CN114479463B - Extrusion-grade PPS composite material and preparation method thereof - Google Patents
Extrusion-grade PPS composite material and preparation method thereof Download PDFInfo
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- CN114479463B CN114479463B CN202210172899.XA CN202210172899A CN114479463B CN 114479463 B CN114479463 B CN 114479463B CN 202210172899 A CN202210172899 A CN 202210172899A CN 114479463 B CN114479463 B CN 114479463B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/59—Screws characterised by details of the thread, i.e. the shape of a single thread of the material-feeding screw
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical Kinetics & Catalysis (AREA)
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- Extrusion Moulding Of Plastics Or The Like (AREA)
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Abstract
The invention provides an extrusion grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 50-60 parts of PPS; 10-12 parts of organosilicon copolymer PC; 25-35 parts of a toughening agent; 0.5-2 parts of a lubricant; 0.5-1.5 parts of carbon black. According to the invention, linear PPS is used as a first matrix resin, organic silicon copolymerized PC is used as a second matrix resin, toughening and modification are carried out through optimized combination of multiple functional toughening agents, and meanwhile, a proper lubricant system and an optimized screw combination are adopted, so that the problems of pits on the inner wall and the outer wall of a pipe in the extrusion processing process and dirt residue on an extrusion die head are solved, and the finally prepared PPS composite material has good ductility, chemical solvent resistance and extrusion bending and shaping performances.
Description
Technical Field
The invention belongs to the field of modification of high polymer materials, and relates to an extrusion grade PPS pipe composite material with high elongation, high impact and easy bending and shaping and a preparation method thereof.
Background
Polyphenylene sulfide (PPS for short) is a special engineering plastic containing thiophenyl on a molecular main chain, a molecular chain is formed by alternately arranging benzene rings and sulfur atoms, and the structural regularity of the molecular chain is high, so that the crystallinity of the polyphenylene sulfide is high and the melting point of the polyphenylene sulfide is high; secondly, because the benzene ring and the sulfur atom form conjugation; and the sulfur atom is in an unsaturated state, and after oxidation, the thioether bond can be changed into a sulfoxide group, or adjacent macromolecules form an oxygen bridge branch or crosslink, so that the thermal stability and the oxygen stability are very outstanding; thirdly, because the polarity of the sulfur atom is conjugated by the benzene ring and is restrained by high crystallinity, the PPS has the characteristics of non-polarity or weak polarity, and therefore, the electrical insulation property, the dielectric property and the chemical medium resistance of the PPS are also outstanding. Because PPS has good compatibility with many polymers and additives, it can be modified by a variety of means to improve its mechanical and other properties. The method is widely applied to the fields of electronics, automobiles, machinery and chemical industry.
Compared with engineering plastic polyamide (commonly called nylon PA), polyphenylene sulfide, one of the special engineering plastics, has lower impact, is applied to high-temperature-resistant pipelines of automobiles, needs toughening modification and meets the requirement of bending and shaping. Most of automobile pipelines require higher hydrolysis resistance and glycol resistance, and conventional engineering plastics are difficult to meet the high requirements of hydrolysis resistance and glycol resistance on long-period aging, so that a good application field is provided for toughening and modifying PPS.
However, PPS has the problems of high brittleness, poor toughness, and poor compatibility and dispersibility with a toughening agent. Meanwhile, the problem of pits on the inner wall and the outer wall of the pipe exists in the extrusion process, and the problem of dirt residue on an extrusion die head exists. Therefore, a method for improving the toughness, the dispersion and the compatibility with the toughening agent, and improving the ductility, the chemical solvent resistance and the extrusion bending and shaping performance of the PPS needs to be found.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an extrusion grade PPS composite material and a preparation method thereof. The invention adopts linear PPS as matrix resin, reduces the crystallinity of the resin by adopting silicon copolymerized PC for extrusion and blending, then adopts optimized combination of a plurality of functionalized toughening agents for toughening and modification, and simultaneously adopts a proper lubricant system and optimized screw combination to solve the problems of pits on the inner wall and the outer wall of a pipe in the extrusion processing process and dirt residue on an extrusion die head, so that the finally prepared PPS composite material has good ductility, chemical solvent resistance and extrusion bending and shaping performances.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a PPS composite material, which comprises the following components in parts by weight:
wherein the toughening agent comprises a main toughening agent and an auxiliary toughening agent.
In a preferred embodiment of the present invention, the PPS is a linear PPS having a melt index of 50g/10min to 500g/10min.
In a preferable embodiment of the invention, the melt index of the organosilicon co-PC is 10g/10min-15g/10min.
In a preferable embodiment of the present invention, the mass ratio of the main toughening agent to the auxiliary toughening agent is (2-4): 1.
As a preferred embodiment of the present invention, the main toughening agent includes any one of or a combination of at least two of glycidyl methacrylate grafted ethylene octene copolymer (POE-g-GMA), ethylene glycidyl methacrylate-vinyl alcohol copolymer (E-GMA-VA), or ethylene butyl acrylate-glycidyl methacrylate copolymer (PTW).
In a preferred embodiment of the present invention, the auxiliary toughening agent is maleic anhydride grafted hydrogenated styrene-butadiene block copolymer (SEBS-g-MAH).
