CN102604370A - Intelligent waterproof moisture-permeable film and preparation method thereof - Google Patents
Intelligent waterproof moisture-permeable film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an intelligent waterproof moisture-permeable film. A matrix material and a waterproof moisture-permeable functional material are prepared into the waterproof moisture-permeable film by using a screw extruder in a film blowing method or a flow casting method. The preparation method comprises the following steps of: firstly cleaning and drying the matrix material for standby application; secondly, squeezing out a thermoplastic carrier material, inorganic nanometer particles and a processing agent at a certain extrusion temperature by using the extruder in a melt mixing method according to a certain mass ratio to prepare the waterproof moisture-permeable functional material; and finally, preparing the product by adopting the film blowing method or the flow casting method at the extrusion temperature condition of 120 DEG C-250 DEG C after mixing the matrix material and the prepared waterproof moisture-permeable functional material according to a mass ratio of 100:5-200. The intelligent waterproof moisture-permeable film has excellent waterproof moisture-permeable function in all weathers, i.e. a preferential temperature and a humidity range and has the characteristics of simple production technology, low cost of raw materials and high production efficiency.
Description
Technical field
The present invention relates to the preparation and the modification technology field of functional high molecule material, particularly relate to a kind of waterproof humidity-permeant film, specifically a kind of intelligent waterproof humidity-permeant film and preparation method thereof.
Background technology
Water proof and moisture permeable material is many relatively preferably is main with thermoplastic polyurethane for the performance of being sold on the market at present.And urethane (PU) is the macromolecular material that contains urethano group in a kind of molecular chain, can it be divided into thermoplastic polyurethane (TPU) and cross-linked type polyurethane (CPU) by the whether crosslinked of molecular chain wherein.Generally speaking, urethane is mainly got through addition polymerization progressively by polyvalent alcohol, isocyanic ester and small molecule chain extender.Mole proportioning through control isocyanic ester and hydroxyl can obtain to have concurrently the functional high molecule material of excellent mechanical property and superior elasticity, wear resistance, and this type of material has been widely used in fields such as automobile component, caking agent, building decoration, synthetic leather, aeronautical and space technology.
Polymerization reaction mechanism by urethane can know that the generation of polyurethane macromolecular must be attended by the use of polyvalent alcohol, isocyanic ester and small molecule chain extender.And the price of above three kinds of chemical raw materials is all very expensive, particularly wherein isocyanic ester.With 4; 4 '-diphenylmethanediisocyanate (MDI) is an example; Its present market price is all more than 2.5 ten thousand/ton; And domestic also only have can this chemical of scale prodn such as such minority unit of Yantai, Shandong Wan Hua limited-liability company, and its output can not satisfy domestic great demand fully, still need be from a large amount of imports of companies such as German Baeyer.Above-mentioned reason has caused urethane finished product fancy price, is example with the polyether(poly)urethane, and its market price all at 4-5 ten thousand/ton, has seriously hindered its large-scale application in fields such as waterproof humidity-permeant films.
In addition, also there is following problem with TPU as waterproof humidity-permeant film:
Though 1, the waterproof effect of pure TPU film is better, its rate of perviousness is merely 2000g/ (m2)-1 (24h)-1, and Application Areas is very limited.
2, waterproof and pass through wet function singleness can not satisfy the for example request for utilization under the conditions such as high temperature, low temperature, strong shearing force field of round-the-clock and complex environment.
3, the poor mechanical property of film, cracky.
4, the waterproofing and moisture-penetration performances heterogeneity of film.
5, mostly the Waterproof Breathable membrane technique is external major company monopolizations such as America and Europe, costs an arm and a leg.
Just because of having recognized above-mentioned defective; People often also reach the purpose that reduces material cost through adding some such as such mineral fillers such as lime carbonate, talcum powder, permanent white in the actual use of polyurethane material, but regrettably the add-on of this type of mineral filler is very limited.And after add-on surpasses certain value, the mechanical property of polyurethane material will have obvious impairment, can not satisfy the request for utilization of association area.
