CN102337018A - Polyaryletherketone sheet or board - Google Patents
Polyaryletherketone sheet or board Download PDFInfo
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- CN102337018A CN102337018A CN2011102139091A CN201110213909A CN102337018A CN 102337018 A CN102337018 A CN 102337018A CN 2011102139091 A CN2011102139091 A CN 2011102139091A CN 201110213909 A CN201110213909 A CN 201110213909A CN 102337018 A CN102337018 A CN 102337018A
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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
-
- 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
-
- 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 one type of polyaryletherketone sheet material or sheet material with intensity height, characteristics such as high temperature resistant and corrosion-resistant.
Background technology
The polyaryletherketone resinoid is one type of aromaticity semi-crystalline polymer, has temperature classification height, radiation hardness, shock strength height, wear resistance and characteristics such as resistance to fatigue is good, fire-retardant, electrical property excellence.Since commercialization, obtained to use more widely in fields such as aerospace, automobile, electric, chemical industry, machinery and medical treatment.The polyaryletherketone goods that are applied to above-mentioned field generally are the structure-type goods of making through injection molding method; But some Application Areas needs polyaryletherketone sheet material or board product; Key components and parts like 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 pass through the precision optical machinery processing and manufacturing, so just needs to adopt polyaryletherketone plate (sheet) material make precision parts.The particularly startup of the big 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 (like 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.Field such as other field such as automobile, electronics also is like this.The object of the invention is exactly polyaryletherketone sheet material or the sheet material that satisfies the different field demand in order to prepare.
The background technology relevant with the present invention is the compound method technology (Chinese patent: " preparation method of polyether ethersulfone and polyetheretherketoneterpolymer terpolymer " of polyaryletherketone 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 polyetheretherketone 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 poly aryl ether ketone, its preparation method and the application aspect viscosity modifier " of melt viscosity modifiers hyperbranched poly aryl ether ketone; The patent No.: ZL 200810051200.4 can prepare the melt viscosity modifiers that has excellent compatibility with the polyaryletherketone resin).
Summary of the invention
The objective of the invention is to utilize the polyaryletherketone resin; Comprise polyetheretherketone (PEEK), polyether ether ketone ketone (PEEKK), contain biphenyl polyether ether ketone (PEDEK) and contain biphenyl polyether ether ketone ketone (PEDEKK) resin; Through adding high temperature lubricant, melt viscosity modifiers, employing melt extrudes forming method and prepares polyaryletherketone sheet material or sheet material.
The equipment that is used to prepare polyaryletherketone sheet material or sheet material is made up of forcing machine, filtering net, mouthful mould and three-roller calendar; Wherein extruder barrel (resin fusion) temperature is 280～450 ℃; Die temperature is 360～430 ℃, and the three-roller calendar temperature is 50～280 ℃; Through changing or adjustment mouthful mould; Can obtain thickness is polyaryletherketone sheet material or the sheet material of 0.2～20mm; And through 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 the polyaryletherketone resin has HS, characteristic such as high temperature resistant, corrosion-resistant, the polyaryletherketone sheet material of preparation or sheet material have intensity height, characteristics such as high temperature resistant and corrosion-resistant.
The PP Pipe Compound that is used to prepare polyaryletherketone sheet material or sheet material of the present invention; Press each component and 100wt% and calculate, contain 90.0～100.0wt% polyaryletherketone resin, the high temperature lubricant of 0～3.0wt% and the 0～10.0wt% structural formula hyperbranched poly aryl ether ketone shown in V or VI; Prepared sheet material or board dimension are according to the dimensional parameters of mouth mould, three-roller calendar and extruding-out process and decide; Used in the present invention mouthful of Mould Breadth degree is 400～500mm, and die lip thickness is 0.2～2mm, and 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, prepared sheet material of the present invention or sheet material width are 380～500mm, and thickness is 0.2～25mm.It is prepared by following method,
(1) the polyaryletherketone resin after the drying treatment is joined fusion in the extruder barrel with four heating zone through 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; Fused polyaryletherketone resin relies on the rotation of extruder screw to advance, and after being installed on the filtration unit filtration between head and mouthful mould, flows into slit mouth 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 gets into slit mouth mould is shaped to the fusion tablet in temperature is 360～430 ℃ mouth mould;
(3), import three-roller calendar and carry out cooling and shaping then with described fusion tablet diversion mouth mould; Temperature through 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 through adjustment 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 the polyaryletherketone sheet material or the sheet material of different thickness.
Further preferred implementation comprises following four kinds of prescriptions,
Prescription a:
Polyaryletherketone resin 100.0wt%
Prescription b:
Polyaryletherketone resin 98.0～99.5wt%
High temperature lubricant 0.5～2.0wt%
Prescription c:
Polyaryletherketone resin 92.0～98.0wt%
Hyperbranched poly aryl ether ketone polymer 2.0～8.0wt%
Prescription d:
Polyaryletherketone resin 90.0～97.5wt%
High temperature lubricant 0.5～2.0wt%
Hyperbranched poly aryl ether ketone polymer 2.0～8.0wt%
The logarithmic specific concentration viscosity of polyetheretherketone (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.
