CN101168295A - Preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method - Google Patents
Preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method Download PDFInfo
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- CN101168295A CN101168295A CNA2006101140832A CN200610114083A CN101168295A CN 101168295 A CN101168295 A CN 101168295A CN A2006101140832 A CNA2006101140832 A CN A2006101140832A CN 200610114083 A CN200610114083 A CN 200610114083A CN 101168295 A CN101168295 A CN 101168295A
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Abstract
The invention relates to a formula and technique for preparing polyvinyl fluoride thin film by using a melt-out extrusion blowing method. Employing the technique, the polyvinyl fluoride and solvent are homogeneously mixed to form resin paste which is then extruded out in granulate shape via a screw type extrusion machine, or the resin paste is directly melted without granulation and is extruded out to produce a blowing bubble pipe, and the bubble pipe employs the method of in-out simultaneous cooling for roll-up after cooling, then the thin film is dried and shaped via pull-off and expelling solvent. The invention has the advantages of simple preparing technique, rapid film-forming speed, high efficiency and small equipment investment, the prepared film has simultaneous height orientation in the length and breadth directions, the thickness is capable of being controlled, the intensity is high, the degree of transparency is good, besides, the film has good opening performance, and has no compaction, the stability of the size is great.
Description
Technical field
The present invention relates to a kind of technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method, belong to polymer processing field.
Background technology
Polyvinyl fluoride is a kind of function admirable, utilize the very big polymer in space.Film by the PVF preparation has the ability of powerful anti-sunlight, solvent, soda acid, moisture and oxidation, be adapted to any harsh climate and environment, has splendid mechanical performance and ductility simultaneously, and in very wide temperature range, can keep toughness and bendability, therefore in thin-film material, occupy unique, very main status.Because the monomer PVF of PVF has only a fluorine atom that electronegativity is very big, the result forms dipole, and the interaction between dipole makes intermolecular active force increase, and the fusing point that causes polyvinyl fluoride is up to 210～220 ℃, and decomposition temperature also has only about 220 ℃, and is rather approaching between the two.Continue 15～20min under melt temperature, polyvinyl fluoride promptly begins thermal decomposition, continues 5min down at 235 ℃ and just sharply decomposes.These design features of PVF are brought very burden to processing and forming.General polyfluoroethylene resin can not adopt the method for melt processing of common thermoplastic resin.The preparation method of present existing polyvinyl fluoride thin film has extrusion, solution casting method and rolling process.United States Patent (USP) 2593813 and 3139470 pairs of extrusions are described in detail, and the film thickness of preparation is even, transparency is high; But this method will be through a plurality of operations such as batching, mixing, deaeration, moulding, dryings, and the production cycle is long; And the film strength that makes is lower, need carry out the secondary biaxial tension usually, and production can't be carried out continuously, and cost of equipment is very expensive.Though the solution casting method technical process is simple, it is convenient to implement, and requires that solution concentration is low, power consumption is high, production efficiency is low, even and polyvinyl fluoride at high temperature also be difficult to dissolving, have polymer gel particles.Therefore, the HMW polyvinyl fluoride is unwell to salivation method and is equipped with film.Rolling process generally is not suitable for the crystal polymer thing, because polyvinyl fluoride is the polymer of partially crystallizable, with the rolling process film forming certain difficulty is arranged, and report is few so far.
Melt extrude that the blow moulding cost of equipment is little, power consumption is low, technology is simple, and product have in length and breadth intensity evenly, need not advantages such as side cut, thickness and wide variety be flexible.Therefore, if can realize the blowing film forming of PVF, the breakthrough that will bring essence undoubtedly to the production industry of PVF film.The Dalvor X-6500 series fluororesin of Du Pont's exploitation can adopt blow moulding directly to melt extrude film forming.But this series plastics belongs to the modified product of polyvinyl fluoride, that is to say that conventional PVF resin adopts the technology of blowing thin films not appear in the newspapers.
Summary of the invention
The objective of the invention is at the limitation of prior art and a kind of technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method is provided, its characteristics are that the polyfluoroethylene resin that will in the past can't melt extrude processing directly utilizes screw extruder blowing film forming after plasticising; Technology is simple, rate of film build is high, film forming speed is fast, save the energy; The open and flat degree of film well, intensity height, transparency height, thickness evenly and be easy to regulate.
