenyl ether composition melt into cooling water at the extrusion linear speed of 120m/min, rapidly feeding the polyphenyl ether composition melt into the cooling water at the cooling water temperature of 40 ℃, rapidly pulling the pulling speed of 480m/min through a pulling machine, drying the blowing device, and then pelletizing to obtain polyphenyl ether particles, wherein the diameters of the polyphenyl ether particles are 0.5mm.
The respective material components (i.e., polyphenylene ether composition) were sampled from the outlet of the head before injecting the foaming agent, and the glass transition temperature Tg of the polyphenylene ether composition was measured by a differential scanning calorimeter according to GB/T19466.2-2004 and found to be 160 ℃.
Placing the obtained polyphenyl ether foamable particles into a mould, rapidly heating to 180 ℃ by using microwave, rapidly expanding the polyphenyl ether foamable particles and mutually bonding the polyphenyl ether foamable particles together, and forming to obtain a foamed polyphenyl ether product with the product density of 100kg/m 3 。
Example 3
Extrusion foaming apparatus same as example 1
The foaming agent is n-butane
50 parts of PPO LXR050, 45 parts of HIPS,5 parts of flame retardant TPP,0.1 part of antioxidant 1010,1 part of lubricant ethylene bis stearamide and 1 part of foam cell nucleating agent nano SiO 2 Weighing according to the proportion, adding into a double-screw extruder, wherein the temperature of each section of the double-screw extruder is as follows: injecting cyclopentane into a fourth zone of a double-screw extruder at 220 ℃, 260 ℃, 270 ℃ and 270 ℃, melting and plasticizing various raw materials in the double-screw extruder to obtain a polyphenyl ether composition melt, and uniformly mixing the polyphenyl ether composition melt and a foaming agent, wherein the injection amount of n-butane is 3wt% of the total weight of the polyphenyl ether composition melt, then inputting the polyphenyl ether composition melt into a single-screw extruder through a closed pipeline system, the temperature of each section of the single-screw extruder is slowly reduced from 270 ℃ to 180-220 ℃, the feeding amount is adjusted to be 50kg/h, so that the head pressure is 5MPa, the polyphenyl ether composition melt containing the foaming agent is extruded through a plurality of round holes on a neck mold, the extrusion linear speed is 100m/min, then the polyphenyl ether composition melt rapidly enters cooling water at the cooling water temperature of 40 ℃, the polyphenyl ether composition melt is rapidly pulled by a tractor at the pulling speed of 800m/min, is dried by a blow-drying device, and then is cut into particles to obtain polyphenyl ether foaming particles, and the diameters of the polyphenyl ether particles are 0.6mm.
The material components (i.e., polyphenylene ether composition) were sampled from the outlet of the head before the blowing agent was injected, and the glass transition temperature Tg of the polyphenylene ether composition was measured by a differential scanning calorimeter according to GB/T19466.2-2004 to be 140 ℃.
Placing the obtained polyphenyl ether foamable particles into a mould, rapidly heating to 160 ℃ by using microwave, rapidly expanding the polyphenyl ether foamable particles and mutually bonding the polyphenyl ether foamable particles together, and molding to obtain a foamed polyphenyl ether product with the product density of 150kg/m 3 。
Example 4
The extrusion equipment is the same as that in example 1, except that 280 circular holes with the diameter of 0.8mm are uniformly distributed on the mouth mold of the single-screw extruder
The foaming agent is isopentane
According to the weight, 30 parts of PPO LXR050, 55 parts of ABS,8 parts of flame retardant RDP,0.1 part of antioxidant 1010,1 part of lubricant calcium stearate and 1 part of foam cell nucleating agent talcum powder are weighed according to the proportion and then added into a double-screw extruder, and the temperature of each section of the double-screw extruder is as follows: injecting isopentane into a fourth area of a double-screw extruder at 220 ℃, 260 ℃, 270 ℃ and 270 ℃, melting and plasticizing various raw materials in the double-screw extruder to obtain a polyphenyl ether composition melt, and uniformly mixing the polyphenyl ether composition melt with a foaming agent, wherein the injection amount of the isopentane is 15wt% of the total weight of the polyphenyl ether composition melt, then inputting the mixture into a single-screw extruder through a closed pipeline system, slowly reducing the temperature of each section of the single-screw extruder from the initial 270 ℃ to 160-180 ℃, adjusting the feeding amount to ensure that the head pressure is 15MPa, extruding the polyphenyl ether composition melt containing the foaming agent through a plurality of round holes on a neck mold at the extrusion linear speed of 200m/min, then quickly entering cooling water, ensuring the temperature of the cooling water to be 10 ℃, quickly drawing through a tractor at the drawing speed of 1600m/min, drying through a blow-drying device, and then pelletizing to obtain polyphenyl ether foamable particles with the particle diameter of 0.3mm.
