CN103937242B - The preparation method of biaxial orientation polyphenyl sulfide composite film - Google Patents
The preparation method of biaxial orientation polyphenyl sulfide composite film Download PDFInfo
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- CN103937242B CN103937242B CN201410095068.2A CN201410095068A CN103937242B CN 103937242 B CN103937242 B CN 103937242B CN 201410095068 A CN201410095068 A CN 201410095068A CN 103937242 B CN103937242 B CN 103937242B
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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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/9165—Electrostatic pinning
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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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/365—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pumps, e.g. piston pumps
- B29C48/37—Gear pumps
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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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
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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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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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
-
- 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
- B29C2948/92704—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
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
Abstract
The present invention relates to specialty films preparing technical field, the particularly preparation method of the polyphenyl sulfide composite film of a kind of good toughness, excellent heat resistance, this preparation method has the masterbatch of preparation, curtain coating slab and stretching film forming step. Adopt biaxial orientation polyphenyl sulfide composite film prepared by technical scheme of the present invention to have excellent heat resistance, dimensional stability, hot formability and toughness, biaxial orientation polyphenyl sulfide composite film of the present invention can be applicable to the electrically insulating materials such as motor, transformer, insulated cable or moulding material, circuit base material and mobile phone with fields such as speaker diaphragms.
Description
Technical field
The present invention relates to specialty films preparing technical field, particularly a kind of good toughness, excellent heat resistance is poly-The preparation method of diphenyl sulfide laminated film.
Background technology
Along with the continuous progress of social development and science and technology, people open new technology and new materialSend out more and more extensive, also more and more higher to the application requirements of the insulating materials such as electronics, electrical equipment, especially absolutely electricEdge Material Field there is high heat resistance, hydrolytic resistance, water imbibition is low and moisture absorption is low new material.
Polyphenylene sulfide (PPS) has the heat endurance under excellent chemical resistance and high temperature, water imbibition,Moisture absorption is lower, and has anti-flammability, insulating properties, radiation resistance and good mechanical performance, can extensively answerFor automobile, Aero-Space, electronics and Food Engineering Development aspect. PPS film has the heat-resisting of excellenceProperty, anti-flammability, rigidity, chemical reagent resistance, the excellent feature such as electrical insulating property excellence, agent of low hygroscopicity,Can be used as the insulating materials of basement membrane, capacitor, other electronic components or the equipment of magnetic recording medium. ButThat toughness and the intensity of single PPS material product are poor, are easier to embrittlement, especially PPS film systemProduct, toughness and elongation at break are lower, are difficult to meet the instructions for use of modern society.
Summary of the invention
The technical problem to be solved in the present invention is: exist for single PPS film article of the prior artToughness and elongation at break are lower, are difficult to the problem of the instructions for use that meets modern society, and a kind of each side is providedFace performance is comparatively excellent biaxial orientation polyphenyl sulfide composite film and preparation method thereof all.
