CN110591331A - Modified polyphenylene sulfide or modified polyphenylene oxide foamed bead and preparation method thereof - Google Patents
Modified polyphenylene sulfide or modified polyphenylene oxide foamed bead and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high molecular engineering materials, in particular to modified polyphenylene sulfide or modified polyphenylene oxide foamed beads and a preparation method thereof, wherein the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads comprise the following components in parts by weight: 20-80 parts of polyphenylene sulfide or polyphenylene oxide, 20-80 parts of modified polymer, 10-25 parts of compatilizer, 10-20 parts of toughening agent, 5-10 parts of flame retardant, 1-5 parts of antioxidant aid, 1-5 parts of lubricant, 1-5 parts of coupling agent and 1-10 parts of dispersing agent. The invention can solve the problems of uneven particle size distribution, small multiplying power and low closed porosity of the modified polyphenylene sulfide or modified polyphenylene oxide foaming beads in the prior art.
Description
Technical Field
The invention relates to the technical field of high molecular engineering materials, in particular to modified polyphenylene sulfide or modified polyphenylene oxide foamed beads and a preparation method thereof.
Background
The polyphenylene sulfide or polyphenylene oxide resin is a novel high-performance thermoplastic resin, the strength can reach about 70MPa, which is about 3 times that of polyethylene, the elastic modulus is greater than 2000MPa, the impact resistance of the material is greater than 430J/m, the thermal deformation temperature is as high as 120 ℃, the dimensional stability of the product is good, the creep resistance of the product is the best of five engineering plastics, the long-term use strength has higher reliability, the polyphenylene oxide material also has intrinsic flame retardance, and belongs to low-smoke halogen-free environment-friendly flame retardance, and the resin is acid-base-resistant, water-resistant and good in sanitary performance. The foamed material prepared by taking polyphenylene sulfide or polyphenylene oxide resin as a substrate is expected to replace EVA foamed material.
However, the high-performance polyphenylene sulfide or polyphenylene oxide resin has the defects of high rigidity, high glass transition temperature, difficult orientation, high residual internal stress in the product, poor melt flowability, difficult processing and the like, and the application of the polyphenylene sulfide or polyphenylene oxide resin material is undoubtedly limited by the defects.
Therefore, it is necessary to modify polyphenylene sulfide or polyphenylene ether resin. The polyphenylene sulfide or polyphenylene oxide serving as modified engineering plastic has good thermal property determined by the molecular structure, the glass transition temperature of the polyphenylene sulfide or polyphenylene oxide can reach 120 ℃, and the polyphenylene sulfide or polyphenylene oxide can keep excellent mechanical property, electrical property, thermal insulation property and flame retardant property in a wider temperature range, has good heat resistance and water vapor resistance, and is very suitable for serving as a foaming material.
However, the prior art is harsh on the production conditions of the expanded beads, complicated in process, not beneficial to industrial production, and has the conditions of difficult control of the particle size and gas content of the expanded beads, uneven particle size distribution, small multiplying power, low closed cell ratio and the like.
Therefore, how to produce the modified polyphenylene sulfide or modified polyphenylene oxide expanded beads with uniform particle size distribution, large multiplying power and high closed cell rate and optimize the preparation process thereof is a technical problem which needs to be solved urgently.
Disclosure of Invention
The invention provides a modified polyphenylene sulfide or modified polyphenylene oxide foamed bead and a preparation method thereof, and aims to solve the technical problems of uneven particle size distribution, small multiplying power, low closed porosity and difficult processing of the modified polyphenylene sulfide or modified polyphenylene oxide foamed bead in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides modified polyphenylene sulfide or modified polyphenylene oxide foaming beads, which comprise the following components in parts by weight: 20-80 parts of polyphenylene sulfide or polyphenylene oxide, 20-80 parts of modified polymer, 10-25 parts of compatilizer, 10-20 parts of toughening agent, 5-10 parts of flame retardant, 1-5 parts of antioxidant aid, 1-5 parts of lubricant, 1-5 parts of coupling agent and 1-10 parts of dispersing agent.