In a preferred embodiment of the present invention, the lubricant is PPA fluoropolymer and/or silicone.
In a second aspect, the present invention provides a method for preparing the aforementioned PPS composite material, the method comprising the steps of:
and extruding the PPS/PC alloy particles obtained by extruding the PPS and the organosilicon copolymerization PC according to the formula ratio, the lubricant, the main toughening agent and the carbon black from a main feeding port of a double-screw extruder, and the auxiliary toughening agent from a side feeding port of the double-screw extruder for extrusion granulation.
In a preferred embodiment of the present invention, the method for producing PPS/PC alloy particles obtained by extruding PPS and silicone-copolymerized PC includes:
PPS and organosilicon copolymerization PC are mixed according to the mass ratio of 5:1, extruded from a double-screw extruder for granulation, and then dried.
In a preferred embodiment of the present invention, in the method for producing PPS/PC alloy particles, the temperature of each zone of the twin-screw extruder is controlled to 270 to 300 ℃, and the screw rotation speed is set to 250 to 350rpm.
In a preferred embodiment of the present invention, in the method for producing PPS/PC alloy particles, the extrusion is carried out by discharging from a main feed port of a twin-screw extruder and granulating.
As a preferable scheme of the invention, in the preparation method of the PPS/PC alloy particles, the drying temperature is 130-140 ℃, and the drying time is 4-6h.
In a preferred embodiment of the invention, the ratio of the screw length L to the screw diameter D of the twin-screw extruder is 40 to 48, preferably 48.
As a preferred embodiment of the present invention, ZME elements are added to the screws of the twin-screw extruder.
In a preferred embodiment of the present invention, the screw of the twin-screw extruder is divided into a feeding and conveying section, a melting section, a first venting section, a first mixing section, a second venting section, a second mixing section, a third venting section and a metering section in this order, and a ZME element is added to the second mixing section.
As a preferable scheme of the invention, the feeding conveying section comprises 1 28/28A element, 2 44/44SK element, 1 44/22TS element, 2-4 32/32 element and 2-4 22/22 element in sequence according to the raw material conveying path.
As a preferred embodiment of the present invention, the melting section comprises 2 elements of 45 °/5/28, 1 element of 60 °/4/28, 1 element of 3 elements of 22/22, 1 element of 45 °/5/28, 1 element of 60 °/4/28, 1 element of 90 °/5/32, and 1 element of 28/14L in this order along the feed path.
As a preferable scheme of the invention, the first exhaust section comprises 3-5 44/44 elements in sequence according to the raw material conveying path.
As a preferable mode of the present invention, the first kneading section comprises 1 to 3 32/32 elements, 1 to 3 22/22 elements, 2 45 °/5/28 elements, 1 to 260 °/4/28 elements, 1 to 3 22/22 elements, 1 45 °/5/28 element and 1 90 °/5/32 element in this order along the raw material conveying path.
As a preferable scheme of the invention, the second exhaust section comprises 3-5 44/44 elements in sequence according to the raw material conveying path.
As a preferred embodiment of the present invention, the second mixing section comprises 1 to 3 32/32 elements, 1 to 2 45 °/5/28 elements, 1 to 3 32/32 elements, 2 to 4 ZME22/22 elements and 1 to 3 32/32 elements in this order along the feed conveying path.
As a preferable scheme of the invention, the third exhaust section comprises 3-5 44/44 elements in sequence according to the raw material conveying path.
As a preferable scheme of the invention, the metering section comprises 2-4 32/32 elements and 2-4 22/22 elements in sequence according to the raw material conveying path.
In a preferable embodiment of the present invention, the mass ratio of the main toughening agent discharged from the main feeding port to the auxiliary toughening agent discharged from the side feeding port is (2-4): 1.
As a preferable scheme of the invention, the control temperature of each section of the double-screw extruder is 270-300 ℃, and the screw rotating speed is set to be 250-300 rpm.
In a preferred embodiment of the present invention, after extrusion granulation, the obtained pellets are dried and extruded into a pipe using a single-screw extruder.
As the preferable scheme of the invention, the drying temperature is 130-140 ℃, and the drying time is 4-6h.
As a preferable scheme of the invention, the control temperature of each section of the single-screw extruder is 280-300 ℃, and the screw rotating speed is set to be 200-280 rpm.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, polyphenylene sulfide and organosilicon copolymerization PC are used as raw materials, toughening modification is carried out, the toughening agent combination mode is optimized and combined with the screw element combination mode of a double-screw extruder, so that the prepared extrusion grade PPS composite material can be stably extruded into a pipe with the diameter of about 1cm and the wall thickness of 1mm, the inner wall and the outer wall of the pipe are smooth, and the bending and shaping requirements are met.
The pipe prepared from the PPS composite material has tensile strength of more than 35MPa, elongation of more than 120 percent and notch impact strength of 55kJ/m 2 In the above, the inner and outer walls of the extruded pipe are basically smooth or only have individual pits.