The technical solution adopted for the present invention to solve the technical problems is: a kind of biaxial orientation polyphenylene sulfide is compoundThe preparation method of film, this preparation method has following steps:
(1) masterbatch preparation
According to mass ratio meter, prepare film polyphenylene sulfide resin, organic elastomer and inorganic filler, whereinThe proportioning of film polyphenylene sulfide resin and organic elastomer is 85～99: 1～15, film-grade polyphenylene sulfideThe total amount sum of resin and organic elastomer and the proportioning of inorganic filler are 100: 0.2～0.6; By above-mentioned thingMaterial, according to the charging sequence of film polyphenylene sulfide resin, organic elastomer, inorganic filler, squeezes through twin-screwGo out after machine is extruded and make masterbatch, wherein extruder temperature is between 310～330 DEG C;
(2) curtain coating slab
The masterbatch that step (1) is obtained and film polyphenylene sulfide resin are with mass ratio 1～3: 7～9 ratioExample is mixed, extrudes through double screw extruder melt blending, and be then 30～40 DEG C applying to surface temperatureThe cold roller of electrostatic charge carries out closely sealed cooling curing, the polyphenylene sulfide tape casting diaphragm not stretched when conveying;
Wherein, rate of feeding 25～50r/min, screw speed 150～250r/min, measuring pump rotating speed 25～50r/min, fusion plastification temperature is 310～340 DEG C, die head temperature is 315～345 DEG C;
(3) stretching film forming
The polyphenylene sulfide tape casting diaphragm not stretching that step (2) is obtained carries out biaxial stretch-formed, and drawing process is adoptedWith first longitudinal stretching in the longitudinal direction, then on width, carry out the biaxial stretch-formed successively of cross directional stretchMethod, specific as follows:
A, longitudinal stretching: tape casting diaphragm is sent into longitudinal stretching roller, on the longitudinal direction of film, stretch,Stretching ratio is 2.0～4.0 times, and draft temperature is 90～110 DEG C, then uses the chill roll group of 20～50 DEG CCooling;
B, cross directional stretch: carry out preheating by sending into transverse drawing mill through the sheet of longitudinal stretching, then horizontalStretch, 95 DEG C～120 DEG C of preheat temperatures, preheating time 15～30s; Draft temperature is 100 DEG C～130 DEG C,3.0～5.0 times of stretching ratios; Subsequently this stretched film is carried out carrying out in lax heat on width fixedType, 250 DEG C～270 DEG C of heat setting temperatures, time 10～20s, relaxation rate 2～7%, is finally cooled to room temperature,Obtain biaxial orientation polyphenyl sulfide composite film.
Further, organic elastomer described in step (1) is polyethylene, polypropylene, polytetrafluoroethylene (PTFE), poly-One in ester, Merlon, the particle diameter of inorganic filler is 0.1～3 μ m; Film polyphenylene sulfide resinWith the proportioning of organic elastomer be 85: 15, the total amount sum of film polyphenylene sulfide resin and organic elastomerWith the proportioning of inorganic filler be 100: 0.4; Inorganic filler is silica, glass microballoon, calcium carbonate, sulphurOne in acid barium, titanium dioxide; Preferably 310 DEG C of extruder temperatures.
Described in step (1) and (2), film polyphenylene sulfide resin molecular weight is 4～50,000,315 DEG C timeMelt flow rate 100g/10min.
Preferably, described in step (2), masterbatch and film polyphenylene sulfide resin mass ratio are 2: 8; FeedingSpeed is preferably 35r/min, and screw speed is preferably 205r/min, and measuring pump rotating speed is preferably 38r/min,Fusion plastification temperature is preferably 310 DEG C, and die head temperature is preferably 315 DEG C.
Preferably, in step (3) a, longitudinal stretching multiplying power is 3.5 times, and draft temperature is 93 DEG C; Step(3), in b, cross directional stretch preheat temperature is 113 DEG C, preheating time 15s, draft temperature is 113 DEG C, drawsStretching multiplying power is 3.5 times, and heat setting temperature is 270 DEG C, time 15s, and relaxation rate is 5%.
Beneficial effect: in technical scheme of the present invention, adding of organic elastomer can effectively improve later stage polyphenylStructural strength, toughness and the elongation at break of thioether laminated film; Can effectively improve the adding of inorganic filler thinHeat resistance, thermal dimensional stability and the crystallinity of film, the insulating properties of gained composite are obviously fallenLow; Organic elastomer in preparation method of the present invention and inorganic filler add with the form of masterbatch, and processMelt extrude for twice, make the dispersion of resin in mixed material more even, effectively controlled reunion, makeObtain the more stable uniform of surface property of later stage PPS films, and greatly reduce production costs, improvedProductivity effect. Adopt biaxial orientation polyphenyl sulfide composite film prepared by technical scheme of the present invention to there is excellenceHeat resistance, thermal dimensional stability, hot formability and toughness, can be applicable to motor, transformer, insulated electroThe electrically insulating materials such as cable or moulding material, circuit base material and mobile phone are with fields such as speaker diaphragms.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described. Polypropylene in following embodiment byPetrochemical industry Yang Zi petrochemical industry Co., Ltd of state provides.