Summary of the invention
Technical problem to be solved by this invention is to above-mentioned prior art present situation; Have both good water-repellancy and water vapour permeability function and have production technique simple and provide, the low lattice of product are cheap, draw high a kind of intelligent waterproof humidity-permeant film that intensity is good and production efficiency is high and preparation method thereof.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of intelligent waterproof humidity-permeant film, this waterproof humidity-permeant film comprise body material and Waterproof Breathable functional materials; Said body material is wherein a kind of in polymeric amide, urethane and the polyester, and said Waterproof Breathable functional materials is by inorganic nano-particle with special two-dimentional micropore or three-dimensional micropore structure and hydrophilic thermal plasticity solid support material and processing aid is compound in proportion forms; Said body material and Waterproof Breathable functional materials utilize screw extrusion press to adopt blown film method or casting method to be prepared into the intelligent macromolecule mould material with round-the-clock Waterproof Breathable function by mass parts under 120 ℃-250 ℃ condition than the blending ratio of 100:5-200.
For optimizing technique scheme, the measure of taking also comprises:
The molding thickness of the intelligent macromolecule mould material of above-mentioned preparation is 10nm-200nm.
Above-mentioned thermoplastic carrier's material is one or more in polyamide 6, polyamide 66, polyamide 1010, polymeric amide 12, polyamide 6 10, polyamide 6 12, polyether(poly)urethane, PAUR, poly terephthalic acid polyether glycol ester and the poly terephthalic acid polyester glycol ester.
The above-mentioned inorganic nano-particle with two-dimentional micropore or three-dimensional micropore structure is one or more in molecular sieve, nanometer Al2O3, nanometer SiO2, nano TiO 2, nano imvite, SWCN, multi-walled carbon nano-tubes, zeyssatite and the zeolite.
Above-mentioned processing aid is one or more in antioxidant 1010, phosphorous acid diphenyl ester, polyethylene wax, OPE, calcium stearate, amine hydroxybenzene and the stearic amide.
Above-mentioned blown film method is at least a in moulding of up-draught cold type and the moulding of lower blowing water cold type.
Above-mentioned casting method is that thermoplasticity is extruded at least a in casting method and the solution wet method curtain coating.
The present invention also provides a kind of preparation method of intelligent waterproof humidity-permeant film, and this method may further comprise the steps:
A), with subsequent use after body material cleaning, the drying;
B), thermoplastic carrier's material, the inorganic nano-particle with two-dimentional micropore or three-dimensional micropore structure and processing aid are added evenly to stir in the impeller under normal temperature condition successively than the ratio of 100:5-100:0.5-1 in mass parts and make the function mixing material;
C), be under 120 ℃-250 ℃ the condition, to utilize forcing machine to adopt the method extruding pelletization of melt blending to make the Waterproof Breathable functional materials with above-mentioned function mixing material at extrusion temperature;
D), with above-mentioned subsequent use body material and the above-mentioned Waterproof Breathable functional materials that makes in the ratio uniform mixing of mass parts than 100:5-200 after, utilize single screw extrusion machine under 120 ℃-250 ℃ extrusion temperature condition, to adopt blown film method or casting method preparation cost product.
The rotating speed of above-mentioned step 2 high speed stirrer is 1000r/min.
Melt-blending process in the above-mentioned step 3 is that parallel double-screw is extruded, conical double-screw is extruded, two roller is opened at least a in refining or the banburying, and the molding thickness of this product of above-mentioned preparation moulding is at 10 μ m-200 μ m.
Compared with prior art; The present invention combines the waterproof and moisture permeability of nanotechnology and thermoplastic carrier's material self; Through the size of regulation and control nanoparticle and the state of piling up of the amorphous microcell of macromole; Improve the Waterproof Breathable film properties, make this product can round-the-clock be the function that all has good Waterproof Breathable in optimal temperature and the humidity range.This invention can be widely used in fields such as outdoor goods, clothes, footwear material, base camp tent, and it also has that production technique is simple, starting material are cheap is easy to get and characteristics that production efficiency is high.
Description of drawings
Fig. 1 is the preparating mechanism synoptic diagram of the embodiment of the invention;
Fig. 2 is the waterproofing and moisture-penetration performances figure of the round-the-clock waterproof humidity-permeant film of TPU base of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are described in further detail.
