CN102337018B - Polyaryletherketone sheet or board - Google Patents
Polyaryletherketone sheet or board Download PDFInfo
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- CN102337018B CN102337018B CN2011102139091A CN201110213909A CN102337018B CN 102337018 B CN102337018 B CN 102337018B CN 2011102139091 A CN2011102139091 A CN 2011102139091A CN 201110213909 A CN201110213909 A CN 201110213909A CN 102337018 B CN102337018 B CN 102337018B
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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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
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92647—Thickness
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of polymer materials, and particularly relates to a polyaryletherketone sheet or board with the characteristics of high strength, high-temperature resistance, corrosion resistance and the like. Based on the sum of the components being 100wt%, the polyaryletherketone sheet or board comprises 90.0-100.0wt% of polyaryletherketone resin, 0-3.0wt% of high-temperature lubricant and 0-10.0wt% of hyperbranched polyaryletherketone. The extrusion molding method of the polyaryletherketone sheet or board comprises high-temperature melt extrusion of resin, filtering of melt, introduction of melt to a slit-type neck mold, formation of melt material sheets in the neck mold, introduction of the melt material sheets to a three-roller calender for cooling and molding and other steps. By controlling the molding temperature of the three-roller calender, hypocrystalline or amorphous sheets can be prepared. The prepared polyaryletherketone sheet has the characteristics of high strength, high heat-resistant temperature, corrosion resistance and the like, and has wide application in the high-technology fields, such as aviation and aerospace, weapons and equipment, electronics, automobiles, machinery, petrochemical industry and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to polyaryletherketone sheet material or sheet material that a class has intensity height, the characteristics such as high temperature resistant and corrosion-resistant.
Background technology
The polyaryletherketone resinoid is a class aromaticity semi-crystalline polymer, has that temperature classification height, radiation hardness, shock strength are high, wear resistance and characteristics such as resistance to fatigue is good, fire-retardant, electrical property is excellent.Since commercialization, obtained to use more widely at aerospace, automobile, electric, chemical industry, machinery and the field such as medical.The polyaryletherketone goods that are applied to above-mentioned field generally are the structure-type goods of making by injection molding method, but some Application Areas needs polyaryletherketone sheet material or board product, key components and parts such as industrial circle products such as electronics, automobile, machinery, aerospace, petrochemical compleies, these parts general requirements have very high precision, and quantity is not very many, often need by the precision optical machinery processing and manufacturing, so just need to adopt polyaryletherketone plate (sheet) material to make precision parts.The particularly startup of the large aircraft plan of China, comparatively urgent to the demand of polyaryletherketone sheet material or sheet material, the component of many comparatively small amt of aircraft (such as wear ring, fastening piece etc.) need polyaryletherketone sheet material or sheet material through the mechanical workout manufacturing; The interior trim of aircraft, the interior trim of spacecraft etc. all need polyaryletherketone sheet material or sheet material.The field such as other field such as automobile, electronics also is like this.Purpose of the present invention is exactly polyaryletherketone sheet material or the sheet material that satisfies the different field demand in order to prepare.
Background technology related to the present invention is the synthetic method technology (Chinese patent: " preparation method of polyether ethersulfone and polyetheretherketoneterpolymer terpolymer " of ketone-grouped resin, the patent No.: ZL 200610016723.6 not only can prepare polyether ethersulfone but also can prepare polyether-ether-ketone resin and their multipolymer; " tetramethylene sulfone is the synthetic method that contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer of solvent ", the patent No.: ZL 200610016889.8 not only can prepare and contains biphenyl polyether ether ketone but also can prepare polyether-ether-ketone resin and their multipolymer; " preparation of poly (aryl ether ketone) copolymer ", the patent No.: ZL 01138739.4, not only can prepare polyether-ether-ketone but also can prepare polyether-ether-ketone keto-resin and their multipolymer and " synthesizing of high-viscosity polyether-ether-ketone keto-resin containing biphenyl structure ", the patent No.: ZL 97102708.0, not only can prepare and contain biphenyl polyether ether ketone ketone but also can prepare polyether-ether-ketone keto-resin and their multipolymer) and the technology of preparing (Chinese patent: " hyperbranched polyarylether ketone; its preparation method and the application aspect viscosity modifier " of melt viscosity modifiers hyperbranched polyarylether ketone, the patent No.: ZL 200810051200.4 can prepare the melt viscosity modifiers that has excellent compatibility with ketone-grouped resin).