The objective of the invention is to realize that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method comprises following processing step:
1, in 100 parts of polyfluoroethylene resins, adds 20～200 parts of solvents, add 0～10 part of auxiliary additive then, under 20～80 ℃ of temperature, stir into uniform resin paste with high-speed mixer.
2, with above-mentioned resin paste under 100～200 ℃ of temperature with screw extruder melt extrude, blowing one one-step film forming, or resin paste is prior to granulation in extruder under 50～180 ℃ of temperature, again melt-blown two one-step film formings under 120～200 ℃ of temperature.
3, adopt the mode of the inside and outside cold air drying of bubble pipe to cool off the bubble pipe, remove solvent through hot-rolling or hot drying tunnel afterwards, make that final solvent is less than 5% in the film.
4, dried film rolling after cooling under the tension force condition is the polyvinyl fluoride thin film finished product.
Wherein, PVF resin choice wide range, optional viscosity average molecular weigh be between 300,000～700, any resin between 000.
Solvent is optional to have any in the gamma-butyrolacton, DMF, DMAc, DMP of big dipole moment or mixed solvent that these solvents are prepared according to a certain percentage.
Auxiliary additive is titanium dioxide or various organic pigment.
The present invention has following advantage compared to existing technology:
1, the present invention has changed the method for traditional polyvinyl fluoride system film, adopt plastic sheeting commonly used be blow molded into membrane process, the drying of film, stretching, typing can be carried out simultaneously, the rate of film build height, technical process is simple, equipment investment is few.
2, the resin paste that mixes can directly be utilized screw extruder to melt extrude one-step shaping and make film, need not the extruding pelletization process; Also can adopt granulation, melt-blown two one-step forming films.
3, the present invention adopts the blow moulding film forming, and the blow-up ratio adjustable extent of bubble pipe is wide, controllable thickness; Simultaneously film can be height-oriented on both direction in length and breadth, and film strength height, transparency are good.
4, the present invention adopts the mode of sending cold wind cooling, hot-rolling or passage of heat drying in the bubble pipe outside to remove solvent before rolling, and solvent evaporates speed is fast, and dried film opening is good, do not have contraction, dimensional stability is good.
The specific embodiment
Below by embodiment the present invention is specifically described.It is important to point out that embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment one:
At the 10kg molecular weight is the gamma-butyrolacton that 380,000 PVF resin adds 12kg, stirs swelling under 60 ℃ in high-speed mixer.Resin paste with swelling after good is taken out blowing film forming in the metering feeding device of the double screw extruder of packing into, and extrusion temperature is 145～175 ℃, and the dry heat roll temperature is 175 ℃.The blow-up ratio of film is 5: 1, and hot strength is 66MPa, and transparency is 91%.
Embodiment two:
At the 10kg molecular weight is the DMF that 640,000 PVF resin adds 15kg, under the normal temperature under the effect of stirring in high-speed mixer swelling.Resin paste with swelling after good is taken out blowing film forming in the metering feeding device of the single screw extrusion machine of packing into, and extrusion temperature is 130～155 ℃, and the dry heat roll temperature is 160 ℃.The blow-up ratio of film is 4.5, and hot strength is 58MPa, and transparency is 90%.
Embodiment three
At the 10kg molecular weight is that 520,000 PVF resin adds the gamma-butyrolacton of 13.5kg and the mixed solution (the mixed solution mass ratio is 1: 1) of DMP, under the normal temperature under the effect of stirring in high-speed mixer swelling.Resin paste with swelling after good is taken out granulation in the metering feeding device of the double screw extruder of packing into, and extrusion temperature is 100～175 ℃, uses single screw rod melt-blown film forming afterwards, and blow temperatures is 150～185 ℃.The dry-heat air temperature is 180 ℃.The blow-up ratio of film is 6, and hot strength is 74MPa, and transparency is 90%.
Claims (7)
1. the technology of a preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method, it is characterized in that comprising following processing step: (1) mixes polyvinyl fluoride and solvent at a certain temperature; (2) extrusion-blown modling film forming again after compound adding screw extruder directly melt extrudes the blowing film forming or utilizes the extruder granulation; (3) adopt the inside and outside air-cooled rolling of bubble pipe, the mode through hot-rolling or hot drying tunnel drying removes solvent again, makes that final solvent is less than 0.5% in the film.(4) dried film rolling after cooling is the polyvinyl fluoride thin film finished product.