Hyperbranched poly aryl ether 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; On each position of the terminal x1 of repeating unit, x2, y1, y2, z1 and z2, according to the value of x, y, z or be connected next repeating unit, or connect R and carry out end-blocking;
R is F or
M is
The structural formula of half hitch crystal formation hyperbranched poly aryl ether ketone polymkeric substance 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 above-prepared method is a filtering net, and the polyaryletherketone melt is quantitatively extruded through a filtering net and a mouthful mould;
Preparing method recited above, the polyaryletherketone 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 percent crystallinity of polyaryletherketone sheet material or sheet material can be controlled through the 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 percent 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 material extruding-out process general flow chart.
Symbol 1 is represented the base of high temperature single screw extrusion machine among Fig. 1, and symbol 2 is represented hopper, and symbol 3 is represented the barrel of forcing machine; Wherein symbol I, II, III and IV are represented four heating zone of extruder barrel respectively; Symbol 4 is represented filtering net, and symbol 5 is represented slit mouth mould, and symbol 6 is represented three-roller calendar; Symbol 7 is represented guide deflection sheave, and symbol 8 is represented 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 through specific embodiment below, but embodiment only is used for explanation, does not limit the scope of the invention.
Embodiment 1:
Adopt the preparation of equipment as shown in Figure 1 and process method to gather polyaryletherketone sheet material 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, and 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 forming 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 the thickness and the technology 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 running roller chrome-faced 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 it is of following table to fill a prescription, 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, and the die lip thickness of mouthful mould is 0.5mm, and mouthful mould is 4mm apart from the distance of three-roller calendar; The extruder screw rotating speed is 20rpm, and the extrusion temperature of screw extrusion press is: a district is 300 ℃, and two districts are 360 ℃; Three districts are 380 ℃, and four districts are 380 ℃, and die temperature is 360 ℃; The running roller temperature of three-roller calendar is 80 ℃, and pulling speed is 5m/min, and the running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 240 ℃ of following life-time service.
Embodiment 2:
Of embodiment 1, just the screw speed with screw extrusion press is adjusted into 15rpm, and 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 running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 240 ℃ of following life-time service.
Embodiment 3:
Of embodiment 1, another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, it is of following table to fill a prescription, 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 respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire forming of 80 purposes that invest time outer both sides by 500 purpose central cores, its both sides, and the die lip thickness of mouthful mould is 0.6mm, and mouthful mould is 5mm apart from the distance of three-roller calendar; The extruder screw rotating speed is 20rpm, and the extrusion temperature of screw extrusion press changes into: a district is 320 ℃, and two districts are 370 ℃; Three districts are 390 ℃; Four districts are 390 ℃, and die temperature is 370 ℃, and the running roller temperature of three-roller calendar is 90 ℃; Pulling speed is 8m/min, and the running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 250 ℃ of following life-time service.
Embodiment 4:
Of embodiment 3, just the extrusion temperature with screw extrusion press changes 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 running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 260 ℃ of following life-time service.
Embodiment 5:
Of embodiment 1, just another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, it is of following table to fill a prescription, and the PEEKK resin shown in the structure formula II, logarithmic specific concentration viscosity are 0.76:
PEEKK resin 95wt%
Unformed hyperbranched poly aryl ether ketone 5wt%
The structural formula of unformed hyperbranched poly aryl ether 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 respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire forming of 80 purposes that invest time outer both sides by 500 purpose central cores, its both sides, and the die lip thickness of mouthful mould is 0.8mm, and mouthful mould is 8mm apart from the distance of three-roller calendar; The extruder screw rotating speed is 20rpm, and the extrusion temperature of screw extrusion press changes into: a district is 320 ℃, and two districts are 370 ℃; Three districts are 380 ℃; Four districts are 380 ℃, and die temperature is 370 ℃, and the running roller temperature of three-roller calendar is 250 ℃; Pulling speed is 10m/min, and the running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 260 ℃ of following life-time service.
Embodiment 6:
Of embodiment 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 running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 250 ℃ of following life-time service.
