CN104151752A - Preparation method and application of master batch used for polyvinylidene fluoride film - Google Patents
Preparation method and application of master batch used for polyvinylidene fluoride film Download PDFInfo
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Abstract
The invention discloses a preparation method of a master batch used for a polyvinylidene fluoride film. The preparation method comprises the steps of mixing a polyvinylidene fluoride A resin, a polyvinylidene fluoride B resin, polymethyl methacrylate, titanium dioxide, a mobility modifier and an inner lubricating agent at a room temperature until the materials are stirred uniformly, melt-extruding, cooling and granulating at a temperature of 150-250 DEG C, and drying to obtain the master batch. According to a standard of GB/T3682-2000, melt indexes of the polyvinylidene fluoride A resin and polyvinylidene fluoride B resin at a temperature of 230 DEG C and a load of 5 kg is 30-60 g/10 min and 3-20 g/10 min respectively. Performances such as tensile strength and thermal shrinkage of the film prepared by the preparation method provided by the invention are greatly improved.
Description
Technical field
The present invention relates to field of plastic coloring, be specifically related to preparation method and the application thereof of Masterbatch for a kind of polyvinylidene difluoride film.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) is to be formed by vinylidene (VDF) homopolymerization, is a kind of thermoplastics of excellent performance, and in commercial run, application is very extensive.Although the fusing point of PVDF (165-180 ℃) and decomposition temperature (>350 ℃) differ larger, processing temperature is wide, and its degree of crystallinity is high, and viscosity is large, and poor fluidity causes its working ability poor.
In actual applications, due to polymethylmethacrylate (PMMA) and PVDF consistency better, therefore can suitably add PMMA to reduce the degree of crystallinity of PVDF, improve the processing plasticity-of PVDF, and can also reduce in process of production the cost of material.But PMMA can not show a candle to PVDF at weathering resistance, water vapor barrier property, so the amount of PMMA can not add too much, and less PMMA makes PVDF melt viscosity in extruding curtain coating process excessive, is unfavorable for the film forming that stretches.What therefore improve PVDF can processing fluidity be a problem that needs in the industry solution.
In addition, in PVDF film forming process, also can add in right amount some white inorganic pigments, as titanium dioxide etc., to improve opacifying power, ageing resistance of thin-film material etc.But research shows, these mineral dyes are dispersed poor in resin matrix, very easily reunite and cause film to produce defect.And in patent CN102666715, mention the polyvinylidene fluoride resin that has used two kinds of different melting index, and wherein a kind of is pellet, and another kind is powder, and this resin combination there will be skewness to a certain extent in actual production process.
Summary of the invention
That the object of the invention is to exist for above-mentioned fluorine-contained film or processing characteristics is not good or cause the problems such as film defects is more because mineral dye disperses inequality, provide that a kind of melt flow property is good, processing characteristics is good, mineral filler good dispersity, the good PVDF base film of over-all properties moulding Masterbatch.Object of the present invention is achieved by the following technical programs.
The technical scheme of a first aspect of the present invention provides the preparation method of a kind of polyvinylidene difluoride film with Masterbatch, comprise following steps: by polyvinylidene difluoride (PVDF) A resin, polyvinylidene difluoride (PVDF) B resin, polymethylmethacrylate, titanium dioxide, mobility properties-correcting agent, internal lubricant, at room temperature be mixed to material stirring even, at 150-250 ℃, melt extrude, cooling, granulation, dry after and get final product;
Described polyvinylidene difluoride (PVDF) A resin and polyvinylidene difluoride (PVDF) B resin, according to GB/T3682-2000 standard, under 230 ℃, 5kg load, melting index is for being respectively 30-60g/10min, and 3-20g/10min.
The Masterbatch that provides a kind of method providing according to technique scheme to prepare of the technical scheme of a second aspect of the present invention.
The technical scheme of a third aspect of the present invention provides Masterbatch that a kind of technical scheme of second aspect present invention provides for prepare the application of sun power backboard protective membrane by thermoplastic film's moulding process.
The method providing according to first aspect present invention technical scheme:
Described stirring in some embodiments, refers to the rotating speed mixing 5-20min with 300-1000r/min.
Embodiments of the present invention reactor used is high-speed mixer, and extrusion equipment is twin screw extruder.
In some embodiments, the mass ratio of polyvinylidene difluoride (PVDF) A resin, polyvinylidene difluoride (PVDF) B resin is 20:80-80:20.
In some embodiments, the quality sum of polyvinylidene difluoride (PVDF) A, B resin and the mass ratio of polymethylmethacrylate are 60:40-95:5.