The material components were sampled from the outlet of the head before the blowing agent was injected, and the glass transition temperature Tg of the polyphenylene ether composition was measured by a differential scanning calorimeter according to GB/T19466.2-2004 to give a result of 120 ℃.
The obtained polyphenyl is put intoPlacing the foamable ether particles into a mold, heating to 140 deg.C with high pressure hot steam, rapidly expanding and bonding the foamable ether particles together, and molding to obtain foamed polyphenylene ether product with density of 30kg/m 3 。
Example 5
The extrusion foaming equipment is the same as that in example 1, except that 200 round holes with the diameter of 1mm are uniformly distributed on the die
The foaming agent is n-pentane
By weight, 20 parts of PPO LXR050, 68.6 parts of SEBS,8 parts of flame retardant RDP,0.1 part of antioxidant 1010,0.3 part of lubricant polytetrafluoroethylene and 3 parts of foam cell nucleating agent nano SiO 2 Weighing according to the proportion, adding into a double-screw extruder, wherein the temperature of each section of the double-screw extruder is as follows: injecting n-pentane into a fourth area of a double-screw extruder at 220 ℃, 260 ℃ and 260 ℃, melting and plasticizing various raw materials in the double-screw extruder to obtain a polyphenyl ether composition melt, and uniformly mixing the polyphenyl ether composition melt and a foaming agent, wherein the injection amount of the n-pentane is 10wt% of the total weight of the polyphenyl ether composition melt, then inputting the mixture into a single-screw extruder through a closed pipeline system, the temperature of each section of the single-screw extruder is slowly reduced from the initial 260 ℃ to 140-160 ℃, adjusting the feeding amount to ensure that the head pressure is 10MPa, extruding the polyphenyl ether composition melt containing the foaming agent through a plurality of round holes on a die, the extrusion linear speed is 100m/min, then quickly entering cooling water, the cooling water temperature is 10 ℃, quickly drawing through a drawing machine at the drawing speed of 800m/min, drying through a blow-drying device, and then pelletizing to obtain polyphenyl ether foamable particles, and the particle diameter is 0.3mm.
The material components (i.e., polyphenylene ether composition) were sampled from the outlet of the head before the blowing agent was injected, and the glass transition temperature Tg of the polyphenylene ether composition was measured by a differential scanning calorimeter according to GB/T19466.2-2004 to be 110 ℃.
Placing the obtained polyphenyl ether foamable particles into a mould, heating to 120 ℃ by high-pressure hot steam, rapidly expanding the polyphenyl ether foamable particles, mutually bonding the polyphenyl ether foamable particles together, and molding to obtain a foamed polyphenyl ether product with the density of 50kg/m 3 。
Therefore, the polyphenyl ether expandable particles prepared by the method can be processed into products with various shapes by the conventional expandable bead molding method. For example: the polyphenyl ether foamable particles prepared by the method are added into a mould, the mould is heated or high-pressure hot steam is introduced, the foamable particles expand by volume when being heated, and the foamable particles are mutually bonded to prepare a molding product.