Embodiment 7:
Of embodiment 1, just another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, it is of following table to fill a prescription, and the PEDEKK resin shown in the structure formula IV, logarithmic specific concentration viscosity are 0.74:
PEDEKK 92wt％
High temperature lubricant 2wt%
The hyperbranched poly aryl ether ketone polymer 6wt% of crystal type
The structural formula of crystal type hyperbranched poly aryl ether 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 respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire forming of 80 purposes that invest time outer both sides by 500 purpose central cores, its both sides, and the die lip thickness of mouthful mould is 0.6mm, and mouthful mould is 8mm apart from the distance of three-roller calendar; The extruder screw rotating speed is 20rpm, and the extrusion temperature of screw extrusion press changes into: a district is 360 ℃, and two districts are 420 ℃; Three districts are 430 ℃; Four districts are 440 ℃, and die temperature is 400 ℃, and the running roller temperature of three-roller calendar is 150 ℃; Pulling speed is 12m/min, and the running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 280 ℃ of following life-time service.
Embodiment 8:
Of embodiment 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 running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 290 ℃ of following life-time service.
Embodiment 9:
Of embodiment 7, just another kind of polyaryletherketone sheet material or sheet material PP Pipe Compound are added the forcing machine hopper, it is of following table to fill a prescription, and the PEDEK resin shown in the structure formula III, logarithmic specific concentration viscosity are 0.76:
PEDEK 94wt％
High temperature lubricant 1wt%
The hyperbranched poly aryl ether ketone polymer 5wt% of crystal type shown in the structure formula VI
Filter screen is for respectively being 200 purposes time skin and the outer 5 layers of stainless (steel) wire forming of 80 purposes that invest time outer both sides by 500 purpose central cores, its both sides, and the die lip thickness of mouthful mould is 0.6mm, and mouthful mould is 8mm apart from the distance of three-roller calendar; The extruder screw rotating speed is 20rpm, and the extrusion temperature of screw extrusion press changes into: a district is 360 ℃, and two districts are 420 ℃; Three districts are 430 ℃; Four districts are 430 ℃, and die temperature is 390 ℃, and the running roller temperature of three-roller calendar is 150 ℃; Pulling speed is 10m/min, and the running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 270 ℃ of following life-time service.
Embodiment 10:
Of embodiment 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 running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 250 ℃ of following life-time service.
Embodiment 11:
Of embodiment 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 running 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; In 30wt% sodium hydroxide and 30wt% aqueous sulfuric acid, soaked respectively 20 days, the apparent and tensile strength of sheet material does not have any variation; Sheet material can be at 250 ℃ of following life-time service.
Claims (10)
1. polyaryletherketone sheet material or sheet material; It is characterized in that: press each component and 100wt% and calculate, contain the polyaryletherketone resin of 90.0～100.0wt%, the high temperature lubricant of 0～3.0wt% and 0～10.0wt% hyperbranched poly aryl ether ketone; And it is prepared by following steps
(1) the polyaryletherketone resin after the drying treatment is joined fusion in the extruder barrel with four heating zone through 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; Fused polyaryletherketone resin relies on the rotation of extruder screw to advance, and after being installed on the filtration unit filtration between head and mouthful mould, flows into slit mouth 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 gets into slit mouth mould is shaped to the fusion tablet in temperature is 360～430 ℃ mouth mould;
(3), import three-roller calendar and carry out cooling and shaping then with described fusion tablet diversion mouth mould; 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.
2. a kind of polyaryletherketone sheet material as claimed in claim 1 or sheet material is characterized in that: the polyaryletherketone resin is polyetheretherketone PEEK resin, polyether ether ketone ketone PEEKK resin, contains biphenyl polyether ether ketone PEDEK resin or contain biphenyl polyether ether ketone ketone PEDEKK resin.
3. a kind of polyaryletherketone sheet material as claimed in claim 2 or sheet material; It is characterized in that: the logarithmic specific concentration viscosity of polyetheretherketone 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
4. a kind of polyaryletherketone sheet material as claimed in claim 2 or sheet material; It is characterized in that: 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
5. a kind of polyaryletherketone sheet material as claimed in claim 2 or sheet material; It is characterized in that: 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
6. a kind of polyaryletherketone sheet material as claimed in claim 2 or sheet material; It is characterized in that: 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
7. a kind of polyaryletherketone sheet material as claimed in claim 1 or sheet material is characterized in that: described filtration unit is a filtering net.
8. a kind of polyaryletherketone sheet material as claimed in claim 1 or sheet material is characterized in that: described clearance type mouth mould has best bright finish.
9. a kind of polyaryletherketone sheet material as claimed in claim 1 or sheet material is characterized in that: the hyperbranched poly aryl ether ketone comprises two kinds of unformed and half hitch crystal formations, the structural formula of unformed hyperbranched polymer shown in (V),
Wherein, x, y, z represent the quantity of repeating unit on the branched structure, are 1～50 integer; On each position of the terminal x1 of repeating unit, x2, y1, y2, z1 and z2, according to the value of x, y, z or be connected next repeating unit, or connect R and carry out end-blocking;
R is F or
M is
The structural formula of half hitch crystal formation hyperbranched poly aryl ether ketone polymkeric substance 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.
10. 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 that German Wacker company produces.
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