Embodiment mono-
A preparation method for biaxial orientation polyphenyl sulfide composite film, this preparation method has following steps:
(1) masterbatch preparation
According to mass ratio meter, prepare film polyphenylene sulfide resin, polypropylene and silica, wherein filmLevel polyphenylene sulfide and polyacrylic proportioning are 85: 15, film polyphenylene sulfide resin and polyacrylic totalThe proportioning of amount sum and silica is 100: 0.4; By above-mentioned material according to film polyphenylene sulfide resin,The charging sequence of polypropylene, silica adds double screw extruder, first by film polyphenylene sulfide resin andPolypropylene fully stirs and obtains hybrid resin, adds subsequently silica in hybrid resin, squeezes through twin-screwAfter going out, make masterbatch, extruder temperature is 310 DEG C;
(2) curtain coating slab
The masterbatch that step (1) is obtained mixes with the mass ratio ratio of 2: 8 with film polyphenylene sulfide resin,Extrude through double screw extruder melt blending, then to surface temperature be 30 DEG C to apply the cold roller of electrostatic charge defeatedWhen sending, carry out closely sealed cooling curing, thus the polyphenylene sulfide tape casting diaphragm not stretched, wherein meltingPlasticization temperature is at 310 DEG C, 315 DEG C of die head temperatures, and rate of feeding 35r/min, screw speed 205r/min,Measuring pump rotating speed 38r/min;
(3) stretching film forming
The polyphenylene sulfide tape casting diaphragm not stretching that step (2) is obtained carries out biaxial stretch-formed, and drawing process is adoptedWith first longitudinal stretching in the longitudinal direction, then on width, carry out the biaxial stretch-formed successively of cross directional stretchMethod, concrete steps are as follows:
A, longitudinal stretching: tape casting diaphragm is sent into longitudinal stretching roller, on the longitudinal direction of film, stretch,Stretching ratio is 3.5 times, and draft temperature is 93 DEG C, then uses the chill roll group of 20～50 DEG C cooling;
B, cross directional stretch: carry out cross directional stretch, preheating by sending into transverse drawing mill through the sheet of longitudinal stretching113 DEG C of temperature, preheating time 15s; Draft temperature is 113 DEG C, 3.5 times of stretching ratios; Subsequently this is drawnStretch film and on width, carry out in lax carrying out thermal finalization, 270 DEG C of heat setting temperatures, time 15s,Relaxation rate 5%, is finally cooled to room temperature, obtains biaxial orientation polyphenyl sulfide composite film.
Embodiment bis-
A preparation method for biaxial orientation polyphenyl sulfide composite film, this preparation method has following steps:
(1) masterbatch preparation
According to mass ratio meter, prepare film polyphenylene sulfide resin, polypropylene and silica, wherein filmLevel polyphenylene sulfide and polyacrylic proportioning are 85: 15, film polyphenylene sulfide resin and polyacrylic totalThe proportioning of amount sum and silica is 100: 0.4; By above-mentioned material according to film polyphenylene sulfide resin,The charging sequence of polypropylene, silica adds double screw extruder, first by film polyphenylene sulfide resin andPolypropylene fully stirs and obtains hybrid resin, adds subsequently silica in hybrid resin, squeezes through twin-screwAfter going out, make masterbatch, extruder temperature is 320 DEG C;
(2) curtain coating slab
The masterbatch that step (1) is obtained mixes with the mass ratio ratio of 2: 8 with film polyphenylene sulfide resin,Extrude through double screw extruder melt blending, then to surface temperature be 35 DEG C to apply the cold roller of electrostatic charge defeatedWhen sending, carry out closely sealed cooling curing, thus the polyphenylene sulfide tape casting diaphragm not stretched, wherein meltingPlasticization temperature is at 320 DEG C, 315 DEG C of die head temperatures, and rate of feeding 35r/min, screw speed 200r/min,Measuring pump rotating speed 45r/min;
(3) stretching film forming
The polyphenylene sulfide tape casting diaphragm not stretching that step (2) is obtained carries out biaxial stretch-formed, and drawing process is adoptedWith first longitudinal stretching in the longitudinal direction successively, then on width, carry out the biaxial stretch-formed of cross directional stretchMethod, concrete steps are as follows:
A, longitudinal stretching: tape casting diaphragm is sent into longitudinal stretching roller, on the longitudinal direction of film, stretch,Stretching ratio is 2.5 times, and draft temperature is 90 DEG C, then uses the chill roll group of 20～50 DEG C cooling;
B, cross directional stretch: carry out cross directional stretch, preheating by sending into transverse drawing mill through the sheet of longitudinal stretching108 DEG C of temperature, preheating time 20s; Draft temperature is 112 DEG C, 4.0 times of stretching ratios; Subsequently this is drawnStretch film and on width, carry out in lax carrying out thermal finalization, 250 DEG C of heat setting temperatures, time 10s,Relaxation rate 2%, is finally cooled to room temperature, obtains biaxial orientation polyphenyl sulfide composite film.