The polyphenylene sulfide or polyphenylene oxide is modified by a modified polymer, and the compatilizer promotes the polyphenylene sulfide or polyphenylene oxide, the flame retardant and the antioxidant to be combined to obtain a stable high-molecular blend through intermolecular bonding force; the antioxidant can delay the oxidation process of the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads, so that the aging of the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads is slowed down, and the service life of the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads is prolonged; the flame retardant is a functional auxiliary agent for endowing the high molecular polymer with flame retardancy, and the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads have a flame-retardant function by adding the flame retardant; the auxiliary antioxidant helps the antioxidant to be fully mixed, so that the oxidation resistance of the modified polyphenylene sulfide or modified polyphenylene oxide foamed bead is ensured, and the service life is prolonged; the toughening agent can give better flexibility to the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads, and can prevent the problems of low elongation, large brittleness, easy generation of cracks, rapid expansion, fatigue resistance and the like after curing; the coupling agent can enhance the interface performance of the material and improve the mechanical strength of the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads; the dispersing agent prevents the sedimentation and agglomeration of particles, prevents the material from being unable to disperse uniformly due to difficulty in dissolution, and affects the quality of the expanded beads finally obtained. The problems of uneven particle size distribution, small multiplying power and low closed-cell rate of the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads in the prior art are solved through the materials and the proportion.
In an alternative embodiment, the modified polymer comprises the following components in equal parts by weight: HIPS, PP, BS, ABS, PE, PPS, PA, GPPS.
The HIPS is impact-resistant polystyrene, the PP is polypropylene, the BS is dodecyl dimethyl aminoethylenolactone, the ABS is a terpolymer of three monomers of acrylonitrile (A), butadiene (B) and styrene (S), the PE is polyethylene, the PPS is polyether plastic, the PA is general engineering plastic, the GPPS is general polystyrene (GPPS) Polystyrene (PS), and the polyphenylene sulfide or polyphenylene oxide can be modified and the mechanical property of the modified polymer can be enhanced by the modified polymer obtained by the materials in equal mass ratio.
In an alternative embodiment, the compatibilizer comprises the following components in parts by weight: PP-g-MAH, PE-g-MAH, EPDM, SHBS-g-MAH, POE-g-GMA.
The PP-g-MAH is PP grafted maleic anhydride, the PE-g-MAH is maleic anhydride grafted polyethylene, the EPDM is ethylene propylene diene monomer rubber, the SHBS-g-MAH is SHBS grafted maleic anhydride, and the POE-g-GMA is methacrylic acid glycidyl ester grafted ethylene-octene copolymer. The polymers are combined into a whole by the materials in equal mass ratio, so that the auxiliary agent for stabilizing the blend is obtained, and the compatilizer greatly improves the bonding force among different polymers to form a stable structure.
In an optional scheme, the toughening agent comprises the following components in parts by weight: polybutene, LCP, EPDM, SBS, SEBS, polyolefin elastomers.
The LCP is an industrial liquid crystal polymer, the EPDM is ethylene propylene diene monomer, the SBS is sodium bisulfite, the SEBS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-butylene copolymer obtained by hydrogenation of polybutadiene as a middle elastic block. The toughening agent can increase the flexibility of the expanded beads and does not affect other main properties of the expanded beads.
In an alternative arrangement, the first and second electrodes may be,
the flame retardant comprises the following components in parts by weight: phosphoric ester flame retardants and inorganic nano flame retardants;
the inorganic nano flame retardant comprises the following components in parts by weight: nano aluminum hydroxide, nano magnesium hydroxide, red phosphorus, zinc borate, nano antimony oxide, nano molybdenum compound, layered silicate and anhydrous magnesium carbonate.
The flame retardant can increase the flame resistance of the high polymer material, and does not reduce the heat resistance and the mechanical strength of the high polymer material; the flame retardant has extremely high decomposition temperature, so that the flame retardant is not decomposed at the processing temperature; the durability and the weather resistance are good.