Summary of the invention
The objective of the invention is to utilize ketone-grouped resin, comprise polyether-ether-ketone (PEEK), polyether ether ketone ketone (PEEKK), contain biphenyl polyether ether ketone (PEDEK) and contain biphenyl polyether ether ketone ketone (PEDEKK) resin, by adding high temperature lubricant, melt viscosity modifiers, employing melt extrudes forming method and prepares polyaryletherketone sheet material or sheet material.
Equipment for the preparation of polyaryletherketone sheet material or sheet material is comprised of forcing machine, filtering net, mouthful mould and three-roller calendar, wherein extruder barrel (resin melting) temperature is 280～450 ℃, die temperature is 360～430 ℃, and the three-roller calendar temperature is 50～280 ℃; By changing or adjust a mouthful mould, can obtain thickness is polyaryletherketone sheet material or the sheet material of 0.2～20mm, and by control three-roller calendar setting temperature can produce half hitch crystalline state or unformed shape sheet material, when the three-roller calendar setting temperature is 160～280 ℃, can produce half hitch crystalline state sheet material or sheet material, when the three-roller calendar setting temperature is 50～160 ℃ and sheet metal thickness during less than 6mm, can produce unformed shape sheet material or sheet material.Because ketone-grouped resin has high strength, the characteristic such as high temperature resistant, corrosion-resistant, the polyaryletherketone sheet material of preparation or sheet material have intensity height, the characteristics such as high temperature resistant and corrosion-resistant.
PP Pipe Compound for the preparation of polyaryletherketone sheet material or sheet material of the present invention, pressing each component and 100wt% calculates, contain 90.0～100.0wt% ketone-grouped resin, the high temperature lubricant of 0～3.0wt% and the 0～10.0wt% structural formula hyperbranched polyarylether ketone shown in V or VI, prepared sheet material or board dimension are according to the mouth mould, the dimensional parameters of three-roller calendar and extruding-out process and decide, used in the present invention mouthful of Mould Breadth degree is 400～500mm, die lip thickness is 0.2～2mm, the running roller width of three-roller calendar is 500mm, the roller spacing of three-roller calendar is 0.1～25mm, and roller speed (pulling speed) is 0.5～20m/min.Therefore, the prepared sheet material of the present invention or sheet material width are 380～500mm, and thickness is 0.2～25mm.It prepares by the following method,
(1) ketone-grouped resin after the drying treatment is joined melting in the extruder barrel with four heating zone by hopper, the temperature of I heating zone is 280～340 ℃, the temperature of II heating zone is 330～380 ℃, the temperature of III heating zone is 380～420 ℃, and the temperature of IV heating zone is 380～450 ℃; Since the II heating zone, the temperature of each heating zone is higher 0～50 ℃ than last heating zone; The ketone-grouped resin of melting relies on the rotation of extruder screw to advance, and flows into slit mouth mould after being installed on the filtration unit filtration between head and mouthful mould, and the width of mouthful mould is 500mm, and the die lip thickness of mouthful mould is 0.2～2mm;
(2) the polyaryletherketone melt that enters slit mouth mould is shaped to the melting tablet in temperature is 360～430 ℃ mouth mould;
(3) then with described melting tablet diversion mouth mould, import three-roller calendar and carry out cooling and shaping; Temperature by the adjustment three-roller calendar is 50～280 ℃, can obtain unformed or half hitch crystal formation solid polyaryletherketone sheet material or sheet material; Die lip thickness by adjusting slit mouth mould (numerical range is 0.2～2mm), the roller spacing of three-roller calendar (numerical value be 0.1～25mm) and roller speed (0.5～20m/min) can obtain polyaryletherketone sheet material or the sheet material of different thickness.