Embodiment tri-
A preparation method for biaxial orientation polyphenyl sulfide composite film, this preparation method has following steps:
(1) masterbatch preparation
According to mass ratio meter, prepare film polyphenylene sulfide resin, polypropylene and silica, wherein filmLevel polyphenylene sulfide and polyacrylic proportioning are 85: 15, film polyphenylene sulfide resin and polyacrylic totalThe proportioning of amount sum and silica is 100: 0.4; By above-mentioned material according to film polyphenylene sulfide resin,The charging sequence of polypropylene, silica adds double screw extruder, first by film polyphenylene sulfide resin andPolypropylene fully stirs and obtains hybrid resin, adds subsequently silica in hybrid resin, squeezes through twin-screwAfter going out, make masterbatch, extruder temperature is 315 DEG C;
(2) curtain coating slab
The masterbatch that step (1) is obtained mixes with the mass ratio ratio of 2: 8 with film polyphenylene sulfide resin,Extrude through double screw extruder melt blending, then to surface temperature be 37 DEG C to apply the cold roller of electrostatic charge defeatedWhen sending, carry out closely sealed cooling curing, thus the polyphenylene sulfide tape casting diaphragm not stretched, wherein meltingPlasticization temperature is at 315 DEG C, 325 DEG C of die head temperatures, and rate of feeding 35r/min, screw speed 195r/min,Measuring pump rotating speed 38r/min;
(3) stretching film forming
The polyphenylene sulfide tape casting diaphragm not stretching that step (2) is obtained carries out biaxial stretch-formed, and drawing process is adoptedWith first longitudinal stretching in the longitudinal direction successively, then on width, carry out the biaxial stretch-formed of cross directional stretchMethod, concrete steps are as follows:
A, longitudinal stretching: tape casting diaphragm is sent into longitudinal stretching roller, on the longitudinal direction of film, stretch,Stretching ratio is 3 times, and draft temperature is 95 DEG C, then uses the chill roll group of 20～50 DEG C cooling;
B, cross directional stretch: carry out cross directional stretch, preheating by sending into transverse drawing mill through the sheet of longitudinal stretching110 DEG C of temperature, preheating time 20s; Draft temperature is 115 DEG C, 4.5 times of stretching ratios; Subsequently this is drawnStretch film and on width, carry out in lax carrying out thermal finalization, 265 DEG C of heat setting temperatures, time 15s,Relaxation rate 6%, is finally cooled to room temperature, obtains biaxial orientation polyphenyl sulfide composite film.