In an alternative arrangement, the first and second electrodes may be,
the antioxidant is an antioxidant 1076;
the auxiliary antioxidant is auxiliary antioxidant 235;
the lubricant is liquid paraffin;
the coupling agent comprises the following components in parts by weight: silane coupling agent, tai acid ester coupling agent and aluminic acid coupling agent;
the dispersing agent comprises the following components in parts by weight: polyolefin type hyperdispersants, polyether type hyperdispersants, and polyacrylate type hyperdispersants.
The material and the specific gravity can enhance the mechanical strength of the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads, the prepared foamed beads are uniform in foaming, large in multiplying power, high in closed pore rate, uniform and fine in pores, free of shrinkage and collapse, and guaranteed in performance, the material can promote the production of the foamed beads, the thorough degree of the reaction process is improved, and the waste of the material is reduced.
A preparation method of modified polyphenylene sulfide or modified polyphenylene oxide foamed beads comprises the following steps:
(1) material modification: stirring polyphenylene sulfide or polyphenylene oxide, modified polymer, compatilizer, toughening agent, flame retardant, antioxidant, auxiliary antioxidant, lubricant, coupling agent and dispersant in a stirrer for 5-10 min; then heating the mixed materials in an environment of 150-200 ℃ for 30-50 min; extruding the material to prepare a modified polyphenylene sulfide or modified polyphenylene oxide material;
(5) underwater pelletizing: adding the modified polyphenylene sulfide or modified polyphenylene oxide material prepared in the step (1) into a stirrer to stir for 5-10 min; then extruding, and granulating the extruded material under water to obtain modified polyphenylene sulfide or modified polyphenylene oxide granules;
(10) pre-expanded particles: adding supercritical fluid and the modified polyphenylene sulfide or modified polyphenylene oxide granules prepared in the step (5) into a high-pressure reaction kettle, and allowing the supercritical fluid to permeate the granules, wherein the permeation process lasts for 20-40 min, so as to obtain foamed particles; and finally, fluidizing, cooling and cooling the obtained foaming particles to obtain the modified polyphenylene sulfide or modified polyphenylene oxide foaming beads with the foaming ratio of 3-30 times.
The materials of the foaming beads are uniformly mixed, and then the uniformly mixed materials are heated to the most appropriate temperature environment, so that the materials can be subjected to thorough reaction due to the uniform mixing step, and the waste of processing materials is reduced; the heated material is stirred again to remove air bubbles in the material and prevent the air bubbles from generating adverse effects on the product quality; extruding the stirred material under water to quickly cool and solidify the material, and conveniently granulating the material; foaming the obtained granules in a high-pressure reaction kettle, and fluidizing, cooling and cooling the granules after foaming to obtain foamed beads with high foaming ratio; the scheme ensures that the foaming multiplying power of the produced foaming beads is high, the material waste is less, and the quality of the foaming beads is also ensured.
In an optional scheme, the pelletizing precision of the material in the step (5) is controlled to be 0.3 mm-3 mm.
The pelletizing precision of the material is kept between 0.3mm and 3mm, because the pelletizing volume is doubled by foaming, the pelletizing with large volume difference is larger, and the volume difference is larger after foaming. Therefore, the precision of grain cutting is set to be 0.3 mm-3 mm, the size difference of grain cutting is reduced, and the performance of the product is ensured.
In an alternative embodiment, the supercritical fluid in the step (10) is a mixed gas of carbon dioxide and nitrogen.
The mixed gas of carbon dioxide and nitrogen can increase the expansion ratio of the expanded beads and improve the production quality.
According to an optional scheme, the manufacturing method further comprises the step (15), the foamed modified polyphenylene sulfide or modified polyphenylene oxide foamed bead prepared in the step (10) is heated at 120-250 ℃ for 20-30 min under the environment that the air pressure is 0.25-0.55 MPa, and then the heated foamed particles are placed in vacuum for cooling.