Drawings
FIG. 1 is a screw structure of a twin-screw extruder used in example 1 of the present invention;
wherein, the method comprises the following steps of 1-feeding and conveying section, 2-melting section, 3-first exhaust section, 4-first mixing section, 5-second exhaust section, 6-second mixing section, 7-third exhaust section and 8-metering section.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The invention provides a PPS composite material, which comprises the following components in parts by weight:
wherein the toughening agent comprises a main toughening agent and an auxiliary toughening agent.
Wherein the PPS is 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts or 60 parts by weight, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable; the weight parts of the silicone copolymerized PC can be 10 parts, 11 parts or 12 parts, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable; the toughening agent can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts by weight, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable; the lubricant may be present in an amount of 0.5 parts, 0.7 parts, 1 part, 1.3 parts, 1.5 parts, 1.7 parts, or 2 parts by weight, but is not limited to the recited amounts, and other unrecited amounts within the range are equally applicable; the carbon black may be used in an amount of 0.5 parts, 0.7 parts, 1 part, 1.3 parts, 1.5 parts, etc., but the amount is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the carbon black is preferably Bleumina 312# having a high resistance to high-temperature dyeing.
In the invention, the organosilicon group is introduced into the structure of the silicon copolymerization PC, so that the silicon copolymerization PC has the performances of organic materials and inorganic materials, and the properties of hydrolysis resistance, solvent resistance and high and low temperature resistance are greatly improved. By extruding and blending silicon copolymerization PC and PPS, the amorphous and high-viscosity characteristics of the silicon copolymerization PC are utilized to destroy the high crystallization of the PPS, probably because the PC belongs to an amorphous phase and has small molecular polarity and cannot play a role of heterogeneous nucleation on the PPS, and secondly, the melt viscosity of the PC is higher than that of the PPS, so that the melt viscosity of a blending system is higher than that of the PPS, the movement capacity of a PPS molecular chain is reduced, and the crystallization capacity of the PPS is reduced; thereby effectively improving the normal temperature and low temperature toughness and solvent resistance of the PPS material.
In a preferred embodiment of the present invention, the PPS is a linear PPS having a melt index of 50g/10min to 500g/10min, for example, 50g/10min, 100g/10min, 150g/10min, 200g/10min, 250g/10min, 300g/10min, 350g/10min, 400g/10min, 450g/10min, or 500g/10min, but not limited to the values listed, and other values not listed within the range of values are also applicable. The test conditions were 315 ℃ C./5 kg.
As a preferable embodiment of the present invention, the melt index of the silicone copolymer PC is 10g/10min-15g/10min, for example, 10g/10min, 11g/10min, 12g/10min, 13g/10min, 14g/10min or 15g/10min, etc., and the test condition is 300 ℃/1.2kg.
In a preferred embodiment of the present invention, the mass ratio of the primary toughening agent to the secondary toughening agent is (2-4): 1, for example, 2:1, 2.5.
As a preferred embodiment of the present invention, the main toughening agent includes any one of or a combination of at least two of glycidyl methacrylate grafted ethylene-octene copolymer (POE-g-GMA), ethylene glycidyl methacrylate-vinyl alcohol copolymer (E-GMA-VA), or ethylene butyl acrylate-glycidyl methacrylate copolymer (PTW).
In a preferred embodiment of the present invention, the auxiliary toughening agent is maleic anhydride grafted hydrogenated styrene-butadiene block copolymer (SEBS-g-MAH).
In the invention, the main toughening agent and the auxiliary toughening agent are respectively added from the main feeding port and the side feeding port, and the main toughening agent is fed from the main feeding port in consideration of high addition fraction of the main toughening agent and difficult dispersion; secondly, considering that the auxiliary toughening agent has poor temperature resistance, cannot stay in a double-screw extruder for a longer time and has the possibility of degradation, the auxiliary toughening agent is added from side feeding. And moreover, the combination of the screws of the double-screw extruder is optimized, so that the risk of agglomeration and degradation of the toughening agent is reduced.
The invention provides a preparation method of the PPS composite material, which is characterized by comprising the following steps:
and extruding the PPS/PC alloy particles obtained by extruding the PPS and the organosilicon copolymerization PC according to the formula ratio, the lubricant, the main toughening agent and the carbon black from a main feeding port of a double-screw extruder, and the auxiliary toughening agent from a side feeding port of the double-screw extruder for extrusion granulation.
In a preferred embodiment of the present invention, the method for producing PPS/PC alloy particles obtained by extruding PPS and silicone-copolymerized PC includes:
PPS and organosilicon copolymerization PC are mixed according to the mass ratio of 5:1, and then are extruded from a double-screw extruder for granulation, and then are dried.
In a preferred embodiment of the present invention, in the method for producing PPS/PC alloy particles, the temperature of each zone of the twin-screw extruder is controlled to 270 to 300 ℃, for example, 270, 280, 285, 290, 295, or 300 ℃, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable; the screw speed is set to 250rpm to 350rpm, for example, 250rpm, 260rpm, 270rpm, 280rpm, 290rpm or 300rpm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a preferred embodiment of the present invention, in the method for producing PPS/PC alloy particles, the extrusion is carried out by discharging from a main feed port of a twin-screw extruder and granulating by extrusion.