Embodiment tetra-
A preparation method for biaxial orientation polyphenyl sulfide composite film, this preparation method has following steps:
(1) masterbatch preparation
According to mass ratio meter, prepare film polyphenylene sulfide resin, polypropylene and silica, wherein filmLevel polyphenylene sulfide and polyacrylic proportioning are 85: 15, film polyphenylene sulfide resin and polyacrylic totalThe proportioning of amount sum and silica is 100: 0.4; By above-mentioned material according to film polyphenylene sulfide resin,The charging sequence of polypropylene, silica adds double screw extruder, first by film polyphenylene sulfide resin andPolypropylene fully stirs and obtains hybrid resin, adds subsequently silica in hybrid resin, squeezes through twin-screwAfter going out, make masterbatch, extruder temperature is 325 DEG C;
(2) curtain coating slab
The masterbatch that step (1) is obtained mixes with the mass ratio ratio of 2: 8 with film polyphenylene sulfide resin,Extrude through double screw extruder melt blending, then to surface temperature be 38 DEG C to apply the cold roller of electrostatic charge defeatedWhen sending, carry out closely sealed cooling curing, thus the polyphenylene sulfide tape casting diaphragm not stretched, wherein meltingPlasticization temperature is at 330 DEG C, 330 DEG C of die head temperatures, and rate of feeding 33r/min, screw speed 200r/min,Measuring pump rotating speed 45r/min;
(3) stretching film forming
The polyphenylene sulfide tape casting diaphragm not stretching that step (2) is obtained carries out biaxial stretch-formed, and drawing process is adoptedWith first longitudinal stretching in the longitudinal direction, then on width, carry out the biaxial stretch-formed successively of cross directional stretchMethod, concrete steps are as follows:
A, longitudinal stretching: tape casting diaphragm is sent into longitudinal stretching roller, on the longitudinal direction of film, stretch,Stretching ratio is 4.0 times, and draft temperature is 100 DEG C, then uses the chill roll group of 20～50 DEG C cooling;
B, cross directional stretch: carry out cross directional stretch, preheating by sending into transverse drawing mill through the sheet of longitudinal stretching115 DEG C of temperature, preheating time 15s; Draft temperature is 118 DEG C, 5.0 times of stretching ratios; Subsequently this is drawnStretch film and on width, carry out in lax carrying out thermal finalization, 260 DEG C of heat setting temperatures, time 20s,Relaxation rate 7%, is finally cooled to room temperature, obtains biaxial orientation polyphenyl sulfide composite film.
Comparative example one
Polyphenylene sulfide is extruded to the polyphenylene sulfide stream not stretched through double screw extruder melt blendingProlong diaphragm, wherein fusion plastification temperature is at 310 DEG C, 315 DEG C of die head temperatures, 35 DEG C of cold-roll temperatures, feeding speedDegree 35r/min, screw speed 205r/min, measuring pump rotating speed 38r/min.
By curtain coating cast sheet successively longitudinally, in a lateral direction stretch, wherein 3.5 times of longitudinal stretching multiplying powers,93 DEG C of draft temperatures; Laterally 113 DEG C of preheat temperatures, preheating time 15s, 113 DEG C of draft temperatures, stretch doubly3.5 times of rates, 270 DEG C of heat setting temperatures, heat-setting time 15s, relaxation rate 5%; Finally being cooled to room temperature obtainsTo PPS films.
The performance of the PPS film of above-described embodiment and comparative example gained is as shown in the table:
From the data of upper table, adopt the combination property of the laminated film of the technical scheme gained of embodiment mono-The best, its properties compared with pure PPS film in comparative example 1 all increases, and electric insulation breakdown strengthWithout obviously reducing; Technical parameter in preparation method of composite film arranges percent thermal shrinkage and laterally/longitudinal fractureThe impact of percentage elongation is larger.