2. the technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method as claimed in claim 1 is characterized in that it is 300,000～700,000 PVF resin that described polyvinyl fluoride can be selected viscosity average molecular weigh for use.
3. the technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method as claimed in claim 1, it is characterized in that described solvent can select gamma-butyrolacton, N for use, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAC), repefral (DMP) etc. have the solvent of bigger dipole moment, and its addition is 20～200 parts.
4. the technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method as claimed in claim 1, the solid-liquid mixing temperature can be between 20～80 ℃.
5. the technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method as claimed in claim 1 is characterized in that the mixture of PVF and solvent can directly melt extrude the blowing film forming, and plasticizing effect is good; Or adopting extruder elder generation's granulation blowing film forming again, plasticizing effect is better.
6. the technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method as claimed in claim 1 is characterized in that described screw extruder can be double screw extruder, also can be single screw extrusion machine, adopts the vented extruder effect better.
7. the technology of preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method as claimed in claim 1, the blow-up ratio that it is characterized in that film is 1～7, and draw ratio is 1～7, and the intensity in length and breadth of product is even.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2006101140832A CN101168295A (en) | 2006-10-27 | 2006-10-27 | Preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method |
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| CNA2006101140832A CN101168295A (en) | 2006-10-27 | 2006-10-27 | Preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method |
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| CN101168295A true CN101168295A (en) | 2008-04-30 |
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| CNA2006101140832A Pending CN101168295A (en) | 2006-10-27 | 2006-10-27 | Preparation of polyvinyl fluoride thin film by fusion extrusion blow molding method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675777A (en) * | 2011-03-03 | 2012-09-19 | 黄莲华 | Manufacture method for biaxially oriented PVDF thin film |
| CN105431275A (en) * | 2013-07-02 | 2016-03-23 | 温德默勒&霍乐沙两合公司 | Extrusion die for a film-blowing head and blowing head |
| CN107624515A (en) * | 2017-10-24 | 2018-01-26 | 建瓯市元润塑料有限公司 | Black fungus open air cultivating bacteria bag and its preparation and application method |
| CN108051136A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山合力仪表有限责任公司 | A kind of preparation method of diaphragm pressure gage isolation diaphragm |
| CN110167218A (en) * | 2019-05-16 | 2019-08-23 | 信义汽车玻璃(深圳)有限公司 | Manufacturing method, electric heating film and the electrified regulation laminated glass of electric heating film |
| CN111441139A (en) * | 2020-03-27 | 2020-07-24 | 四川东方绝缘材料股份有限公司 | Preparation method of liquid crystal polymer film |
| CN111673999A (en) * | 2020-05-08 | 2020-09-18 | 中天科技精密材料有限公司 | Preparation method and preparation system of transparent film |
-
2006
- 2006-10-27 CN CNA2006101140832A patent/CN101168295A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675777A (en) * | 2011-03-03 | 2012-09-19 | 黄莲华 | Manufacture method for biaxially oriented PVDF thin film |
| CN105431275A (en) * | 2013-07-02 | 2016-03-23 | 温德默勒&霍乐沙两合公司 | Extrusion die for a film-blowing head and blowing head |
| CN105431275B (en) * | 2013-07-02 | 2017-04-05 | 温德默勒&霍乐沙两合公司 | Extrusion die and blowing head for sheet blowing head |
| CN107624515A (en) * | 2017-10-24 | 2018-01-26 | 建瓯市元润塑料有限公司 | Black fungus open air cultivating bacteria bag and its preparation and application method |
| CN108051136A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山合力仪表有限责任公司 | A kind of preparation method of diaphragm pressure gage isolation diaphragm |
| CN110167218A (en) * | 2019-05-16 | 2019-08-23 | 信义汽车玻璃(深圳)有限公司 | Manufacturing method, electric heating film and the electrified regulation laminated glass of electric heating film |
| CN111441139A (en) * | 2020-03-27 | 2020-07-24 | 四川东方绝缘材料股份有限公司 | Preparation method of liquid crystal polymer film |
| CN111441139B (en) * | 2020-03-27 | 2022-07-05 | 四川东方绝缘材料股份有限公司 | Preparation method of liquid crystal polymer film |
| CN111673999A (en) * | 2020-05-08 | 2020-09-18 | 中天科技精密材料有限公司 | Preparation method and preparation system of transparent film |
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Application publication date: 20080430 |