In a preferred embodiment of the present invention, the drying temperature in the method for producing the PPS/PC alloy particles is 130 to 140 ℃, for example, 130 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃, or 140 ℃, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable; the drying time is 4-6h, such as 4h, 5h or 6h, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred embodiment of the present invention, the ratio of the screw length L to the screw diameter D of the twin-screw extruder in the method for producing the PPS composite material is 40 to 48, for example, 40, 42, 44, 46 or 48, but the ratio is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and 48 is preferred.
As a preferable mode of the invention, ZME elements are added to the screws of the twin-screw extruder in the preparation method of the PPS composite material.
In a preferred embodiment of the present invention, the screw of the twin-screw extruder is divided into a feeding and conveying section, a melting section, a first venting section, a first mixing section, a second venting section, a second mixing section, a third venting section and a metering section in this order, and a ZME element is added to the second mixing section.
As a preferable scheme of the invention, the feeding conveying section comprises 1 28/28A element, 2 44/44SK element, 1 44/22TS element, 2-4 32/32 element (for example, 2, 3 or 4) and 2-4 22/22 element (for example, 2, 3 or 4) in sequence according to the raw material conveying path, and further preferably comprises 1 28/28A element, 2 44/44SK element, 1 44/22TS element, 2 32/32 element and 2 22/22 element in sequence according to the raw material conveying path.
As a preferable mode of the present invention, the melting section comprises 2 elements of 45 °/5/28, 1 element of 60 °/4/28, 1 to 3 elements of 22/22 (for example, 1, 2 or 3), 1 element of 45 °/5/28, 1 element of 60 °/4/28, 1 element of 90 °/5/32 and 1 element of 28/14L in this order in the raw material conveying path, and further preferably comprises 2 elements of 45 °/5/28, 1 element of 60 °/4/28, 1 element of 22/22, 1 element of 45 °/5/28, 1 element of 60 °/4/28, 1 element of 90 °/5/32 and 1 element of 28/14L in this order in the raw material conveying path.
In a preferred embodiment of the present invention, the first exhaust gas flow path includes 3 to 5 44/44 elements (e.g., 3, 4, or 5 elements) in order of the material transport path, and more preferably includes 3 44/44 elements in order of the material transport path.
In a preferred embodiment of the present invention, the first mixing section comprises, in order along the raw material conveying path, 1 to 3 32/32 elements (e.g., 1, 2 or 3), 1 to 3 22/22 elements (e.g., 1, 2 or 3), 2 45 °/5/28 elements, 1 to 260 °/4/28 elements, 1 to 3 22/22 elements (e.g., 1, 2 or 3), 1 45 °/5/28 element and 1 90 °/5/32 element, and further preferably comprises, in order along the raw material conveying path, 1 32/32 element, 1 22/22 element, 2 45 °/5/28 elements, 160 °/4/28 element, 1 22/22 element, 1 45 °/5/28 element and 1 90 °/5/32 element.
In a preferred embodiment of the present invention, the second exhaust section comprises 3 to 5 44/44 elements (e.g., 3, 4, or 5), and more preferably 3 44/44 elements in sequence along the material conveying path.
As a preferred embodiment of the present invention, the second mixing section comprises, in order from 1 to 3 32/32 elements (e.g., 1, 2 or 3), from 1 to 2 45 °/5/28 elements, from 1 to 3 32/32 elements (e.g., 1, 2 or 3), from 2 to 4 ZME22/22 elements (e.g., 2, 3 or 4) and from 1 to 3 32/32 elements (e.g., 1, 2 or 3), and further preferably comprises, in order from the feed conveying path, 1 32/32 element, 1 45 °/5/28 element, 1 32/32 element, 2 ZME22/22 elements and 1 ZME 32/32 element.
In a preferred embodiment of the present invention, the third exhaust gas stage comprises 3 to 5 44/44 elements (e.g., 3, 4 or 5 elements) in sequence along the material conveying path, and more preferably comprises 3 44/44 elements in sequence along the material conveying path.
In a preferred embodiment of the present invention, the metering section comprises 2 to 4 32/32 elements (e.g., 2, 3, or 4) and 2 to 4 22/22 elements (e.g., 2, 3, or 4) in this order along the material conveying path, and more preferably comprises 2 32/32 elements and 2 22/22 elements in this order along the material conveying path. In the invention, by optimizing the combination mode of the thread elements in the double-screw extruder, on one hand, the compatibility and the dispersibility of each component of the material can be improved, and the elongation and the notch impact strength of the material are greatly improved; on the other hand, the combination of a proper lubricant system solves the problems of pits on the inner wall and the outer wall of the pipe in the extrusion processing process and dirt residues on the extrusion die head.
In a preferred embodiment of the present invention, the mass ratio of the main toughening agent discharged from the main feeding port to the auxiliary toughening agent discharged from the side feeding port is (2-4): 1, for example, 2:1, 2.5, 3:1, 3.5, 1 or 4:1, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the temperature control in each section of the twin-screw extruder is 270 ℃ to 300 ℃, for example 270 ℃, 280 ℃, 285 ℃, 290 ℃, 295 ℃, or 300 ℃, but is not limited to the values listed, and other values not listed in the range of values are also applicable; the screw speed is set to 250rpm to 300rpm, for example, 250rpm, 260rpm, 270rpm, 280rpm, 290rpm, 300rpm, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In a preferred embodiment of the present invention, after extrusion granulation, the obtained particles are dried and then extruded into a pipe by a single-screw extruder.