Comparative example 1
The raw materials and the extrusion equipment used were the same as in example 1, except that the extrusion die was a porous underwater pelletizing system, and as a result: the head pressure and the extrusion system pressure caused by underwater cutting are higher than 30MPa, so that the head is blocked and normal production cannot be realized.
Comparative example 2
The materials and the extrusion equipment were the same as in example 3 except that the cooling water temperature was 60 ℃ and the drawing speed was 200m/min, and the diameter of the obtained expandable fine particles of polyphenylene ether was more than 2mm, and a molded article having a wall thickness of less than 5mm could not be formed.
Comparative example 3
The raw materials used were the same as in example 3, and the extruder part was the same, except that the pellets were produced by underwater pelletizing from the head outlet of the extruder at a maximum yield of 30kg/h, a water temperature of 80 ℃ and a water pressure of 2.0bar to give expandable polyphenylene ether beads having a diameter of 4 to 5mm, and the same molding process as in example 3 was used to give molded articles having a density of 150kg/m 3 The mechanical properties are shown in Table 1.
Comparative example 4
The raw materials used were the same as in example 4, and the extruder part was the same, except that the pellets were produced by underwater pelletization from the outlet of the extruder head at a maximum yield of 30kg/h, a water temperature of 80 ℃ and a water pressure of 2.0bar, and the expandable polyphenylene ether beads having a diameter of 4 to 5mm were obtained by the same molding process as in example 3, and the molded articles had a density of 50kg/m 3 . The mechanical property profiles of examples 3 and 4 of the present invention and comparative examples 3 and 4 are shown in table 1.
TABLE 1 mechanical properties of examples 3,4 and comparative examples 3,4
Figure BDA0003787836550000131
Because the method adopts the processes of extrusion, cooling, traction and granulation, the problems of head temperature reduction and sharp rise of melt pressure in the head caused by underwater granulation are effectively solved, so that a material system with higher viscosity can be processed, for example, a polyphenyl ether resin composition with the polyphenyl ether content of more than 80wt% can be prepared by adopting the technical scheme of the invention in embodiment 1, and when the underwater granulation process is adopted in comparative example 1, the mouth mold of the head is blocked and normal production cannot be realized; similarly, by using the process of the present invention, the melt temperature of the polyphenylene ether composition containing the blowing agent can be lowered to a lower level, so that the cell structure of the obtained foamed article is more uniform, and the phenomenon of cell coalescence and cell breakage caused by the need to maintain a higher temperature of the melt containing the blowing agent for normal production during underwater pelletization is overcome, so that the molded articles of examples 3 and 4 of the present invention have higher mechanical strength than those of comparative examples 3 and 4.
In addition, the present invention rapidly cools the extruded material using cooling water 100 ℃ lower than the glass transition temperature of the polyphenylene ether composition, and thus, the extrusion apparatus having the same configuration can have higher productivity than the underwater pelletizing process, and the production efficiency is improved, as shown by the maximum productivity of examples 3 and 4 and comparative examples 3 and 4 in table 1.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that: any person skilled in the art can modify or improve the technical solutions described in the foregoing embodiments or make equivalent substitutions for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A method for preparing polyphenyl ether foamable particles is characterized by comprising the following steps:
s1, adding a polyphenyl ether composition into an extruder for melting and plasticizing to obtain a polyphenyl ether composition melt, wherein the polyphenyl ether composition comprises, by weight, 20-90 parts of polyphenyl ether, 10-80 parts of a styrene-based polymer, 0-10 parts of a flame retardant, 0.1-0.3 part of an antioxidant, 0.5-3 parts of a foam cell nucleating agent and 0.5-3 parts of a lubricant;
s2, injecting a physical foaming agent into the polyphenyl ether composition melt and uniformly mixing to form a polyphenyl ether composition melt containing the foaming agent;
s3, reducing the temperature of the polyphenyl ether composition melt containing the foaming agent to a temperature 40-60 ℃ above the glass transition temperature of the polyphenyl ether composition to obtain a cooled polyphenyl ether composition melt containing the foaming agent;
and S4, extruding the cooled polyphenyl ether composition melt containing the foaming agent through a plurality of round holes of an extrusion die on a machine head, rapidly cooling, and then drawing, drying and granulating to obtain polyphenyl ether foamable particles with the diameter of less than or equal to 1mm.
