CN104474913A - Anti-pollution hollow fiber internal pressure intensifying membrane as well as preparation method and spinneret plate for achieving preparation method - Google Patents
Anti-pollution hollow fiber internal pressure intensifying membrane as well as preparation method and spinneret plate for achieving preparation method Download PDFInfo
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Abstract
The invention provides an anti-pollution hollow fiber internal pressure intensifying membrane which comprises a filtering membrane layer and a hollow structure, wherein the filtering membrane layer is made of a membrane preparation liquid; two or more long fibers are arranged in the filtering membrane layer; the length direction of the long fibers is identical to that of the hollow fiber internal pressure intensifying membrane; the long fibers have shrinkage different from that of the membrane preparation liquid in a gel bath. As the long fibers are added into the hollow fiber membrane, and the long fibers and the membrane preparation liquid have different gel speeds and shrinkage degrees in the gel bath, the fiber shrinkage can be controlled by selecting long fibers of different rigidity degrees and strength degrees, and the irregular degrees of internal channels of the hollow fiber membrane are further controlled. As the internal channels are rugged, and water inside the internal channels can form turbulent flow, the flashing intensity of water flow is improved, and the pollution degree of the membrane is effectively reduced finally.
Description
[technical field]
The present invention relates to hollow-fibre membrane, particularly a kind of antipollution, interior pressure enhancement type hollow fiber film, also relate to the preparation method of described hollow-fibre membrane, realize the spinneret of described preparation method and the spinning equipment containing described spinneret.
[background technology]
Along with industrial development, municipal sewage generation and complexity also increase thereupon, not only day by day complicated in MBR municipal wastewater field water environment, the difficulty of the feedwater such as running water field water treatment also strengthens further, and the complexity of pollutant, the further variation of water quality propose higher requirement to the resistance tocrocking of film.
In present stage major part water engineering employing, press mold filters, washing away of tunica fibrosa internal channel high speed current, significantly can reduce fouling membrane, but day by day severe along with water environment, needing to make tunica fibrosa internal channel to have flow velocity and higher scouring intensity faster could contamination containment further.
[summary of the invention]
The object of the invention is to overcome prior art defect, a kind of hollow-fibre membrane with the internal channel of certain flexibility is provided, to improve the scouring intensity of current in film silk inside, obtain the pressure-bearing degree of higher film, reduce the pollution level of film.
To achieve these goals, the invention provides a kind of antipollution hollow fiber internal pressure and strengthen film, described hollow fiber internal pressure strengthens film and has the filtration rete and hollow structure be made up of preparation liquid, two or more long fibres are provided with in described filtration rete, described long stapled length direction is consistent with the length direction that described hollow fiber internal pressure strengthens film, and described long fibre has the contraction different from preparation liquid in coagulation bath
In the present invention, preferably long stapled shrinkage factor is 50-98%.
Preferably, described long fibre is selected from terylene, polyamide fibre, aramid fiber or polypropylene fiber, described long fibre 150D/36F ~ 420D/72F.
The present invention also provides above-mentioned antipollution hollow fiber internal pressure to strengthen the preparation method of film, and described preparation method comprises the following steps:
(1) preparation liquid is prepared
At 40-70 DEG C, by masking resin, solvent, additive according to weight ratio 10-30:60-80:10-20 mix, stir, negative pressure deaeration, obtains masking feed liquid;
(2) core liquid is prepared
At 20-40 DEG C, solvent and water are mixed according to weight ratio 20-40:60-80, stir, negative pressure deaeration, obtains core liquid;
(3) apply
Adopt hollow-fibre membrane spinning-drawing machine, after long fibre is put silk, to long fibre coating adhesion force promoter composition at 30-70 DEG C, then make two or more long fibres simultaneously by the coated preparation liquid of spinneret;
(4) gel, arrangement, drying
Enter coagulation bath after coating preparation liquid, coagulation bath temperature is 60-80 DEG C, after arrangement, drying, receive silk, obtains antipollution hollow fiber internal pressure and strengthens film.
In the present invention, described masking resin is selected from Kynoar (PVDF), polyvinyl chloride (PVC), polyether sulfone (PES) or polyacrylonitrile (PAN).
According to one preferred embodiment, described adhesion force promoter composition is the adhesion promoter of 30:60:10 by weight: solvent: ethanol.
In the present invention, described adhesion promoter is PET adhesion promoter.
The antipollution hollow fiber internal pressure that the present invention also provides above-mentioned antipollution hollow fiber internal pressure enhancing film or above-mentioned preparation method to obtain strengthens the purposes of film in water treatment.