Shown in Fig. 1 to 2, a kind of intelligent waterproof humidity-permeant film of the present invention is characterized in that: this waterproof humidity-permeant film comprises body material and Waterproof Breathable functional materials; Said body material is wherein a kind of in polymeric amide, urethane and the polyester, and said Waterproof Breathable functional materials is by inorganic nano-particle with special two-dimentional micropore or three-dimensional micropore structure and hydrophilic thermal plasticity solid support material and processing aid is compound in proportion forms; Said body material and Waterproof Breathable functional materials utilize screw extrusion press to adopt blown film method or casting method to be prepared into the intelligent macromolecule mould material with round-the-clock Waterproof Breathable function by mass parts under 120 ℃-250 ℃ condition than the blending ratio of 100:5-200.Nano material has bigger surface-area, will show tangible nano effect when the size of particle is little during to a dimensioning, often is used to enhancing, the toughening modifying of material.Body material of the present invention can adopt any one in polymeric amide, urethane and the polyester; Body material is through combining with nanotechnology; The size of utilization regulation and control inorganic nano-particle and polymer microcell can be improved the harmony of waterproof humidity-permeant film effectively; Improve the mechanical property of film, product is reached satisfy the request for utilization under round-the-clock and the complicated environmental condition.The present invention have good Waterproof Breathable function and its starting material cheap, be easy to get, have the high characteristics of production efficiency, be specially adapted to fields such as outdoor goods, clothes, footwear material, base camp tent.
For further optimizing product performance, among the embodiment, the molding thickness of the intelligent macromolecule mould material of the present invention's preparation is 10nm-200nm.
Above-mentioned thermoplastic carrier's material is one or more in polyamide 6, polyamide 66, polyamide 1010, polymeric amide 12, polyamide 6 10, polyamide 6 12, polyether(poly)urethane, PAUR, poly terephthalic acid polyether glycol ester and the poly terephthalic acid polyester glycol ester.
The above-mentioned inorganic nano-particle with two-dimentional micropore or three-dimensional micropore structure is one or more in molecular sieve, nanometer Al2O3, nanometer SiO2, nano TiO 2, nano imvite, SWCN, multi-walled carbon nano-tubes, zeyssatite and the zeolite.
Above-mentioned processing aid is one or more in antioxidant 1010, phosphorous acid diphenyl ester, polyethylene wax, OPE, calcium stearate, amine hydroxybenzene and the stearic amide.
Above-mentioned blown film method is at least a in moulding of up-draught cold type and the moulding of lower blowing water cold type.
Above-mentioned casting method is that thermoplasticity is extruded at least a in casting method and the solution wet method curtain coating.
The present invention also provides a kind of preparation method of intelligent waterproof humidity-permeant film, and this method may further comprise the steps:
A, with body material clean, dry back is subsequent use;
B, thermoplastic carrier's material, the inorganic nano-particle with two-dimentional micropore or three-dimensional micropore structure and processing aid are added evenly to stir in the impeller under normal temperature condition successively than the ratio of 100:5-100:0.5-1 in mass parts and make the function mixing material;
C, be under 120 ℃-250 ℃ the condition, to utilize forcing machine to adopt the method extruding pelletization of melt blending to make the Waterproof Breathable functional materials with above-mentioned function mixing material at extrusion temperature;
D, with above-mentioned subsequent use body material and the above-mentioned Waterproof Breathable functional materials that makes in the ratio uniform mixing of mass parts than 100:5-200 after, utilize single screw extrusion machine under 120 ℃-250 ℃ extrusion temperature condition, to adopt blown film method or casting method preparation cost product.
The rotating speed of above-mentioned step b high speed stirrer is 1000r/min.
Melt-blending process among the above-mentioned step c is that parallel double-screw is extruded, conical double-screw is extruded, two roller is opened at least a in refining or the banburying, and the molding thickness of this product of above-mentioned preparation moulding is at 10 μ m-200 μ m.
Embodiment one,
At first subsequent use behind the polyamide 1010 cleaning-drying with body material.
Secondly under normal temperature condition; In impeller, add polyether(poly)urethane 100g, molecular sieve 50g, polyethylene wax 0.2g, calcium stearate 0.1g, 0.05g antioxidant 1010 and 0.05g phosphorous acid diphenyl ester successively; Stir under the stirrer 1000r/min condition make the function mixing material after; Adopt parallel double-screw extruder under the condition of 180 ℃ of extrusion temperatures, the function mixing material that obtains to be carried out extruding pelletization again, make the Waterproof Breathable functional materials.
And then by mass ratio 100:30 subsequent use polyamide 1010 and the above-mentioned Waterproof Breathable functional materials that makes in above-mentioned dry back put in the barrel of upward type single screw extrusion machine, at 230 ℃ of condition compacted unders for being the polyamide-based waterproof humidity-permeant film of water proof and moisture permeable material with the polyether(poly)urethane.
Each item technical indicator of the polyamide-based waterproof humidity-permeant film that the present invention makes is following:
Resistance to hydrostatic pressure is that to draw high intensity be that 42MPa, elongation at break are 550% for 5024g m-2 24-h, film greater than 10000mm H2O, water transmitance.