2. The method for preparing expandable polyphenylene ether microparticles according to claim 1, wherein the intrinsic viscosity of the polyphenylene ether is 35 to 50mL/g.
3. The method for preparing the expandable poly (phenylene ether) microparticles of claim 1, wherein the styrene-based polymer is at least one of polystyrene, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene-styrene block copolymer, and hydrogenated styrene-butadiene-styrene.
4. The method for producing expandable fine particles of polyphenylene ether according to claim 1, wherein said flame retardant is at least one of tricresyl phosphate, resorcinol-bis-diphenyl phosphate, liquid tetraphenyl bisphenol A diphosphate, or solid tetraphenyl bisphenol A diphosphate.
5. The process for preparing expandable polyphenylene ether particles according to claim 1, wherein the foam cell nucleating agent is talc or SiO 2 At least one of calcium carbonate, wollastonite, sepiolite and nano calcium silicate.
6. The method for preparing expandable microparticles of polyphenylene ether according to claim 1, wherein said lubricant is at least one of zinc stearate, calcium stearate, pentaerythritol stearate, stearic acid amide, glyceryl monostearate, erucamide, ethylene bis stearic acid amide, hyperbranched compound, polytetrafluoroethylene.
7. The method of preparing foamable microparticles of polyphenylene ether according to claim 1, wherein the physical blowing agent is n-butane, isobutane, n-pentane, isopentane, cyclopentane, cyclohexane, heptane, ethanol, 1, 2-tetrafluoroethane (HFC-134 a), 1-difluoroethane (HFC-152 a), trans 1-3, 3-tetrafluoropropene (HFO-1234 ze), trans 1-chloro-3, 3-trifluoropropene (HCFO), CO 2 、H 2 At least one of O.
8. The method for preparing expandable polyphenylene ether particles according to claim 1, wherein in step S4, the cooled melt of polyphenylene ether composition containing the foaming agent is extruded through a plurality of circular holes of an extrusion die on a machine head, immediately enters a cooling water tank for rapid cooling, is dried by a tractor and an air-cooled drying device, and enters a granulator for granulation, wherein the diameter of the circular holes is less than or equal to 2mm, and the melt pressure at the extrusion die on the machine head is greater than or equal to 5Mpa.
9. The process for producing expandable fine particles of polyphenylene ether according to claim 8, wherein T is T in step S4 g The temperature of the cooling water is more than or equal to minus 130 ℃ and less than or equal to T g -100 ℃ of which T is g Is the glass transition temperature of the polyphenylene ether composition.
10. The method for producing the polyphenylene ether foamable microparticle according to claim 1, wherein in step S4, the drawing line speed is 1.5 to 20 times the extrusion line speed.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2030646A1 (en) * 1989-12-27 1991-06-28 Richard Brian Allen Process for producing expandable termoplastic microparticles
CN109054337A (en) * 2018-06-06 2018-12-21 广东奔迪新材料科技有限公司 A kind of formula of Noryl expanded bead, preparation method and applications
CN109605708A (en) * 2018-12-14 2019-04-12 北京化工大学 A kind of thermoplastic polyester foam shaping by extrusion method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2030646A1 (en) * 1989-12-27 1991-06-28 Richard Brian Allen Process for producing expandable termoplastic microparticles
CN109054337A (en) * 2018-06-06 2018-12-21 广东奔迪新材料科技有限公司 A kind of formula of Noryl expanded bead, preparation method and applications
CN109605708A (en) * 2018-12-14 2019-04-12 北京化工大学 A kind of thermoplastic polyester foam shaping by extrusion method

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