The present invention also provides the spinneret realizing preparation method, described spinneret comprises spinnerette body 11, be positioned at the preparation liquid import 12 of spinnerette body 11 side, the core liquid import 13 being positioned at spinnerette body 11 opposite side and the spinning outlet 15 being positioned at spinnerette body 11 bottom, mutually isolated preparation liquid path 14 and core liquid path 16 is had in the middle part of spinnerette body 11, preparation liquid path 14 exports 15 with preparation liquid import 12 and spinning and is communicated with, core liquid path 16 exports 15 with core liquid import 13 and spinning and is communicated with, described spinnerette body 11 top also has two or more fiber paths 17, the end of fiber path 17 is communicated with preparation liquid path 14.
The present invention also provides the spinning-drawing machine containing above-mentioned spinneret.
The technical scheme that present invention will be further described below:
The compressive resistance of existing hollow fiber internal pressure film is relatively low, fracture pressure is generally less than 0.3MPa, when operating pressure is too high (when generally exceeding 0.2MPa) easily there is rete and break, therefore cannot use higher pressure and flow velocity faster, thus limit scouring intensity.
In addition, because hollow-fibre membrane internal channel is through-type passage, according to hydrodynamics, during operation, flow rate of liquid is reduced to tube wall gradually by pipeline center, therefore the flow velocity on tube wall namely on rete is the lowest part of channel interior flow velocity, therefore significantly reduce scouring effect, reduce contamination resistance.
The present invention sets about from change hollow-fibre membrane inner passage shape, a kind of antipollution hollow fiber internal pressure is provided to strengthen film, described hollow fiber internal pressure strengthens film and has the filtration rete and hollow structure be made up of preparation liquid, by being provided with more than two or two long fibres in described filtration rete, and described long stapled length direction is consistent with the length direction that described hollow fiber internal pressure strengthens film, and described long fibre has the shrinkage factor different from preparation liquid in coagulation bath, make the gelation rate of rete in gel process and final shrinkage degree different from long stapled shrinkage degree, the effect that pipeline is rugged can be caused during contraction, rete tube wall is made to occur fold, form and there is erose hollow structure passage.
In the present invention, preferably long stapled shrinkage factor is 2-50%.Term " shrinkage factor " should be understood to long fibre in coagulation bath after heat shrinkable, the shaping rear length of long fibre and the difference of raw footage and the ratio of long fibre raw footage.Generally, long stapled shrinkage factor can not be very large, and too high shrinkage factor easily causes film silk to break in gel, type-approval process on the other hand, causes film silk cannot be shaping, and therefore long stapled shrinkage factor should be not more than 50%.But long stapled shrinkage factor should be greater than 0, the length namely after gel should be less than raw footage, just can guarantee that fold appears in rete tube wall, forms and has erose hollow structure passage, film silk contamination resistance is improved.
Preferably, described long fibre is selected from terylene, polyamide fibre, aramid fiber or polypropylene fiber.If use two or more different long fibres can not cause the serious difference of shrinkage factor and cause the consequence cannot shaped in coagulation bath simultaneously, then also can multiple different long fibre used in combination, as long as the hollow structure of hollow-fibre membrane can be made to produce to be bent, it is irregularly shaped to form.Generally, the long fibre of 150D ~ 420D, 36 ~ 72F all can realize the present invention, considers the difference of thicknesses of layers, when the thicknesses of layers of hollow-fibre membrane is thicker, may adopt the long fibre that D/F number is larger.
In term " D/F ", D refers to danier, is the thickness index of fiber or yarn.D refers to fiber or the weight grams of yarn when official regain of 9000 meters long, and the larger yarn of D number is thicker.
F refers to spinneret orifice number, and the fiber of identical D number or yarn F are more large more soft.
The preparation method that above-mentioned antipollution hollow fiber internal pressure strengthens film comprises the following steps:
(1) preparation liquid is prepared
At 40-70 DEG C, by masking resin, solvent, additive according to weight ratio 10-30:60-80:10-20 mix, stir, negative pressure deaeration, obtains masking feed liquid.
In the present invention, masking resin is the routine selection that hollow-fibre membrane is prepared in this area, such as be selected from Kynoar (PVDF), polyvinyl chloride (PVC), polyether sulfone (PES) or polyacrylonitrile (PAN), other preparation liquid materials being applicable to the wet-layer preparation of hollow-fibre membrane are also applicable to the present invention.Mixing between preparation liquid not of the same race belongs to prior art, and those skilled in the art can repeat to implement, and does not repeat at this.