Embodiment two,
At first choose behind the polyether(poly)urethane body material cleaning-drying subsequent use.
Secondly under normal temperature condition; In impeller, add poly terephthalic acid polyether glycol ester 100g, nanometer SiO2 10g, nanometer Al2O3 90g, polyethylene wax 0.3g, calcium stearate 0.3g, 0.1g antioxidant 1010 and 0.05g phosphorous acid diphenyl ester successively; Stir under the stirrer 1000r/min condition make the function mixing material after; Adopt parallel double-screw extruder under 210 ℃ of conditions, the function mixing material that obtains to be carried out extruding pelletization again, make the Waterproof Breathable functional materials.
And then by mass ratio 100:100 subsequent use polyether(poly)urethane body material and the above-mentioned Waterproof Breathable functional materials that makes in above-mentioned dry back put in the barrel of upward type single screw extrusion machine, at 220 ℃ of condition compacted unders for being the polyurethane-base waterproof humidity-permeant film of water proof and moisture permeable material with poly terephthalic acid polyether glycol ester.
Each item technical indicator of the polyurethane-base waterproof humidity-permeant film that the present invention makes is following:
Resistance to hydrostatic pressure is that the intensity that draws high of 4236g m-2 24-h, film is that 46 Mpa, elongation at break are 465% greater than 10000mm H2O, water transmitance.
Embodiment three,
At first choose behind the poly terephthalic acid polyether glycol ester group body material cleaning-drying subsequent use.
Secondly under normal temperature condition; In impeller, add 100g polyamide 6, multi-walled carbon nano-tubes 3g, 2g nano TiO 2, polyethylene wax 0.3g, calcium stearate 0.2g, 0.2g antioxidant 1010 and 0.1g phosphorous acid diphenyl ester successively; Stir under the stirrer 1000r/min condition make the function mixing material after; Adopt parallel double-screw extruder under 210 ℃ of conditions, the function mixing material that obtains to be carried out extruding pelletization again, make the Waterproof Breathable functional materials.
And then by mass ratio 100:200 subsequent use poly terephthalic acid polyether glycol ester and the above-mentioned Waterproof Breathable functional materials that makes in above-mentioned dry back put in the barrel of upward type single screw extrusion machine, at 230 ℃ of condition compacted unders for being the poly terephthalic acid polyether glycol ester group waterproof humidity-permeant film of water proof and moisture permeable material with the polymeric amide.
Each item technical indicator of this poly terephthalic acid polyether glycol ester group waterproof humidity-permeant film is following:
Resistance to hydrostatic pressure is 3292g m-2 24-h greater than 10000mm H2O, water transmitance, and the intensity that draws high of film is that 48Mpa, elongation at break are 420%.
Embodiment four,
At first choose behind the polyether(poly)urethane body material cleaning-drying subsequent use.
Secondly under normal temperature condition; In impeller, add polyether(poly)urethane 100g, nanometer Al2O3 30g, zeyssatite 50g, polyethylene wax 0.3g, calcium stearate 0.25g, 0.3g antioxidant 1010 and 0.15g phosphorous acid diphenyl ester successively; Stir under the stirrer 1000r/min condition make the function mixing material after; Adopt parallel double-screw extruder under 180 ℃ of conditions, the function mixing material that obtains to be carried out extruding pelletization again, make the Waterproof Breathable functional materials.
And then by mass ratio 100:100 subsequent use polyether(poly)urethane and the above-mentioned Waterproof Breathable functional materials that makes in above-mentioned dry back put in the barrel of upward type single screw extrusion machine, at 190 ℃ of condition compacted unders for being the polyurethane-base waterproof humidity-permeant film of water proof and moisture permeable material with the polyether(poly)urethane.
Each item technical indicator of the polyurethane-base waterproof humidity-permeant film that the present invention makes is following:
Resistance to hydrostatic pressure is greater than 10000mm H2O, and the water transmitance is 6245g m-2 24-h, and the intensity that draws high of film is that 35Mpa, elongation at break are 580%.