The steps further improve the production quality of the expanded beads, improve the closed cell rate of the expanded beads, ensure that the cells are uniform and fine, and reduce the content of oxygen.
Compared with the prior art, the modified polyphenylene sulfide or modified polyphenylene oxide foamed bead and the preparation method thereof provided by the invention have the following advantages:
adding supercritical fluid into a high-pressure reaction kettle to prepare the expanded beads with uniform expansion and large multiplying power; by selecting materials and setting the proportion, the foamed beads with uniform and fine foam holes and no shrinkage and collapse can be obtained, and the foamed beads have the characteristics of flame retardance and long service life; by controlling the temperature and the atmospheric pressure environment of the expanded beads, expanded beads having a high closed cell content can be obtained. The preparation method of the expanded beads can reduce the waste amount of materials, better control the particle size of the expanded beads and the gas content of the beads, and ensure the uniform distribution of the particle size.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The following examples are intended only to provide a possible solution and are not intended to limit the invention.
The first embodiment is as follows: 20-80 parts of polyphenylene sulfide or polyphenylene oxide, 20-80 parts of modified polymer, 10-25 parts of compatilizer, 10-20 parts of toughening agent, 5-10 parts of flame retardant, 1-5 parts of antioxidant aid, 1-5 parts of lubricant, 1-5 parts of coupling agent and 1-10 parts of dispersing agent.
The modified polymer comprises the following components in parts by weight: HIPS, PP, BS, ABS, PE, PPS, PA and GPPS, and the materials are put into a stirrer and mechanically stirred for 5min to prepare the modified polymer.
The compatilizer comprises the following components in parts by weight: PP-g-MAH, PE-g-MAH, EPDM, SHBS-g-MAH and POE-g-GMA, and the materials are placed into a stirrer and mechanically stirred for 10min at the temperature of 130-150 ℃ to prepare the compatilizer.
The toughening agent comprises the following components in parts by weight: the toughening agent is prepared by mechanically stirring polybutylene, LCP, EPDM, SBS, SEBS and polyolefin elastomer in a stirrer at 110-130 ℃ for 30 min.
The flame retardant comprises the following components in parts by weight: phosphoric ester flame retardants and inorganic nano flame retardants; the materials of the flame retardant are mixed in a stirrer, slowly heated until the temperature is raised to 200-250 ℃, then discharged and cooled, and the flame retardant is melted and extruded.
The inorganic nano flame retardant comprises the following components in parts by weight: nano aluminum hydroxide, nano magnesium hydroxide, red phosphorus, zinc borate, nano antimony oxide, nano molybdenum compound, layered silicate and anhydrous magnesium carbonate. The inorganic nano flame retardant can be obtained by mechanically stirring and mixing the materials.
The antioxidant is an antioxidant 1076;
the auxiliary antioxidant is auxiliary antioxidant 235;
the lubricant is liquid paraffin;
the coupling agent comprises the following components in parts by weight: silane coupling agent, tai acid ester coupling agent and aluminic acid coupling agent; and (3) uniformly mixing the materials by using a stirrer to prepare the coupling agent.
The dispersing agent comprises the following components in parts by weight: the polyolefin type hyperdispersant, the polyether type hyperdispersant and the polyacrylate type hyperdispersant are uniformly mixed by a stirrer to prepare the dispersant.
A preparation method of modified polyphenylene sulfide or modified polyphenylene oxide foamed beads comprises the following steps:
(1) material modification: stirring polyphenylene sulfide or polyphenylene oxide, modified polymer, compatilizer, toughening agent, flame retardant, antioxidant, auxiliary antioxidant, lubricant, coupling agent and dispersant in a stirrer for 5-10 min; then heating the mixed materials in an environment of 150-200 ℃ for 30-50 min; extruding the material to prepare a modified polyphenylene sulfide or modified polyphenylene oxide material;
(5) underwater pelletizing: adding the modified polyphenylene sulfide or modified polyphenylene oxide material prepared in the step (1) into a stirrer to stir for 5-10 min; and then extruding, and granulating the extruded material under water to obtain modified polyphenylene sulfide or modified polyphenylene oxide granules, wherein the granule cutting precision of the modified polyphenylene sulfide or modified polyphenylene oxide granules is controlled to be 0.3-3 mm.