Similarly, the component of coagulation bath and consumption also belong to the knowledge that those skilled in the art have grasped, and such as water, dimethylacetylamide (DMAC) or their mixture are all conventional coagulation baths.
Solvent is also the routine selection that hollow-fibre membrane is prepared in this area, such as dimethylacetylamide (DMAC), dimethyl formamide (DMF), nitrogen methyl pyrrolidone (NMP) or triethyl phosphate (TEP), or other solvents that can select.
In the present invention, additive such as polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG).
(2) core liquid is prepared
At 20-40 DEG C, solvent and water are mixed according to weight ratio 20-40:60-80, stir, negative pressure deaeration, obtains core liquid;
(3) apply
Adopt hollow-fibre membrane spinning-drawing machine, after long fibre is put silk, to long fibre coating adhesion force promoter composition at 30-70 DEG C, then make two or more long fibres simultaneously by the coated preparation liquid of spinneret;
The purposes of adhesion force promoter composition is that long fibre and rete are more combined closely, and can not be separated and cause film silk to break both when ensureing systolic dyssynchrony in coagulation bath.Its principle active component is adhesion promoter, such as, adopt the adhesion promoter of 30:60:10 by weight: solvent: ethanol, is coated on long fibre, till long fibre moistened surface by the form of spraying.
Adhesion promoter of the present invention is PET adhesion promoter, the KS610 type adhesion promoter that such as German KENO sells.
(4) gel, arrangement, drying
Enter coagulation bath after coating preparation liquid, coagulation bath temperature is 60-80 DEG C, after arrangement, drying, receive silk, obtains antipollution hollow fiber internal pressure and strengthens film.
Above-mentioned antipollution hollow fiber internal pressure strengthens film and can be applicable to water treatment.
In order to realize above-mentioned preparation method, the present invention improves spinneret, it comprises spinnerette body 11, be positioned at the preparation liquid import 12 of spinnerette body 11 side, the core liquid import 13 being positioned at spinnerette body 11 opposite side and the spinning outlet 15 being positioned at spinnerette body 11 bottom, mutually isolated preparation liquid path 14 and core liquid path 16 is had in the middle part of spinnerette body 11, preparation liquid path 14 exports 15 with preparation liquid import 12 and spinning and is communicated with, core liquid path 16 exports 15 with core liquid import 13 and spinning and is communicated with, described spinnerette body 11 top also has two or more fiber paths 17, the end of fiber path 17 is communicated with preparation liquid path 14.
The present invention strengthens film to prepared antipollution hollow fiber internal pressure and has carried out intensity and pure water flux.
Described antipollution hollow fiber internal pressure strengthens the fracture strength that film strength refers to single film, is by electronic universal material testing machine, and the mensuration power (unit N) broken needed for single film obtains.
Described pure water flux flux detector is tested under 0.1MPa, 25 DEG C of conditions.
The present invention by adding long fibre in the rete of hollow-fibre membrane, by long fibre and preparation liquid, there is in coagulation bath different gelation rates and shrinkage degree, control filament contraction by the long fibre of selection different rigidity, varying strength, thus control the degree of irregularity of the internal channel of hollow-fibre membrane.Because internal channel is rugged, current can form turbulent flow in internal channel, thus improve current scour intensity, the final pollution level effectively reducing film.
[accompanying drawing explanation]
Fig. 1 is the structural representation of spinning-drawing machine of the present invention;
Fig. 2 is the structural representation of spinneret of the present invention;
Fig. 3 is the architectural difference schematic diagram of hollow-fibre membrane of the present invention and existing ordinary hollow tunica fibrosa;
Fig. 4 is the structure chart of hollow-fibre membrane section under magnifying glass of embodiment 1;
Fig. 5 is the structure chart of hollow-fibre membrane section under magnifying glass of embodiment 2;
Fig. 6 is the structure chart of doughnut film outer surface under magnifying glass of embodiment 2;
Fig. 7 is the structure chart of hollow-fibre membrane section under magnifying glass of comparative examples;
Fig. 8 is the structure chart of doughnut film outer surface under magnifying glass of comparative examples.
Wherein, 1, wire-feed motor; 2, long fibre volume; 3, long fibre; 4, adhesion promoter flush coater; 5, adhesion promoter holding vessel; 6, material liquid tank; 7, spinneret; 8, coagulation bath; 9, silk machine is received; 10, wire drawing wheel; 11, spinnerette body; 12, preparation liquid import; 13, core liquid import; 14, preparation liquid path; 15, spinning outlet; 16, core liquid path; 17, fiber path.