Further preferred implementation comprises following four kinds of prescriptions,
Prescription a:
Ketone-grouped resin 100.0wt%
Prescription b:
Ketone-grouped resin 98.0～99.5wt%
High temperature lubricant 0.5～2.0wt%
Prescription c:
Ketone-grouped resin 92.0～98.0wt%
Hyperbranched polyarylether ketone polymer 2.0～8.0wt%
Prescription d:
Ketone-grouped resin 90.0～97.5wt%
High temperature lubricant 0.5～2.0wt%
Hyperbranched polyarylether ketone polymer 2.0～8.0wt%
The logarithmic specific concentration viscosity of polyether-ether-ketone (PEEK) resin is 0.76～0.80, melting index is 12～30g/10min, and its structural formula is shown in (I), and n is 〉=1 integer, the expression polymerization degree.
The logarithmic specific concentration viscosity of polyether ether ketone ketone (PEEKK) resin is 0.74～0.80, melting index is 20～40g/10min, and its structural formula is shown in (II), and n is 〉=1 integer, the expression polymerization degree.
The logarithmic specific concentration viscosity that contains biphenyl polyether ether ketone (PEDEK) resin is 0.74～0.80, melting index is 20～40g/10min, and its structural formula is shown in (III), and n is 〉=1 integer, the expression polymerization degree.
The logarithmic specific concentration viscosity that contains biphenyl polyether ether ketone ketone (PEDEKK) resin is 0.72～0.78, melting index is 20～40g/10min, and its structural formula is shown in (IV), and n is 〉=1 integer, the expression polymerization degree.
High temperature lubricant is particulate state or the pulverulent GENIOPLAST Pellet S that German Wacker company produces.
The hyperbranched polyarylether ketone polymer comprises two kinds of unformed and half hitch crystal formations, and the structural formula of unformed hyperbranched polymer is shown in (V):
Wherein, x, y, z represent the quantity of repeating unit on the branched structure, are 1～50 integer; Repeating unit terminal x1, x2, y1, y2, z1 are connected each position with z2 on, according to the value of x, y, z or connect next repeating unit, or connect R and carry out end-blocking;
R be F or
M is
The structural formula of half hitch crystal formation hyperbranched polyarylether ketone polymer is shown in (VI):
Wherein n is the positive integer more than or equal to 2, and x, y are positive number, and 3＜x/y＜7.
Filtration unit described in the upper noodle producing method is filtering net, and the polyaryletherketone melt is through filter screen and mouthful mould squeezing out quantitative;
Preparation method recited above, ketone-grouped resin carries out pre-dried before melt extruding moulding, and drying temperature is 130～150 ℃, and the time is 3～12 hours.
In the present invention, the degree of crystallinity of polyaryletherketone sheet material or sheet material can be controlled by roller temperature and the roller speed of regulation and control three-roller calendar, adopts low roller temperature, high roller speed can make unformed or low-crystallinity polyaryletherketone sheet material or sheet material; Adopt high roll temperature, low roller speed can make hypocrystalline or high-crystallinity polyaryletherketone sheet material or sheet material; Can take the heating anneal heat setting method to improve the degree of crystallinity of polyaryletherketone sheet material or sheet material, thereby make polyaryletherketone sheet material or the raisings such as timber intensity and heat resisting temperature that make.
Description of drawings
Fig. 1: polyaryletherketone sheet material or sheet extrusion moulding process general flow chart.
Symbol 1 represents the base of high temperature single screw extrusion machine among Fig. 1, symbol 2 represents hopper, symbol 3 represents the barrel of forcing machine, wherein symbol I, II, III and IV represent respectively four heating zone of extruder barrel, symbol 4 represents filtering net, and symbol 5 represents slit mouth mould, and symbol 6 represents three-roller calendar, symbol 7 represents guide deflection sheave, and symbol 8 represents polyaryletherketone sheet material or sheet material.