(10) Pre-expanded particles: adding supercritical fluid and the modified polyphenylene sulfide or modified polyphenylene oxide granules prepared in the step (5) into a high-pressure reaction kettle, and allowing the supercritical fluid to permeate the granules, wherein the supercritical fluid is a mixed gas of carbon dioxide and nitrogen, the volume ratio of the carbon dioxide to the nitrogen is 1:1, and the permeation process lasts for 20-40 min, so as to obtain foamed particles; and finally, fluidizing, cooling and cooling the obtained foaming particles, wherein the fluidizing temperature can be 210 ℃, and obtaining the modified polyphenylene sulfide or modified polyphenylene oxide foaming beads with the foaming ratio of 3-30 times.
(15) The quality is improved: and (2) heating the foamed modified polyphenylene sulfide or modified polyphenylene oxide foamed beads prepared in the step (10) at 120-250 ℃ for 20-30 min under the environment of 0.25-0.55 MPa of air pressure, and then cooling the heated foamed particles in vacuum.
The first embodiment effectively solves the technical problems of small multiplying power, low closed pore rate and difficult processing of the modified polyphenylene sulfide or modified polyphenylene oxide foamed beads, and the prepared foamed beads have uniform particle size distribution.
Example two: the invention provides modified polyphenylene sulfide or modified polyphenylene oxide foaming beads, which comprise the following components in parts by weight: 30 parts of polyphenylene sulfide or polyphenylene oxide, 20 parts of modified polymer, 15 parts of compatilizer, 15 parts of flexibilizer, 5 parts of flame retardant, 2 parts of antioxidant, 1 part of auxiliary antioxidant, 1 part of lubricant, 1 part of coupling agent and 10 parts of dispersing agent.
The modified polymer comprises the following components in parts by weight: HIPS, PP, BS, ABS, PE, PPS, PA and GPPS, and the materials are put into a stirrer and mechanically stirred for 5min to prepare the modified polymer.
The compatilizer comprises the following components in parts by weight: PP-g-MAH, PE-g-MAH, EPDM, SHBS-g-MAH and POE-g-GMA, and the materials are put into a stirrer and mechanically stirred for 10min at the temperature of 150 ℃ to prepare the compatilizer.
The toughening agent comprises the following components in parts by weight: the toughening agent is prepared by mechanically stirring polybutylene, LCP, EPDM, SBS, SEBS and polyolefin elastomer in a stirrer at 130 ℃ for 30 min.
The flame retardant comprises the following components in parts by weight: phosphoric ester flame retardants and inorganic nano flame retardants; the materials of the flame retardant are mixed in a stirrer, slowly heated until the temperature is raised to 250 ℃, then discharged and cooled, and the flame retardant is melted and extruded.
The inorganic nano flame retardant comprises the following components in parts by weight: nano aluminum hydroxide, nano magnesium hydroxide, red phosphorus, zinc borate, nano antimony oxide, nano molybdenum compound, layered silicate and anhydrous magnesium carbonate. The inorganic nano flame retardant can be obtained by mechanically stirring and mixing the materials.
The antioxidant is an antioxidant 1076;
the auxiliary antioxidant is auxiliary antioxidant 235;
the lubricant is liquid paraffin;
the coupling agent comprises the following components in parts by weight: silane coupling agent, tai acid ester coupling agent and aluminic acid coupling agent; and (3) uniformly mixing the materials by using a stirrer to prepare the coupling agent.
The dispersing agent comprises the following components in parts by weight: the polyolefin type hyperdispersant, the polyether type hyperdispersant and the polyacrylate type hyperdispersant are uniformly mixed by a stirrer to prepare the dispersant.