[detailed description of the invention]
Following examples are used for explaining technical scheme of the present invention without limitation.Those skilled in the art can use for reference content of the present invention, the links such as suitable change structure, annexation, material, parameter, size, technique realize other object corresponding, its relevant change does not all depart from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all should be deemed to be included within scope of the present invention.
In the present invention, if no special instructions, term " ratio " (:) is weight part ratio, and " % " is percetage by weight.
Embodiment 1
Adopt hollow-fibre membrane spinning-drawing machine as shown in Figure 1, similar with the common spinning-drawing machine of this area, comprise wire-feed motor, material liquid tank, spinneret, coagulation bath and receipts silk machine, wherein, at the adhesion promoter holding vessel that spinneret and material liquid tank upstream are also provided with adhesion promoter flush coater and are attached thereto, before coating preparation liquid, can carry out to long fibre the process spraying adhesion promoter in advance.
Spinneret as shown in Figure 2, except with conventional spinneret same design except, it has two-way or fiber path, for passing through long fibre.
Preparation preparation liquid: according to the Kynoar of 30:70:10, dimethylacetylamide (DMAC) and PVP at 50 DEG C, stir, negative pressure deaeration, obtains masking feed liquid.
Preparation core liquid: according to 3:7, DMAC and water are mixed at 30 DEG C, obtain core liquid after deaeration.
Preparation adhesion force promoter composition: at 40 DEG C according to 30:60:10 by KS610 type adhesion promoter: DMAC: ethanol mixes, obtains adhesion force promoter composition.
Long fibre uses two 150D/36F polyster fibres arranged side by side.
Start spinning-drawing machine, after long fibre is put silk, to polyster fibre spraying adhesion force promoter composition at 50 DEG C, then at 60 DEG C, pass through the coated preparation liquid of spinneret, then enter the water-bath of 60 DEG C, after sizing, after arrangement, drying, receive silk.
Cut open by gained film silk, at amplification Microscopic observation, as shown in Figure 3, there is distortion in the inwall of hollow structure, produces bending.
Run with 80LMH Heng Tong amount in interior press mold testing arrangement, filter secondary clarifier effluent, pressure progressively rises in time, and record operating pressure, recording its maximum operating pressure is 0.22MPa.
Run with 65LMH Heng Tong amount in interior press mold testing equipment, filter secondary clarifier effluent, pressure progressively rises in time, record operating pressure, per half an hour pressure increase 1KPa.
The hollow fiber internal pressure of description of test embodiment 1 strengthens film and can bear higher pressure (0.22MPa), can have higher flux, and rate of pressure rise (per half an hour pressure increase 1KPa) shows that antipollution situation is better than existing hollow-fibre membrane.
Embodiment 2
Identically with embodiment 1 carry out, difference is:
Preparation preparation liquid: according to the polyether sulfone of 10:60:20, dimethyl formamide (DMF) and polyethylene glycol at 40 DEG C, stir, negative pressure deaeration, obtains masking feed liquid.
Preparation core liquid: according to 10:40, DMF and water are mixed at 40 DEG C, obtain core liquid after deaeration.
Preparation adhesion force promoter composition: at 45 DEG C according to 30:60:10 by KS620 type adhesion promoter: DMF: ethanol mixes, obtains adhesion force promoter composition.
Long fibre uses two 250D/48F nylon fibres arranged side by side.
Start spinning-drawing machine, after long fibre is put silk, to polyster fibre spraying adhesion force promoter composition at 60 DEG C, then at 50 DEG C, the coated preparation liquid of spinneret is passed through, then enter the coagulation bath (the 60%DMAC aqueous solution of 70 DEG C) of 80 DEG C, after sizing, after arrangement, drying, receive silk.
Cut open by gained film silk, at amplification Microscopic observation, as shown in Figure 4, there is distortion in the inwall of hollow structure, produces more bending.
By film silk at amplification Microscopic observation, as shown in Figure 5, can see that outside appearance is out of shape.
Run with 80LMH Heng Tong amount in interior press mold testing arrangement, filter secondary clarifier effluent, record operating pressure, recording its maximum operating pressure is 0.22MPa.
Run with 65LMH Heng Tong amount in interior press mold testing arrangement, filter secondary clarifier effluent, pressure progressively rises in time, record operating pressure, pressure increase 1KPa per hour.
Experiment confirms that embedding fiber can make hollow fiber internal pressure enhancing film bear higher pressure (0.22MPa), has simultaneously and has higher flux.After embedding high D/F number fiber, the rugged degree of internal channel rises, and contamination resistance promotes (pressure increase 1KPa per hour).