In the present invention, if not refer in particular to, all equipment and subsidiary material etc. all can be buied from market or the plastic working industry is commonly used.
Embodiment
Further specify the present invention below by specific embodiment, but embodiment only is used for explanation, does not limit the scope of the invention.
Embodiment 1:
Adopt as shown in Figure 1 the poly-polyaryletherketone sheet material of equipment and process method preparation or sheet material.The screw diameter of employed single screw extrusion machine is
L/D=28, heating system is the electrically heated of 4 districts, top temperature is 450 ℃; Filtering net is for by 600 purpose central cores, its both sides respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire that form of 80 purposes that invest time outer both sides; The width of slit mouth mould is 500mm, and the die lip thickness of slit mouth mould can be regulated and control between 0.2～2mm, the die lip internal surface high polish of mouthful mould; The mouth mould can be adjusted between 3～20mm according to thickness and the technique of formed sheet apart from the distance of three-roller calendar; The running roller diameter of three-roller calendar is 150mm, and the running roller width is 500mm, and top temperature is 280 ℃, and roller surface chromium plating and high polish, pulling speed are 0～20m/min, and the running roller spacing is 0.1～25mm.
A kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, and prescription is as described in the following table, and the PEEK resin shown in the structure formula I, logarithmic specific concentration viscosity are 0.80:
PEEK resin 99wt%
High temperature lubricant 1wt%
Filtering net is aforesaid 5 layers of stainless (steel) wire, the die lip thickness of mouth mould is 0.5mm, and mouthful mould is 4mm apart from the distance of three-roller calendar, and the extruder screw rotating speed is 20rpm, the extrusion temperature of screw extrusion press is: a district is 300 ℃, two districts are 360 ℃, and three districts are 380 ℃, and four districts are 380 ℃, die temperature is 360 ℃, the running roller temperature of three-roller calendar is 80 ℃, and pulling speed is 5m/min, and the roller surface spacing is 0.3mm.Making width is 400mm, and thickness is the transparent unformed PEEK sheet material of 0.3mm.The tensile strength of sheet material is 90MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 240 ℃ of lower life-time service.
Embodiment 2:
As described in Example 1, just the screw speed with screw extrusion press is adjusted into 15rpm, extrusion temperature changes into: a district is 300 ℃, two districts are 365 ℃, and three districts are 385 ℃, and four districts are 385 ℃, die temperature changes 365 ℃ into, the running roller temperature of three-roller calendar is 80 ℃, and pulling speed is 5m/min, and the roller surface spacing is 0.2mm.Making width is 400mm, and thickness is the transparent unformed PEEK sheet material of 0.2mm.The tensile strength of sheet material is 90MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 240 ℃ of lower life-time service.
Embodiment 3:
As described in Example 1, another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, prescription is as described in the following table, and the PEEKK resin shown in the structure formula II, logarithmic specific concentration viscosity are 0.76:
PEEKK resin 98wt%
High temperature lubricant 2wt%
Filtering net is for by 500 purpose central cores, its both sides respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire that form of 80 purposes that invest time outer both sides, the die lip thickness of mouth mould is 0.6mm, the mouth mould is 5mm apart from the distance of three-roller calendar, the extruder screw rotating speed is 20rpm, the extrusion temperature of screw extrusion press changes into: a district is 320 ℃, two districts are 370 ℃, three districts are 390 ℃, four districts are 390 ℃, die temperature is 370 ℃, the running roller temperature of three-roller calendar is 90 ℃, and pulling speed is 8m/min, and the roller surface spacing is 0.3mm.Making width is 400mm, and thickness is the unformed PEEKK sheet material of 0.3mm.The tensile strength of sheet material is 100MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 250 ℃ of lower life-time service.