In some embodiments, the mass ratio of the quality sum of polyvinylidene difluoride (PVDF) A, B resin and polymethylmethacrylate, titanium dioxide, mobility properties-correcting agent, internal lubricant is 100:5-30:1-5:1-10.
In some embodiments, described mobility properties-correcting agent is selected from phthalate, diester class, phosphoric acid ester or polyol ester class, and its boiling point is not less than 150 ℃.
In some embodiments, internal lubricant is selected from stearic acid, ricinolic acid, calcium stearate, lead stearate, stearic acid dibutyl tin, stearic amide, paraffin, polyethylene wax or oxidized polyethlene wax.
The water using in embodiments of the present invention is deionized water.
" room temperature " of the present invention represents the temperature of 20-30 ℃.
The definition "or" that the present invention uses represents alternatives, if suitable, they can be combined, and that is to say, term "or" comprises independent alternatives that each is listed and their combination.For example, " mobility properties-correcting agent is selected from phthalate, diester class, phosphoric acid ester or polyol ester class " represents that mobility modification can be a kind of among Phthalates, diester class, phosphoric acid ester, polyvalent alcohol Ester, can be also its more than one combination.
Unless clearly state in contrast, otherwise all scopes that the present invention quotes comprised end value.For example, " take 300-1000r/min rotating speed stir " represents that the scope of stirring velocity R is 300r/min≤R≤1000r/min.
Beneficial effect of the present invention is to introduce in formula two kinds of PVDF resin alloys of different melting index, is beneficial to the melt fluidity that increases resin; In addition, in formula, also suitably add mobility properties-correcting agent and internal lubricant, guaranteeing that on the basis of original material performance, the resin raw material that makes of maximum possible mixes with auxiliary agent; It is even that these two kinds of modes are all beneficial to material plasticizing, guarantees film performance homogeneous, the minimizing film forming defect of maximum possible.
Embodiment
The following stated be the preferred embodiment of the present invention, the present invention protects is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, some distortion and the improvement made, all belong to protection scope of the present invention.Raw material used in embodiment all can obtain by commercial sources.
The starting material and the manufacturer thereof that in embodiment 1-6, adopt are as follows:
Polyvinylidene difluoride (PVDF) (PVDF): SOLEF 6010, U.S. Solvay company; JHR 500, Zhejiang Ju Hua group.
Polymethylmethacrylate (PMMA): High Impact Grade VDR, French Arkema company.
Titanium dioxide (TiO
2): R103 rutile-type, du pont company.
Dioctyl phthalate (DOP) (DOP): electrical grade, Shandong, Shandong softening agent limited-liability company.
Poly(oxyethylene glycol) 400 (PEG 400): DOW, Guangzhou Gong Xin Chemical Co., Ltd..
Calcium stearate: nano level, the high close friend in Shandong and auxiliary agent company limited.
Polyethylene wax: EL-WAX, permanent safe chemical industry.
Embodiment 1
By the formula in table 1, take raw material, under room temperature, in high-speed mixer, mix, until material stirring is even, above-mentioned compound is joined in twin screw extruder, at 150-250 ℃, melt extrude, cooling, granulation, obtain high melt fluidity Masterbatch for polyvinylidene difluoride film after dry.
Masterbatch is joined to fusion plastification in single Screw Extrusion casting machine, fusion plastification temperature 190-220 ℃, screw speed 30r/min, again via sheet material/film mouth mould, 230 ℃ of die temperatures, by the moulding of casting and stretching device, after by film through 140 ℃ of heat treatment shapings, then trimming, after corona treatment, cooling rolling obtains polyvinylidene difluoride (PVDF) base film.
Above-mentioned film is made to the thick film of 25 μ m, press (85 ℃ of its tensile strength of ASTM D882 standard testing, its percent thermal shrinkage of ISO 11501 standard testings, its water vapor transmission rate (WVTR) of ISO15106 standard testing, its dielectric breakdown voltage of ASTM D149 standard testing, its surface tension of ASTM D2578 standard testing, two 85 tests, 85%RH, 3000h), the performance index of its xanthochromia index of ASTM E313-05 standard testing.Test result is in Table 2.
Embodiment 2
By the formula in table 1, take raw material, under room temperature, in high-speed mixer, mix, until material stirring is even, above-mentioned compound is joined in twin screw extruder, at 150-250 ℃, melt extrude, cooling, granulation, obtain high melt fluidity Masterbatch for polyvinylidene difluoride film after dry.