A preparation method of modified polyphenylene sulfide or modified polyphenylene oxide foamed beads comprises the following steps:
(1) material modification: stirring polyphenylene sulfide or polyphenylene oxide, modified polymer, compatilizer, toughening agent, flame retardant, antioxidant, auxiliary antioxidant, lubricant, coupling agent and dispersant in a stirrer for 10 min; then heating the mixed materials in an environment of 200 ℃ for 50 min; extruding the material to prepare a modified polyphenylene sulfide or modified polyphenylene oxide material;
(5) underwater pelletizing: adding the modified polyphenylene sulfide or modified polyphenylene oxide material prepared in the step (1) into a stirrer and stirring for 10 min; and then extruding, and cutting the extruded material into granules under water to obtain the modified polyphenylene sulfide or modified polyphenylene oxide granules, wherein the cutting precision of the modified polyphenylene sulfide or modified polyphenylene oxide granules is controlled to be 3 mm.
(10) Pre-expanded particles: adding supercritical fluid and the modified polyphenylene sulfide or modified polyphenylene oxide granules prepared in the step (5) into a high-pressure reaction kettle, and allowing the supercritical fluid to permeate the granules, wherein the supercritical fluid is a mixed gas of carbon dioxide and nitrogen, the volume ratio of the carbon dioxide to the nitrogen is 1:1, and the permeation process lasts for 40min to obtain foamed particles; and finally, fluidizing, cooling and cooling the obtained foaming particles, wherein the fluidizing temperature is 210 ℃, and the modified polyphenylene sulfide or modified polyphenylene oxide foaming beads with the foaming ratio of 30 times are obtained.
(15) The quality is improved: and (3) heating the foamed modified polyphenylene sulfide or modified polyphenylene oxide foamed bead prepared in the step (10) at 250 ℃ for 30min under the environment of 0.55MPa of air pressure, and then cooling the heated foamed bead in vacuum.
The second embodiment effectively solves the technical problems of non-uniform particle size distribution, low closed porosity and difficult processing of the modified polyphenylene sulfide or modified polyphenylene oxide foam beads, and the prepared foam beads have extremely high multiplying power.
Example three: the invention provides modified polyphenylene sulfide or modified polyphenylene oxide foaming beads, which comprise the following components in parts by weight: 25 parts of polyphenylene sulfide or polyphenylene oxide, 25 parts of modified polymer, 15 parts of compatilizer, 15 parts of flexibilizer, 5 parts of flame retardant, 1 part of antioxidant, 1 part of auxiliary antioxidant, 1 part of lubricant, 2 parts of coupling agent and 10 parts of dispersing agent.
The modified polymer comprises the following components in parts by weight: HIPS, PP, BS, ABS, PE, PPS, PA and GPPS, and the materials are put into a stirrer and mechanically stirred for 5min to prepare the modified polymer.
The compatilizer comprises the following components in parts by weight: PP-g-MAH, PE-g-MAH, EPDM, SHBS-g-MAH and POE-g-GMA, and the materials are put into a stirrer and mechanically stirred for 10min at the temperature of 140 ℃ to prepare the compatilizer.
The toughening agent comprises the following components in parts by weight: the toughening agent is prepared by mechanically stirring polybutylene, LCP, EPDM, SBS, SEBS and polyolefin elastomer in a stirrer at 120 ℃ for 30 min.
The flame retardant comprises the following components in parts by weight: phosphoric ester flame retardants and inorganic nano flame retardants; the materials of the flame retardant are mixed in a stirrer, slowly heated until the temperature rises to 225 ℃, then discharged, cooled and melted to extrude the flame retardant.
The inorganic nano flame retardant comprises the following components in parts by weight: nano aluminum hydroxide, nano magnesium hydroxide, red phosphorus, zinc borate, nano antimony oxide, nano molybdenum compound, layered silicate and anhydrous magnesium carbonate. The inorganic nano flame retardant can be obtained by mechanically stirring and mixing the materials.