In a preferred embodiment of the present invention, the drying temperature is 130 to 140 ℃, for example 130 ℃, 132 ℃, 134 ℃, 136 ℃, 138 ℃ or 140 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable; the drying time is 4-6h, such as 4h, 5h or 6h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred embodiment of the present invention, the temperature control in each zone of the single screw extruder is 280 ℃ to 300 ℃, such as 280 ℃, 285 ℃, 290 ℃, 295 ℃, or 300 ℃, but is not limited to the values listed, and other values not listed in the range of values are also applicable; the screw rotation speed is set to 200rpm to 280rpm, for example, 200rpm, 210rpm, 220rpm, 230rpm, 240rpm, 250rpm, 260rpm, 270rpm or 280rpm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The following are typical but non-limiting examples of the invention:
the raw materials used in the following examples were of the type:
the PPS is GAF02 (poly lion), the silicone copolymerized PC is AG1950 (Japanese gloss), the flexibilizer POE-GMA (Engler light), E-GMA-VA (Sumitomo chemical) and PTW (DuPont), SEBS-MAH (Engler light), and the used lubricant is PPA9000H (Lu Juhua chemical), silicone (Sichuan morning light) and carbon black Bleumani 312# (Phillips).
Example 1:
the embodiment provides an extrusion grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: PPS GAF02:55 parts of (1); silicone copolypc AG1950:11 parts of (1); POE-g-GMA:24 parts of a binder; SEBS-g-MAH:8 parts of a mixture; PPA9000H:0.5 part; silicone: 0.5 part, carbon black Bleumina 312#:1 part.
The preparation method comprises the following steps:
(1) PPS and organosilicon copolymerization PC are added into a high-speed mixer according to the proportion of 5:1 for mixing for 2min, and are extruded and granulated to obtain alloy particles;
(2) Adding 66 parts of alloy particles and the rest materials except the SEBS-g-MAH in the proportion into a high-speed mixer for mixing for 2min, feeding the SEBS-g-MAH from a side feed through the optimized main feed of the double-screw extruder, and extruding to obtain modified particles; wherein, the set temperature of each section of the temperature of the double-screw extruder is as follows: 270 ℃, 280 ℃, 290 ℃, 295 ℃, 300 ℃ and setting the screw rotation speed to be low speed of 280rpm;
(3) The modified particles are subjected to injection molding to form ISO standard sample strips and extruded pipes, wherein the injection molding temperature is 290 ℃, 300 ℃, and the extruded pipe temperature is 280 ℃, 290 ℃, 300 ℃;
wherein the structure of the optimized twin-screw extruder in the step (2) is shown in figure 1 and comprises a 1-feeding conveying section, a 2-melting section, a 3-first exhaust section, a 4-first mixing section, a 5-second exhaust section, a 6-second mixing section, a 7-third exhaust section and an 8-metering section which are sequentially divided; and the 1-feeding conveying section comprises 1 28/28A element, 2 44/44SK element, 1 44/22TS element, 2 32/32 element and 2 22/22 element in turn according to the raw material conveying path; 2-the melting section comprises 2 45 °/5/28 elements, 160 °/4/28 element, 1 22/22 element, 1 45 °/5/28 element, 160 °/4/28 element, 1 90 °/5/32 element and 1 28/14L element in this order along the feed conveying path; 3-the first exhaust section comprises 3 44/44 elements in sequence according to the raw material conveying path; 4-the first mixing section comprises 1 32/32 element, 1 22/22 element, 2 45 °/5/28 element, 160 °/4/28 element, 1 22/22 element, 1 45 °/5/28 element and 1 90 °/5/32 element in sequence according to the raw material conveying path; 5-the second exhaust section comprises 3 44/44 elements in sequence according to the raw material conveying path; 6-the second mixing section comprises 1 32/32 element, 1 45 °/5/28 element, 1 32/32 element, 2 ZME22/22 element and 1 32/32 element in sequence according to the raw material conveying path; 7-the third exhaust section comprises 3 44/44 elements in turn according to the raw material conveying path; the 8-metering section comprises 2 32/32 elements and 2 22/22 elements in sequence according to the raw material conveying path.
Example 2:
the embodiment provides an extrusion grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: PPS GAF02:55 parts of (1); silicone copolypc AG1950:11 parts of (1); E-GMA-VA:24 parts of (1); SEBS-g-MAH:8 parts of a mixture; PPA9000H:0.5 part; silicone: 0.5 parts of carbon black Bleumana 312#:1 part.
The preparation method comprises the following steps:
(1) PPS and organosilicon copolymerization PC are added into a high-speed mixer according to the proportion of 5:1 for mixing for 2min, and are extruded and granulated to obtain alloy particles;
(2) Adding 66 parts of alloy particles and the rest materials except the SEBS-g-MAH in the proportion into a high-speed mixer, mixing for 2min, feeding the optimized main feed of the double-screw extruder (the structure is the same as that in the embodiment 1), feeding the SEBS-g-MAH from the side, and extruding to obtain modified particles; wherein, the set temperature of each section of the temperature of the double-screw extruder is as follows: 270 ℃, 280 ℃, 290 ℃, 295 ℃, 300 ℃ and setting the screw rotation speed to be low speed of 280rpm;
(3) And injection molding the modified particles into ISO standard sample bars and extruded pipes, wherein the injection molding temperature is 290 ℃, 300 ℃, and the extruded pipe temperature is 280 ℃, 290 ℃, 300 ℃.