Masterbatch is joined to fusion plastification in single Screw Extrusion casting machine, fusion plastification temperature 200-230 ℃, screw speed 20r/min, again via sheet material/film mouth mould, 220 ℃ of die temperatures, by the moulding of casting and stretching device, after by film through 150 ℃ of heat treatment shapings, then trimming, after corona treatment, cooling rolling obtains polyvinylidene difluoride (PVDF) base film.
Above-mentioned film is made to the thick film of 25 μ m, press (85 ℃ of its tensile strength of ASTM D882 standard testing, its percent thermal shrinkage of ISO 11501 standard testings, its water vapor transmission rate (WVTR) of ISO15106 standard testing, its dielectric breakdown voltage of ASTM D149 standard testing, its surface tension of ASTM D2578 standard testing, two 85 tests, 85%RH, 3000h), the performance index of its xanthochromia index of ASTM E313-05 standard testing.Test result is in Table 2.
Embodiment 3
By the formula in table 1, take raw material, under room temperature, in high-speed mixer, mix, until material stirring is even, above-mentioned compound is joined in twin screw extruder, at 150-250 ℃, melt extrude, cooling, granulation, obtain high melt fluidity Masterbatch for polyvinylidene difluoride film after dry.
Masterbatch is joined to fusion plastification in single Screw Extrusion casting machine, fusion plastification temperature 210-230 ℃, screw speed 50r/min, again via sheet material/film mouth mould, 220 ℃ of die temperatures, by the moulding of casting and stretching device, after by film through 150 ℃ of heat treatment shapings, then trimming, after corona treatment, cooling rolling obtains polyvinylidene difluoride (PVDF) base film.
Above-mentioned film is made to the thick film of 25 μ m, press (85 ℃ of its tensile strength of ASTM D882 standard testing, its percent thermal shrinkage of ISO 11501 standard testings, its water vapor transmission rate (WVTR) of ISO15106 standard testing, its dielectric breakdown voltage of ASTM D149 standard testing, its surface tension of ASTM D2578 standard testing, two 85 tests, 85%RH, 3000h), the performance index of its xanthochromia index of ASTM E313-05 standard testing.Test result is in Table 2.
Embodiment 4
By the formula in table 1, take raw material, under room temperature, in high-speed mixer, mix, until material stirring is even, above-mentioned compound is joined in twin screw extruder, at 150-250 ℃, melt extrude, cooling, granulation, obtain high melt fluidity Masterbatch for polyvinylidene difluoride film after dry.
Masterbatch is joined to fusion plastification in single Screw Extrusion casting machine, fusion plastification temperature 200-220 ℃, screw speed 100r/min, again via sheet material/film mouth mould, 210 ℃ of die temperatures, by the moulding of casting and stretching device, after by film through 140 ℃ of heat treatment shapings, then trimming, after corona treatment, cooling rolling obtains polyvinylidene difluoride (PVDF) base film.
Above-mentioned film is made to the thick film of 25 μ m, press (85 ℃ of its tensile strength of ASTM D882 standard testing, its percent thermal shrinkage of ISO 11501 standard testings, its water vapor transmission rate (WVTR) of ISO15106 standard testing, its dielectric breakdown voltage of ASTM D149 standard testing, its surface tension of ASTM D2578 standard testing, two 85 tests, 85%RH, 3000h), the performance index of its xanthochromia index of ASTM E313-05 standard testing.Test result is in Table 2.
Embodiment 5
By the formula in table 1, take raw material, under room temperature, in high-speed mixer, mix, until material stirring is even, above-mentioned compound is joined in twin screw extruder, at 150-250 ℃, melt extrude, cooling, granulation, obtain high melt fluidity Masterbatch for polyvinylidene difluoride film after dry.
Masterbatch is joined to fusion plastification in single Screw Extrusion casting machine, fusion plastification temperature 200-230 ℃, screw speed 50r/min, again via sheet material/film mouth mould, 220 ℃ of die temperatures, by the moulding of casting and stretching device, after by film through 150 ℃ of heat treatment shapings, then trimming, after corona treatment, cooling rolling obtains polyvinylidene difluoride (PVDF) base film.
Above-mentioned film is made to the thick film of 25 μ m, press (85 ℃ of its tensile strength of ASTM D882 standard testing, its percent thermal shrinkage of ISO 11501 standard testings, its water vapor transmission rate (WVTR) of ISO15106 standard testing, its dielectric breakdown voltage of ASTM D149 standard testing, its surface tension of ASTM D2578 standard testing, two 85 tests, 85%RH, 3000h), the performance index of its xanthochromia index of ASTM E313-05 standard testing.Test result is in Table 2.