The antioxidant is an antioxidant 1076;
the auxiliary antioxidant is auxiliary antioxidant 235;
the lubricant is liquid paraffin;
the coupling agent comprises the following components in parts by weight: silane coupling agent, tai acid ester coupling agent and aluminic acid coupling agent; and (3) uniformly mixing the materials by using a stirrer to prepare the coupling agent.
The dispersing agent comprises the following components in parts by weight: the polyolefin type hyperdispersant, the polyether type hyperdispersant and the polyacrylate type hyperdispersant are uniformly mixed by a stirrer to prepare the dispersant.
A preparation method of modified polyphenylene sulfide or modified polyphenylene oxide foamed beads comprises the following steps:
(1) material modification: stirring polyphenylene sulfide or polyphenylene oxide, modified polymer, compatilizer, toughening agent, flame retardant, antioxidant, auxiliary antioxidant, lubricant, coupling agent and dispersant in a stirrer for 8 min; heating the mixed materials at 175 deg.C for 40 min; extruding the material to prepare a modified polyphenylene sulfide or modified polyphenylene oxide material;
(5) underwater pelletizing: adding the modified polyphenylene sulfide or modified polyphenylene oxide material prepared in the step (1) into a stirrer and stirring for 8 min; and then extruding, and cutting the extruded material into granules under water to obtain the modified polyphenylene sulfide or modified polyphenylene oxide granules, wherein the cutting precision of the modified polyphenylene sulfide or modified polyphenylene oxide granules is controlled to be 1.5 mm.
(10) Pre-expanded particles: adding supercritical fluid and the modified polyphenylene sulfide or modified polyphenylene oxide granules prepared in the step (5) into a high-pressure reaction kettle, and allowing the supercritical fluid to permeate the granules, wherein the supercritical fluid is a mixed gas of carbon dioxide and nitrogen, the volume ratio of the carbon dioxide to the nitrogen is 1:1, and the permeation process lasts for 30min to obtain foamed particles; and finally, fluidizing, cooling and cooling the obtained foaming particles, wherein the fluidizing temperature is 210 ℃, and obtaining the modified polyphenylene sulfide or modified polyphenylene oxide foaming beads with the foaming ratio of 16 times.
(15) The quality is improved: and (3) heating the foamed modified polyphenylene sulfide or modified polyphenylene oxide foamed bead prepared in the step (10) at 185 ℃ for 25min under the environment of 0.4MPa of air pressure, and then cooling the heated foamed particles in vacuum.
The modified polyphenylene sulfide or modified polyphenylene oxide foam beads prepared in the third embodiment have the advantages of uniform particle size distribution, high closed cell rate, convenience in processing and large multiplying power of the prepared foam beads.
The above are only preferred embodiments of the present invention, which are intended to show the outstanding technical effects and advantages of the present invention, and are not intended to limit the technical solutions of the present invention. It should be understood by those skilled in the art that all modifications, changes or alternative technical features made based on the technical contents of the present invention should be included in the technical scope of the appended claims.
Claims (10)
1. The modified polyphenylene sulfide or modified polyphenylene oxide foamed bead is characterized by comprising the following components in parts by weight: 20-80 parts of polyphenylene sulfide or polyphenylene oxide, 20-80 parts of modified polymer, 10-25 parts of compatilizer, 10-20 parts of toughening agent, 5-10 parts of flame retardant, 1-5 parts of antioxidant aid, 1-5 parts of lubricant, 1-5 parts of coupling agent and 1-10 parts of dispersing agent.
2. The modified polyphenylene sulfide or modified polyphenylene ether expanded bead as claimed in claim 1, wherein: the modified polymer comprises the following components in parts by weight: HIPS, PP, BS, ABS, PE, PPS, PA, GPPS.
3. The modified polyphenylene sulfide or modified polyphenylene ether expanded bead as claimed in claim 1, wherein: the compatilizer comprises the following components in parts by weight: PP-g-MAH, PE-g-MAH, EPDM, SHBS-g-MAH, POE-g-GMA.
4. The modified polyphenylene sulfide or modified polyphenylene ether expanded bead as claimed in claim 1, wherein: the toughening agent comprises the following components in parts by weight: polybutene, LCP, EPDM, SBS, SEBS, polyolefin elastomers.