Example 3:
the embodiment provides an extrusion grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: PS GAF02:55 parts of (1); silicone copolypc AG1950:11 parts of (1); PTW:24 parts of (1); SEBS-g-MAH:8 parts of a mixture; PPA9000H:0.5 part; silicone: 0.5 parts of carbon black Bleumana 312#:1 part.
The preparation method comprises the following steps:
(1) PPS and organosilicon copolymerization PC are added into a high-speed mixer according to the proportion of 5:1 for mixing for 2min, and are extruded and granulated to obtain alloy particles;
(2) Adding 66 parts of alloy particles and the rest materials except the SEBS-g-MAH in the proportion into a high-speed mixer, mixing for 2min, feeding the optimized main feed of the double-screw extruder (the structure is the same as that in the embodiment 1), feeding the SEBS-g-MAH from the side, and extruding to obtain modified particles; wherein, the set temperature of each section of the temperature of the double-screw extruder is as follows: 270 ℃, 280 ℃, 290 ℃, 295 ℃, 300 ℃ and the screw rotation speed is set to be low speed 280rpm;
(3) And injection molding the modified particles into ISO standard sample bars and extruded pipes, wherein the injection molding temperature is 290 ℃, 300 ℃, and the extruded pipe temperature is 280 ℃, 290 ℃, 300 ℃.
Comparative example 1:
the comparative example provides an extrusion-grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: PPS GAF02:55 parts of a binder; silicone copolypc AG1950:11 parts of (1); POE-g-GMA:24 parts of (1); SEBS-g-MAH:8 parts of a mixture; PPA9000H:0.5 part; silicone: 0.5 parts of carbon black Bleumana 312#:1 part.
The preparation method comprises the following steps:
(1) PPS and organosilicon copolymerization PC are added into a high-speed mixer according to the proportion of 5:1 for mixing for 2min, and are extruded and granulated to obtain alloy particles;
(2) Adding 66 parts of alloy particles and the rest materials in the proportion into a high-speed mixer, mixing for 2min, and extruding to obtain modified particles by feeding the optimized main feed of the double-screw extruder (the structure is the same as that in the embodiment 1); wherein, the set temperature of each section of the temperature of the double-screw extruder is as follows: 270 ℃, 280 ℃, 290 ℃, 295 ℃, 300 ℃ and setting the screw rotation speed to be low speed of 280rpm;
(3) And injection molding the modified particles into ISO standard sample bars and extruded pipes, wherein the injection molding temperature is 290 ℃, 300 ℃, and the extruded pipe temperature is 280 ℃, 290 ℃, 300 ℃.
Comparative example 2:
the comparative example provides an extrusion grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: PPS GAF02:55 parts of (1); silicone copolypc AG1950:11 parts of (1); POE-g-GMA:24 parts of a binder; SEBS-g-MAH:8 parts of a mixture; PPA9000H:0.5 part; silicone: 0.5 parts of carbon black Bleumana 312#:1 part.
The preparation method comprises the following steps:
(1) PPS and organosilicon copolymerization PC are added into a high-speed mixer according to the proportion of 5:1 for mixing for 2min, and are extruded and granulated to obtain alloy particles;
(2) Adding 66 parts of alloy particles and the rest materials except the SEBS-g-MAH in the proportion into a high-speed mixer for mixing for 2min, feeding materials through a main feed of a common double-screw extruder, feeding materials through an SEBS-g-MAH from a side feed, and extruding to obtain modified particles; wherein, the set temperature of each section of the temperature of the double-screw extruder is as follows: 270 ℃, 280 ℃, 290 ℃, 295 ℃, 300 ℃ and setting the screw rotation speed to be low speed of 280rpm;
(3) And injection molding the modified particles into ISO standard sample bars and extruded pipes, wherein the injection molding temperature is 290 ℃, 300 ℃, and the extruded pipe temperature is 280 ℃, 290 ℃, 300 ℃.
Comparative example 3:
the comparative example provides an extrusion grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: PPS GAF02:55 parts of (1); silicone copolypc AG1950:11 parts; POE-g-GMA:24 parts of (1); SEBS-g-MAH:8 parts of a mixture; PPA9000H:0.5 part; silicone: 0.5 parts of carbon black Bleumana 312#:1 part.
The preparation method comprises the following steps:
(1) Adding the materials except the SEBS-g-MAH into a high-speed mixer according to a proportion, mixing for 2min, feeding the materials from the side through an optimized main feed of a double-screw extruder (the structure is the same as that in the embodiment 1), and extruding to obtain modified particles; wherein, the set temperature of each section of the temperature of the double-screw extruder is as follows: 270 ℃, 280 ℃, 290 ℃, 295 ℃, 300 ℃ and the screw rotation speed is set to be low speed 280rpm;
(3) And injection molding the modified particles into ISO standard sample bars and extruded pipes, wherein the injection molding temperature is 290 ℃, 300 ℃, and the extruded pipe temperature is 280 ℃, 290 ℃, 300 ℃.