Claims (4)
1. a preparation method for biaxial orientation polyphenyl sulfide composite film, is characterized in that: this preparation method's toolHave the following steps:
(1) masterbatch preparation
According to mass ratio meter, prepare film polyphenylene sulfide resin, organic elastomer and inorganic filler, itsIn, the proportioning of film polyphenylene sulfide resin and organic elastomer is 85～99: 1～15, film-grade polyphenylThe total amount sum of sulfide resin and organic elastomer and the proportioning of inorganic filler are 100: 0.2～0.6; By upperState material according to the charging sequence of film polyphenylene sulfide resin, organic elastomer, inorganic filler, through two spiral shellsBar extruder is made masterbatch after extruding, and wherein extruder temperature is between 310～330 DEG C;
(2) curtain coating slab
The masterbatch that step (1) is obtained and film polyphenylene sulfide resin are with mass ratio 1～3: 7～9 ratioExample is mixed, extrudes through double screw extruder melt blending, and be then 30～40 DEG C applying to surface temperatureThe cold roller of electrostatic charge carries out closely sealed cooling curing when conveying, thus the polyphenylene sulfide casting films not stretchedSheet;
(3) stretching film forming
The polyphenylene sulfide tape casting diaphragm not stretching that step (2) is obtained carries out biaxial stretch-formed, and drawing process is adoptedWith first longitudinal stretching in the longitudinal direction, then on width, carry out the biaxial stretch-formed successively of cross directional stretchMethod, concrete steps are as follows:
A, longitudinal stretching: tape casting diaphragm is sent into longitudinal stretching roller, on the longitudinal direction of film, stretch,Stretching ratio is 2.0～4.0 times, and draft temperature is 90～110 DEG C, then uses the chill roll group of 20～50 DEG CCooling;
B, cross directional stretch: carry out preheating, preheat temperature by sending into transverse drawing mill through the sheet of longitudinal stretching95 DEG C～120 DEG C, preheating time 15～30s; Then cross directional stretch, draft temperature is 100 DEG C～130 DEG C,3.0～5.0 times of stretching ratios;
Subsequently this stretched film is carried out in lax carrying out thermal finalization, heat setting temperature on width250 DEG C～270 DEG C, time 10～20s, relaxation rate 2～7%, is finally cooled to room temperature, obtains biaxial orientationPolyphenyl sulfide composite film;
Described organic elastomer is one in polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyester, MerlonKind; Inorganic filler is the one in silica, glass microballoon, calcium carbonate, barium sulfate, titanium dioxide.
2. the preparation method of biaxial orientation polyphenyl sulfide composite film according to claim 1, its featureBe: the rate of feeding of the double screw extruder described in step (2) is 25～50r/min, and screw speed is150～250r/min, measuring pump rotating speed is 25～50r/min, fusion plastification temperature is 310～340 DEG C, mouldTemperature is 315～345 DEG C.
3. the preparation method of biaxial orientation polyphenyl sulfide composite film according to claim 1, its featureBe: the stretching ratio described in step (3) a is 3.5 times, and draft temperature is 93 DEG C; In step (3) bDescribed preheat temperature is 113 DEG C, and be 15s preheating time, and draft temperature is 113 DEG C, and stretching ratio is3.5 times, heat setting temperature is 270 DEG C, and heat-setting time is 15s, and relaxation rate is 5%.
4. the preparation method of biaxial orientation polyphenyl sulfide composite film according to claim 2, its featureBe: the rate of feeding of the double screw extruder described in step (2) is 35r/min, and screw speed is205r/min, measuring pump rotating speed is 38r/min, and fusion plastification temperature is 310 DEG C, and die head temperature is315℃。
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| CN105926168B (en) * | 2016-05-12 | 2018-01-30 | 武汉纺织大学 | A kind of preparation method of the polyphenylene sulfide fibre perforated membrane of biaxial tension |
| CN106003747B (en) * | 2016-05-12 | 2018-02-13 | 武汉纺织大学 | A kind of preparation method of the polyester fiber perforated membrane of biaxial tension |
| CN105922605B (en) * | 2016-05-12 | 2018-01-30 | 武汉纺织大学 | A kind of preparation method of the polypropylene non-woven fabric porous fiber film of biaxial tension |
| CN106554620B (en) * | 2016-11-24 | 2019-04-05 | 扬州亚宝新材料科技有限公司 | A kind of PPS films and preparation method thereof |
| CN106497059B (en) * | 2016-11-24 | 2019-04-05 | 扬州亚宝新材料科技有限公司 | Double membranes of a kind of polyphenylene sulfide and preparation method thereof |
| CN108099148A (en) * | 2017-12-05 | 2018-06-01 | 聚石化学（长沙）有限公司 | The ventilated membrane and its production technology of a kind of property |
| CN111477876A (en) * | 2019-01-24 | 2020-07-31 | 东丽先端材料研究开发（中国）有限公司 | Multilayer film, current collector, pole piece and battery |
| CN112477085B (en) * | 2020-10-23 | 2022-06-21 | 浙江新和成特种材料有限公司 | Preparation method of high-crystallinity polyphenylene sulfide film and product thereof |
| CN115386118A (en) * | 2022-09-16 | 2022-11-25 | 青岛宇田化工有限公司 | Preparation method of polyphenylene sulfide biaxially oriented film |
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