Embodiment 4:
As described in Example 3, just the extrusion temperature of screw extrusion press is changed into: a district is 320 ℃, and two districts are 375 ℃, three districts are 395 ℃, and four districts are 400 ℃, and die temperature is 370 ℃, the running roller temperature of three-roller calendar is 250 ℃, and pulling speed is 5m/min, and the roller surface spacing is 0.5mm.Making width is 400mm, and thickness is the half hitch crystal formation PEEKK sheet material of 0.5mm.The tensile strength of sheet material is 108MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 260 ℃ of lower life-time service.
Embodiment 5:
As described in Example 1, just another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, prescription is as described in the following table, and the PEEKK resin shown in the structure formula II, logarithmic specific concentration viscosity are 0.76:
PEEKK resin 95wt%
Unformed hyperbranched polyarylether ketone 5wt%
The structural formula of unformed hyperbranched polyarylether ketone is shown in (V), and its number-average molecular weight is 11.7 * 10
3, weight-average molecular weight is 62.2 * 10
3, dispersion index PDI is 5.3.
Filtering net is for by 500 purpose central cores, its both sides respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire that form of 80 purposes that invest time outer both sides, the die lip thickness of mouth mould is 0.8mm, the mouth mould is 8mm apart from the distance of three-roller calendar, the extruder screw rotating speed is 20rpm, the extrusion temperature of screw extrusion press changes into: a district is 320 ℃, two districts are 370 ℃, three districts are 380 ℃, four districts are 380 ℃, die temperature is 370 ℃, the running roller temperature of three-roller calendar is 250 ℃, and pulling speed is 10m/min, and the roller surface spacing is 0.5mm.Making width is 400mm, and thickness is the half hitch crystal formation PEEKK sheet material of 0.5mm.The tensile strength of sheet material is 110MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 260 ℃ of lower life-time service.
Embodiment 6:
As described in Example 5, just the die lip thickness with the mouth mould is adjusted into 0.5mm, and the running roller temperature of three-roller calendar is adjusted into 100 ℃, and pulling speed is 10m/min, and the roller surface spacing is 0.3mm.Making width is 400mm, and thickness is the unformed PEEKK sheet material of 0.3mm.The tensile strength of sheet material is 100MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 250 ℃ of lower life-time service.
Embodiment 7:
As described in Example 1, just another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, prescription is as described in the following table, and the PEDEKK resin shown in the structure formula IV, logarithmic specific concentration viscosity are 0.74:
PEDEKK 92wt％
High temperature lubricant 2wt%
Crystal type hyperbranched polyarylether ketone polymer 6wt%
The structural formula of crystal type hyperbranched polyarylether ketone is shown in (VI), and it adopts the vitriol oil is that the logarithmic specific concentration viscosity that solvent records is 0.14dL/g.
Filtering net is for by 500 purpose central cores, its both sides respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire that form of 80 purposes that invest time outer both sides, the die lip thickness of mouth mould is 0.6mm, the mouth mould is 8mm apart from the distance of three-roller calendar, the extruder screw rotating speed is 20rpm, the extrusion temperature of screw extrusion press changes into: a district is 360 ℃, two districts are 420 ℃, three districts are 430 ℃, four districts are 440 ℃, die temperature is 400 ℃, the running roller temperature of three-roller calendar is 150 ℃, and pulling speed is 12m/min, and the roller surface spacing is 0.3mm.Making width is 380mm, and thickness is the unformed PEDEKK sheet material of 0.3mm.The tensile strength of sheet material is 109MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 280 ℃ of lower life-time service.
Embodiment 8:
As described in Example 7, just the thickness with mouth mould die lip is adjusted into 1.5mm, and the running roller temperature of three-roller calendar is adjusted into 280 ℃, and pulling speed is 4m/min, and the roller surface spacing is 1.2mm.Making width is 400mm, and thickness is the half hitch crystal formation PEDEKK sheet material of 1.2mm.The tensile strength of sheet material is 116MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 290 ℃ of lower life-time service.