Comparative example 4:
the comparative example provides an extrusion grade PPS composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: PPS GAF02:55 parts of (1); common PC (luxi PC 1609-11): 11 parts; POE-g-GMA:24 parts of (1); SEBS-g-MAH:8 parts of a mixture; PPA9000H:0.5 part; silicone: 0.5 parts of carbon black Bleumana 312#:1 part.
The preparation method is the same as that in example 1.
Comparative example 5:
this comparative example provides an extrusion grade PPS composite and method of making the same, with the same composition and proportions as in example 1.
The preparation method comprises the following steps:
(1) PPS and organosilicon copolymerization PC are added into a high-speed mixer according to the proportion of 5:1 for mixing for 2min, and are extruded and granulated to obtain alloy particles;
(2) Adding 66 parts of alloy particles and the rest materials except POE-g-GMA in the proportion into a high-speed mixer for mixing for 2min, feeding and discharging the POE-g-GMA from the side through the optimized main feeding of the double-screw extruder (the structure is the same as that in the embodiment 1), and extruding to obtain modified particles; wherein, the set temperature of each section of the temperature of the double-screw extruder is as follows: 270 ℃, 280 ℃, 290 ℃, 295 ℃, 300 ℃ and the screw rotation speed is set to be low speed 280rpm;
(3) And injection molding the modified particles into ISO standard sample bars and extruded pipes, wherein the injection molding temperature is 290 ℃, 300 ℃, and the extruded pipe temperature is 280 ℃, 290 ℃, 300 ℃.
In order to further illustrate the beneficial effects of the technical scheme of the invention, the samples obtained in the examples 1-3 and the comparative examples 1-5 are subjected to performance detection. The test results are shown in table 1 below, in which the test standards are ISO standards.
TABLE 1 composite Performance test Table for examples 1-3 and comparative examples 1-5
For the modified PPS extruded pipe, the tensile strength of the material is more than 30MPa, the elongation is more than 70 percent and the notch impact is strong according to the actual use standardDegree of 45kJ/m 2 The mechanical property of the product is maintained above 80% after soaking for 1000h under the condition of 130 ℃ coolant.
From the test results of the examples 1-3, the POE-g-GMA and SEBS-g-MAH combined toughening PPS mechanical property and the best smoothness degree of the inner wall and the outer wall are selected; PTW or E-GMA-VA and SEBS are selected to be combined to toughen PPS, although the mechanical property of the PPS is higher than that of example 1, the inner wall and the outer wall of the PPS have individual pits, and the PTW or E-GMA-VA has a high polar group proportion, so that agglomeration phenomenon still exists in the extrusion process, even gas is generated by degradation, and the pits are generated.
Comparative examples 1-3 and comparative examples 1-5 it can be seen that comparative example 1 employs a complete blending feeding mode of SEBS-g-MAH with other materials; comparative example 2 extrusion with a common screw; comparative example 3 silicone copolypc was not extrusion blended with PPS first; the comparative example 4 adopts a common PC material, the elongation at break and the impact strength of the material are lower, and the low-temperature and normal-temperature toughness is caused due to the lower molecular chain movement capability and flexibility of the common PC compared with the silicon copolymerized PC; comparative example 5 POE-g-GMA was fed from the side feed port and SEBS-g-MAH was fed from the main feed port, not only was the elongation at break and notched impact strength of the material affected, but also the surface of the extruded pipe was not smooth due to the lack of uniform dispersion of the primary toughener and degradation of the secondary toughener.
Compared with the appearance of the pipe prepared in the embodiment 1-3, the mechanical property and the appearance of the composite material prepared in the 5 modes are poorer, and the larger difference of the mechanical property is the elongation and the notch impact strength; compared with the comparative example, the elongation and the notch impact strength of the materials in the examples 1 to 3 are respectively improved by 380 to 550 percent and 20 to 66 percent, which shows that the high crystallization of the PPS is destroyed by extruding the organosilicon copolymer PC and the PPS; the toughening agent adopts a combined processing mode of main feeding and side feeding, so that the risks of agglomeration and degradation of the toughening agent are reduced; the screw combination mode is optimized, the compatibility and the dispersibility of each component of the material are further improved, and the elongation and the notch impact strength of the material are greatly improved; from the results of comparative examples 1-5, it is seen that the three factors of blending and extruding silicone co-PC and PPS, side feeding the toughening agent and optimizing the screw combination have important influences on the performance and appearance of the material.