5. The modified polyphenylene sulfide or modified polyphenylene ether expanded bead as claimed in claim 1, wherein: the flame retardant comprises the following components in parts by weight: phosphoric ester flame retardants and inorganic nano flame retardants;
the inorganic nano flame retardant comprises the following components in parts by weight: nano aluminum hydroxide, nano magnesium hydroxide, red phosphorus, zinc borate, nano antimony oxide, nano molybdenum compound, layered silicate and anhydrous magnesium carbonate.
6. The modified polyphenylene sulfide or modified polyphenylene ether expanded bead as claimed in claim 1, wherein:
the antioxidant is an antioxidant 1076;
the auxiliary antioxidant is auxiliary antioxidant 235;
the lubricant is liquid paraffin;
the coupling agent comprises the following components in parts by weight: silane coupling agent, tai acid ester coupling agent and aluminic acid coupling agent;
the dispersing agent comprises the following components in parts by weight: polyolefin type hyperdispersants, polyether type hyperdispersants, and polyacrylate type hyperdispersants.
7. A method for preparing the modified polyphenylene sulfide or modified polyphenylene ether expanded beads as claimed in any one of claims 1 to 6, comprising the steps of:
(1) material modification: stirring polyphenylene sulfide or polyphenylene oxide, modified polymer, compatilizer, toughening agent, flame retardant, antioxidant, auxiliary antioxidant, lubricant, coupling agent and dispersant in a stirrer for 5-10 min; then heating the mixed materials in an environment of 150-200 ℃ for 30-50 min; extruding the material to prepare a modified polyphenylene sulfide or modified polyphenylene oxide material;
(5) underwater pelletizing: adding the modified polyphenylene sulfide or modified polyphenylene oxide material prepared in the step (1) into a stirrer to stir for 5-10 min; then extruding, and granulating the extruded material under water to obtain modified polyphenylene sulfide or modified polyphenylene oxide granules;
(10) pre-expanded particles: adding supercritical fluid and the modified polyphenylene sulfide or modified polyphenylene oxide granules prepared in the step (5) into a high-pressure reaction kettle, and allowing the supercritical fluid to permeate the granules, wherein the permeation process lasts for 20-40 min, so as to obtain foamed particles; and finally, fluidizing, cooling and cooling the obtained foaming particles to obtain the modified polyphenylene sulfide or modified polyphenylene oxide foaming beads with the foaming ratio of 3-30 times.
8. The method for producing modified polyphenylene sulfide or modified polyphenylene ether expanded beads according to claim 7, wherein: and (5) controlling the grain cutting precision of the material to be 0.3-3 mm.
9. The method for producing modified polyphenylene sulfide or modified polyphenylene ether expanded beads according to claim 7, wherein: the supercritical fluid in the step (10) is a mixed gas of carbon dioxide and nitrogen.
10. The method for producing modified polyphenylene sulfide or modified polyphenylene ether expanded beads according to claim 7, wherein: the manufacturing method also comprises a step (15), wherein the foamed modified polyphenylene sulfide or modified polyphenylene oxide foamed bead prepared in the step (10) is heated at 120-250 ℃ for 20-30 min under the environment of 0.25-0.55 MPa of air pressure, and then the heated foamed particles are placed in vacuum for cooling.
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| CN201910760677.8A CN110591331A (en) | 2019-08-16 | 2019-08-16 | Modified polyphenylene sulfide or modified polyphenylene oxide foamed bead and preparation method thereof |
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| WO2022030293A1 (en) * | 2020-08-03 | 2022-02-10 | ダイキン工業株式会社 | Foam molding composition, foamed molded body, electric wire, method for manufacturing foamed molded body, and method for manufacturing electric wire |
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| CN114736505A (en) * | 2022-04-22 | 2022-07-12 | 无锡会通轻质材料股份有限公司 | Foaming polyphenyl ether polypropylene composite bead and wafer packaging box |
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