Embodiment 9:
As described in Example 7, just another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, prescription is as described in the following table, and the PEDEK resin shown in the structure formula III, logarithmic specific concentration viscosity are 0.76:
PEDEK 94wt％
High temperature lubricant 1wt%
Crystal type hyperbranched polyarylether ketone polymer 5wt% shown in the structure formula VI
Filter screen is for by 500 purpose central cores, its both sides respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire that form of 80 purposes that invest time outer both sides, the die lip thickness of mouth mould is 0.6mm, the mouth mould is 8mm apart from the distance of three-roller calendar, the extruder screw rotating speed is 20rpm, the extrusion temperature of screw extrusion press changes into: a district is 360 ℃, two districts are 420 ℃, three districts are 430 ℃, four districts are 430 ℃, die temperature is 390 ℃, the running roller temperature of three-roller calendar is 150 ℃, and pulling speed is 10m/min, and the roller surface spacing is 0.3mm.Making width is 400mm, and thickness is the unformed PEDEK sheet material of 0.3mm.The tensile strength of sheet material is 112MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 270 ℃ of lower life-time service.
Embodiment 10:
As described in Example 1, just the distance with mouth mould die lip is adjusted into 11mm, and the distance of mouthful mould and three-roller calendar is adjusted into 10mm, and the running roller temperature of three-roller calendar is 220 ℃, and pulling speed is 5m/min, and the roller surface spacing is 10mm.Making width is 400mm, and thickness is the half hitch crystal formation PEEK sheet material of 10mm.The tensile strength of sheet material is 96MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 250 ℃ of lower life-time service.
Embodiment 11:
As described in Example 1, just the distance with mouth mould die lip is adjusted into 15mm, and the distance of mouthful mould and three-roller calendar is adjusted into 12mm, and the running roller temperature of three-roller calendar is 240 ℃, and pulling speed is 2m/min, and the roller surface spacing is 14mm.Making width is 400mm, and thickness is the half hitch crystal formation PEEK sheet material of 14mm.The tensile strength of sheet material is 96MPa; Soaked respectively 20 days in 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, the apparent and tensile strength of sheet material is not any change; Sheet material can be at 250 ℃ of lower life-time service.
Claims (4)
1. a polyaryletherketone sheet material or sheet material, it is characterized in that: press each component and 100wt% and calculate, contain the ketone-grouped resin of 90.0～100.0wt%, the hyperbranched polyarylether ketone of the high temperature lubricant of 0～3.0wt% and 0～10.0wt%, and it is prepared by following steps
(1) ketone-grouped resin after the drying treatment is joined melting in the extruder barrel with four heating zone by hopper, the temperature of I heating zone is 280～340 ℃, the temperature of II heating zone is 330～380 ℃, the temperature of III heating zone is 380～420 ℃, and the temperature of IV heating zone is 380～450 ℃; Since the II heating zone, the temperature of each heating zone is higher 0～50 ℃ than last heating zone; The ketone-grouped resin of melting relies on the rotation of extruder screw to advance, and flows into slit mouth mould after being installed on the filtration unit filtration between head and mouthful mould, and the width of mouthful mould is 500mm, and the die lip thickness of mouthful mould is 0.2～2mm;
(2) the polyaryletherketone melt that enters slit mouth mould is shaped to the melting tablet in temperature is 360～430 ℃ mouth mould;
(3) then with described melting tablet diversion mouth mould, import three-roller calendar and carry out cooling and shaping; The temperature of three-roller calendar is 50～280 ℃, and the roller spacing of three-roller calendar is 0.1～25mm, and roller speed is 0.5～20m/min, is that 380～500mm, thickness are polyaryletherketone sheet material or the sheet material of 0.2～25mm thereby obtain width;