In conclusion, the linear PPS is used as the matrix resin, and the amorphous and high-viscosity characteristics of the organosilicon copolymerized PC are utilized to destroy the high crystallization of the PPS, so that the normal-temperature and low-temperature toughness of the material is improved; the PPS/PC alloy particles are optimally combined, toughened and modified by two functional toughening agents; by adopting a proper lubricant system, the problems of pits on the inner wall and the outer wall of the pipe in the extrusion processing process and dirt residue on the extrusion die head are solved; and meanwhile, the extrusion process is optimized, a double-screw extruder with high length-diameter ratio is mainly adopted, the combination of screw elements is optimized, the effect of mixing and dispersing is enhanced, the dispersion and compatibility problems of the PPS and the toughening agent are solved, and the finally prepared PPS pipe has good ductility, chemical solvent resistance and extrusion, bending and shaping performances.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (13)
1. The preparation method of the PPS composite material is characterized by comprising the following components in parts by weight:
wherein the toughening agent comprises a main toughening agent and an auxiliary toughening agent;
the mass ratio of the main toughening agent to the auxiliary toughening agent is (2-4) to 1;
the main toughening agent comprises any one or the combination of at least two of glycidyl methacrylate grafted ethylene-octene copolymer, ethylene glycidyl methacrylate-vinyl alcohol copolymer or ethylene-butyl acrylate-glycidyl methacrylate copolymer;
the auxiliary toughening agent is maleic anhydride grafted hydrogenated styrene-butadiene block copolymer;
the preparation method of the PPS composite material comprises the following steps:
extruding PPS and organosilicon copolymerization PC according to a formula ratio to obtain PPS/PC alloy particles, a lubricant, a main toughening agent and carbon black, discharging from a main feeding port of a double-screw extruder, discharging an auxiliary toughening agent from a side feeding port of the double-screw extruder, and extruding and granulating;
wherein the ratio of the screw length L to the screw diameter D of the double-screw extruder is 40-48;
a screw of the double-screw extruder is sequentially divided into a feeding conveying section, a melting section, a first exhaust section, a first mixing section, a second exhaust section, a second mixing section, a third exhaust section and a metering section, and a ZME element is added in the second mixing section;
the feeding conveying section comprises 1 28/28A element, 2 44/44SK element, 1 44/22TS element, 2-4 32/32 element and 2-4 22/22 element in sequence according to a raw material conveying path;
the melting section comprises 2 elements of 45 degrees/5/28, 1 element of 60 degrees/4/28, 1 element of 3 elements of 22/22, 1 element of 45 degrees/5/28, 1 element of 60 degrees/4/28, 1 element of 90 degrees/5/32 and 1 element of 28/14L in sequence according to a raw material conveying path;
the first exhaust section comprises 3-5 44/44 elements in sequence according to a raw material conveying path;
the first mixing section comprises 1-3 elements 32/32, 1-3 elements 22/22, 2 elements 45 DEG/5/28, 1-2 elements 60 DEG/4/28, 1-3 elements 22/22, 1 element 45 DEG/5/28 and 1 element 90 DEG/5/32 in sequence according to the raw material conveying path;
the second exhaust section comprises 3-5 44/44 elements in sequence according to the raw material conveying path;
the second mixing section comprises 1-3 32/32 elements, 1-2 45 DEG/5/28 elements, 1-3 32/32 elements, 2-4 ZME22/22 elements and 1-3 32/32 elements in sequence according to the raw material conveying path;
the third exhaust section comprises 3-5 44/44 elements in sequence according to the raw material conveying path;
the metering section comprises 2-4 32/32 elements and 2-4 22/22 elements in sequence according to the raw material conveying path.
2. The method of claim 1, wherein the PPS is a linear PPS having a melt index of 50g/10min to 500g/10min.
3. The preparation method according to claim 1, wherein the melt index of the silicone copolymerized PC is 10g/10min to 15g/10min.
4. The method of manufacturing according to claim 1, wherein the lubricant is a PPA fluoropolymer and/or a silicone.
5. The method according to claim 1, wherein the method for producing the PPS/PC alloy particles obtained by extruding PPS and silicone copolymerized PC comprises:
PPS and organosilicon copolymerization PC are mixed according to the mass ratio of 5:1, extruded from a double-screw extruder for granulation, and then dried.
6. The production method according to claim 5, wherein in the PPS/PC alloy particle production method, the control temperature of each section of the twin-screw extruder is 270 ℃ to 300 ℃, and the screw rotation speed is set to 250rpm to 350rpm.
7. The method according to claim 5, wherein the extruding is carried out by extrusion granulation from a main feed port of a twin-screw extruder in the PPS/PC alloy particle production method.
8. The method according to claim 5, wherein the drying temperature is 130 to 140 ℃ and the drying time is 4 to 6 hours in the PPS/PC alloy particle production method.
9. The preparation method of claim 1, wherein the mass ratio of the main toughening agent discharged from the main feeding port to the auxiliary toughening agent discharged from the side feeding port is (2-4): 1.
10. The production method according to claim 1, wherein the temperature of each section of the twin-screw extruder is controlled to 270 ℃ to 300 ℃ and the screw rotation speed is set to 250rpm to 300rpm.
11. The method according to claim 1, wherein the pellets obtained after the extrusion granulation are dried and extruded into a tube by a single screw extruder.
12. The method according to claim 11, wherein the drying temperature is 130-140 ℃ and the drying time is 4-6h.
13. The method of claim 11, wherein the temperature of each zone of the single screw extruder is controlled to be 280 ℃ to 300 ℃ and the screw rotation speed is set to be 200rpm to 280rpm.
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