Embodiment 6
By the formula in table 1, take raw material, under room temperature, in high-speed mixer, mix, until material stirring is even, above-mentioned compound is joined in twin screw extruder, at 150-250 ℃, melt extrude, cooling, granulation, obtain high melt fluidity Masterbatch for polyvinylidene difluoride film after dry.
Masterbatch is joined to fusion plastification in single Screw Extrusion casting machine, fusion plastification temperature 210-230 ℃, screw speed 60r/min, again via sheet material/film mouth mould, 230 ℃ of die temperatures, by the moulding of casting and stretching device, after by film through 150 ℃ of heat treatment shapings, then trimming, after corona treatment, cooling rolling obtains polyvinylidene difluoride (PVDF) base film.
Above-mentioned film is made to the thick film of 25 μ m, press (85 ℃ of its tensile strength of ASTM D882 standard testing, its percent thermal shrinkage of ISO 11501 standard testings, its water vapor transmission rate (WVTR) of ISO15106 standard testing, its dielectric breakdown voltage of ASTM D149 standard testing, its surface tension of ASTM D2578 standard testing, two 85 tests, 85%RH, 3000h), the performance index of its xanthochromia index of ASTM E313-05 standard testing.Test result is in Table 2.
Comparative example
Get the PVDF base film that commercially available French Arkema company produces, test event is with embodiment 1, and test result is in Table 2.
The formula of the different embodiment of table 1 forms (unit: g)
The Performance Detection of the different embodiment of table 2 and comparative example
Compare with the result of comparative example, embodiment 1-6 gained film integral performance is all better than comparative example, and especially the performance such as the tensile strength of film, percent thermal shrinkage has improvement by a relatively large margin.
Claims (8)
1. the preparation method of Masterbatch for a polyvinylidene difluoride film, it is characterized in that, comprise following steps: by polyvinylidene difluoride (PVDF) A resin, polyvinylidene difluoride (PVDF) B resin, polymethylmethacrylate, titanium dioxide, mobility properties-correcting agent, internal lubricant, at room temperature be mixed to material stirring even, at 150-250 ℃, melt extrude, cooling, granulation, dry after and get final product;
Described polyvinylidene difluoride (PVDF) A resin and polyvinylidene difluoride (PVDF) B resin, according to GB/T3682-2000 standard, under 230 ℃, 5kg load, melting index is for being respectively 30-60g/10min, and 3-20g/10min.
2. preparation method according to claim 1, is characterized in that, the mass ratio of polyvinylidene difluoride (PVDF) A resin, polyvinylidene difluoride (PVDF) B resin is 20:80-80:20.
3. preparation method according to claim 1, is characterized in that, the quality sum of polyvinylidene difluoride (PVDF) A, B resin and the mass ratio of polymethylmethacrylate are 60:40-95:5.
4. preparation method according to claim 1, is characterized in that, the mass ratio of the quality sum of polyvinylidene difluoride (PVDF) A, B resin and polymethylmethacrylate, titanium dioxide, mobility properties-correcting agent, internal lubricant is 100:5-30:1-5:1-10.
5. preparation method according to claim 1, is characterized in that, described mobility properties-correcting agent is selected from phthalate, diester class, phosphoric acid ester or polyol ester class, and its boiling point is not less than 150 ℃.
6. preparation method according to claim 1, is characterized in that, internal lubricant is selected from stearic acid, ricinolic acid, calcium stearate, lead stearate, stearic acid dibutyl tin, stearic amide, paraffin, polyethylene wax or oxidized polyethlene wax.
7. the Masterbatch that preparation method as claimed in claim 1 is prepared.
8. a Masterbatch as claimed in claim 7 is for preparing the application of sun power backboard protective membrane by thermoplastic film's moulding process.
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Cited By (4)
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| CN104829975A (en) * | 2015-05-15 | 2015-08-12 | 江苏昊华光伏科技有限公司 | Mutual-soluble blending method for manufacturing PVDF solar rear panel film raw materials |
| CN104962023A (en) * | 2015-07-20 | 2015-10-07 | 金宝丽科技（苏州）有限公司 | Plastic material and preparation method thereof |
| CN106009427A (en) * | 2016-07-20 | 2016-10-12 | 郑泓 | Special material for white polyvinylidene fluoride cast film |
| CN114133684A (en) * | 2022-01-05 | 2022-03-04 | 立昌科技（赣州）有限公司 | PVDF color master batch, preparation method thereof and PVDF pre-coloring material |
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