Ketone-grouped resin is polyether-ether-ketone PEEK resin, polyether ether ketone ketone PEEKK resin, contains biphenyl polyether ether ketone PEDEK resin or contain biphenyl polyether ether ketone ketone PEDEKK resin;
Wherein, the logarithmic specific concentration viscosity of polyether-ether-ketone PEEK resin is 0.76～0.80, melting index is 12～30g/10min, and its structural formula is shown in (I), and n is 〉=1 integer, the expression polymerization degree,
The logarithmic specific concentration viscosity of polyether ether ketone ketone PEEKK resin is 0.74～0.80, melting index is 20～40g/10min, and its structural formula is shown in (II), and n is 〉=1 integer, the expression polymerization degree,
The logarithmic specific concentration viscosity that contains biphenyl polyether ether ketone PEDEK resin is 0.74～0.80, melting index is 20～40g/10min, and its structural formula is shown in (III), and n is 〉=1 integer, the expression polymerization degree,
The logarithmic specific concentration viscosity that contains biphenyl polyether ether ketone ketone PEDEKK resin is 0.72～0.78, melting index is 20～40g/10min, and its structural formula is shown in (IV), and n is 〉=1 integer, the expression polymerization degree,
The structural formula of hyperbranched polyarylether ketone shown in (V),
Wherein, x, y, z represent the quantity of repeating unit on the branched structure, are 1～50 integer; Repeating unit terminal x1, x2, y1, y2, z1 are connected each position with z2 on, according to the value of x, y, z or connect next repeating unit, or connect R and carry out end-blocking;
R be F or
M is
2. a kind of polyaryletherketone sheet material as claimed in claim 1 or sheet material, it is characterized in that: described filtration unit is filtering net.
3. a kind of polyaryletherketone sheet material as claimed in claim 1 or sheet material, it is characterized in that: described slit mouth mould has best bright finish.
4. a kind of polyaryletherketone sheet material as claimed in claim 1 or sheet material is characterized in that: high temperature lubricant is particulate state or the pulverulent GENIOPLAST Pellet S high temperature lubricant that German Wacker company produces.
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| CN102898808B (en) * | 2012-10-12 | 2015-05-06 | 吉林大学 | Anti-bacterial and anti-mildew polyetheretherketone membrane with excellent gas barrier property and preparation method thereof |
| CN102942780B (en) * | 2012-11-19 | 2014-07-09 | 吉林大学 | Polyether-ether-ketone conductive thin film with controllable conductivity, and preparation method thereof |
| GB201516943D0 (en) | 2015-09-24 | 2015-11-11 | Victrex Mfg Ltd | Polymeric materials |
| CN106243675A (en) * | 2016-08-31 | 2016-12-21 | 中国科学院长春应用化学研究所 | A kind of antibacterial PAEK material and preparation method thereof |
| EP3638736A4 (en) * | 2017-06-15 | 2021-03-10 | Arkema, Inc. | Production of semicrystalline parts from pseudo-amorphous polymers |
| CN108454130A (en) * | 2018-02-05 | 2018-08-28 | 扬州富平新材料有限公司 | A kind of forming method of easy cutting RPET sheet materials |
| EP3835065A3 (en) * | 2019-12-11 | 2021-09-01 | The Boeing Company | Processable polymer, method, and apparatus for additive manufacture |
| WO2021132417A1 (en) * | 2019-12-27 | 2021-07-01 | 三菱ケミカル株式会社 | Composite material member, composite material, mobile object, and method for manufacturing composite material film |
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| CN100553938C (en) * | 2007-10-10 | 2009-10-28 | 长春吉大特塑工程研究有限公司 | A kind of preparation method of polyetheretherketonesteel steel bar |
| CN101357985B (en) * | 2008-09-23 | 2010-12-08 | 吉林大学 | Hyperbranched poly(aryl ether ketone), preparation method and application thereof in viscosity modifier |
| CN102120873B (en) * | 2011-01-19 | 2012-10-10 | 金发科技股份有限公司 | Biaxially-stretched polyaryletherketone film and preparation method thereof |
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