Characteristics of the present invention are: with polymeric amide, urethane, polyester is matrix; The inorganic nano-particle and hydrophilic polyamide, urethane or the polyester that adopt the thermoplastic method for processing will have special pore size must have the Waterproof Breathable materials with function; Adopt blown film or casting method that matrix is mixed with the Waterproof Breathable functional materials again, make intelligent macromolecule film with round-the-clock Waterproof Breathable function.The present invention all has good Waterproof Breathable function in round-the-clock (being optimal temperature and humidity) scope; It is simple to have production technique; Starting material are cheap, be easy to get, and the advantage that production efficiency is high can be widely used in fields such as outdoor goods, clothes, footwear material, base camp tent
Most preferred embodiment of the present invention is illustrated, and various variations or the remodeling made by those of ordinary skills can not depart from the scope of the present invention.
Claims (10)
1. intelligent waterproof humidity-permeant film, it is characterized in that: this waterproof humidity-permeant film comprises body material and Waterproof Breathable functional materials; Said body material is wherein a kind of in polymeric amide, urethane and the polyester, and said Waterproof Breathable functional materials is by inorganic nano-particle with special two-dimentional micropore or three-dimensional micropore structure and hydrophilic thermal plasticity solid support material and processing aid is compound in proportion forms; Said body material and Waterproof Breathable functional materials utilize screw extrusion press to adopt blown film method or casting method to be prepared into the intelligent macromolecule mould material with round-the-clock Waterproof Breathable function by mass parts under 120 ℃-250 ℃ condition than the blending ratio of 100:5-200.
2. a kind of intelligent waterproof humidity-permeant film according to claim 1 is characterized in that: the molding thickness of the intelligent macromolecule mould material of said preparation is 10nm-200nm.
3. a kind of intelligent waterproof humidity-permeant film according to claim 1 is characterized in that: described thermoplastic carrier's material is one or more in polyamide 6, polyamide 66, polyamide 1010, polymeric amide 12, polyamide 6 10, polyamide 6 12, polyether(poly)urethane, PAUR, poly terephthalic acid polyether glycol ester and the poly terephthalic acid polyester glycol ester.
4. a kind of intelligent waterproof humidity-permeant film according to claim 1 is characterized in that: described inorganic nano-particle with two-dimentional micropore or three-dimensional micropore structure is one or more in molecular sieve, nanometer Al2O3, nanometer SiO2, nano TiO 2, nano imvite, SWCN, multi-walled carbon nano-tubes, zeyssatite and the zeolite.
5. a kind of intelligent waterproof humidity-permeant film according to claim 1 is characterized in that: described processing aid is one or more in antioxidant 1010, phosphorous acid diphenyl ester, polyethylene wax, OPE, calcium stearate, amine hydroxybenzene and the stearic amide.
6. a kind of intelligent waterproof humidity-permeant film according to claim 1 is characterized in that: described blown film method is at least a in moulding of up-draught cold type and the moulding of lower blowing water cold type.
7. a kind of intelligent waterproof humidity-permeant film according to claim 1 is characterized in that: described casting method is that thermoplasticity is extruded at least a in casting method and the solution wet method curtain coating.
8. preparation method who realizes the described all-weather intelligent waterproof humidity-permeant film of claim 1, it is characterized in that: this method may further comprise the steps:
A), with subsequent use after body material cleaning, the drying;
B), thermoplastic carrier's material, the inorganic nano-particle with two-dimentional micropore or three-dimensional micropore structure and processing aid are added evenly to stir in the impeller under normal temperature condition successively than the ratio of 100:5-100:0.5-1 in mass parts and make the function mixing material;
C), be under 120 ℃-250 ℃ the condition, to utilize forcing machine to adopt the method extruding pelletization of melt blending to make the Waterproof Breathable functional materials with above-mentioned function mixing material at extrusion temperature;
D), with above-mentioned subsequent use body material and the above-mentioned Waterproof Breathable functional materials that makes in the ratio uniform mixing of mass parts than 100:5-200 after, utilize single screw extrusion machine under 120 ℃-250 ℃ extrusion temperature condition, to adopt blown film method or casting method preparation cost product.
9. the preparation method of a kind of intelligent waterproof humidity-permeant film according to claim 8, it is characterized in that: the rotating speed of described step b high speed stirrer is 1000r/min.
10. the preparation method of a kind of intelligent waterproof humidity-permeant film according to claim 9; It is characterized in that: the melt-blending process among the described step c is that parallel double-screw is extruded, conical double-screw is extruded, two roller is opened at least a in refining or the banburying, and the molding thickness of this product of above-mentioned preparation moulding is at 10 μ m-200 μ m.
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| CN103194058A (en) * | 2013-04-08 | 2013-07-10 | 桂林电子科技大学 | High-thermal-conductive moisture permeable film and preparation method thereof |
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