Embodiment 3
Identically with embodiment 1 carry out, difference is:
Preparation preparation liquid: according to the polyvinyl chloride of 20:80:10, DMAC and NMP at 70 DEG C, stir, negative pressure deaeration, obtains masking feed liquid.
Preparation core liquid: according to 20:20, DMAC and water are mixed at 20 DEG C, obtain core liquid after deaeration.
Preparation adhesion force promoter composition: at 45 DEG C according to 30:60:10 by KS610 type adhesion promoter: DMAC: ethanol mixes, obtains adhesion force promoter composition.
Long fibre uses two 420D/72F polypropylene fibers arranged side by side.
Start spinning-drawing machine, after long fibre is put silk, to polyster fibre spraying adhesion force promoter composition at 30 DEG C, then at 40 DEG C, pass through the coated preparation liquid of spinneret, then enter the coagulation bath (water-bath) of 30 DEG C, after sizing, after arrangement, drying, receive silk.
Observe surfaces externally and internally, similar to embodiment 2.
Embodiment 4 (comparative examples 1)
Identically with embodiment 1 carry out, difference is: do not adopt long fibre silk (using the spinning equipment of prior art).
Observe surfaces externally and internally, as shown in Figure 7,8, hollow structure is straight channel, does not distort.
Run with 80LMH Heng Tong amount in interior press mold testing arrangement, filter secondary clarifier effluent, record operating pressure, recording its maximum operating pressure is 0.20MPa, is starkly lower than the result of embodiment 1-3.
Run with 65LMH Heng Tong amount in interior press mold testing arrangement, filter secondary clarifier effluent, pressure progressively rises in time, and record operating pressure, the film silk pressure increase 2KPa per half an hour of the present embodiment, rate of pressure rise is higher than the result of embodiment 1-3.
The highest operating pressure that experiment proves not embed long stapled ordinary hollow tunica fibrosa is starkly lower than interior pressure enhancing film of the present invention.And not having long fibre to add, the internal channel of hollow-fibre membrane is straight passage structures, is different from rugged internal channel of the present invention, and therefore in running, rate of pressure rise is fast, and contamination resistance declines.
Embodiment 5 (comparative examples 2)
Identically with embodiment 1 carry out, difference is: adopt 150D/96F polyster fibre, and the shrinkage factor of this fiber in coagulation bath and preparation liquid are closely.
Observe surfaces externally and internally, similar to embodiment 4, hollow structure is straight channel, does not distort.
Run with 80LMH Heng Tong amount in interior press mold testing arrangement, filter secondary clarifier effluent, record operating pressure, recording its maximum operating pressure is 0.24MPa.
Run with 65LMH Heng Tong amount in interior press mold testing arrangement, filter secondary clarifier effluent, pressure progressively rises in time, record operating pressure, per half an hour pressure increase 2KPa.
Can be found out by contrast, the film of embodiment 5 is due to after embedding long fibre, and therefore maximum operating pressure increases, and can play the result strengthening maximum operating pressure.But this long fibre silk is consistent with rete shrinkage factor in coagulation bath, therefore can not generate rugged internal channel, so there is no play antipollution effect, so along with film passing running time, its rate of pressure rise is obviously greater than the film of embodiment 1-3.
Embodiment 6 (comparative examples 3)
Identically with embodiment 2 carry out, difference is: do not use any adhesion promoter.
Observe surfaces externally and internally, found that long fibre is deviate from by rete, cause film silk cannot be shaping.
Claims (10)
1. an antipollution hollow fiber internal pressure strengthens film, described hollow fiber internal pressure strengthens film and has the filtration rete and hollow structure be made up of preparation liquid, it is characterized in that being provided with in described filtration rete two or more long fibres, described long stapled length direction is consistent with the length direction that described hollow fiber internal pressure strengthens film, and described long fibre has the shrinkage factor different from preparation liquid in coagulation bath.
2. antipollution hollow fiber internal pressure according to claim 1 strengthens film, it is characterized in that long stapled shrinkage factor is 2-50%.
3. antipollution hollow fiber internal pressure according to claim 1 strengthens film, it is characterized in that long fibre is selected from terylene, polyamide fibre, aramid fiber or polypropylene fiber, described long fibre 150D/36F ~ 420D/72F.
4. the antipollution hollow fiber internal pressure any one of claim 1-3 described in claim strengthens the preparation method of film, it is characterized in that comprising the following steps:
(1) preparation liquid is prepared
At 40-70 DEG C, by masking resin, solvent, additive according to weight ratio 10-30:60-80:10-20 mix, stir, negative pressure deaeration, obtains masking feed liquid;
(2) core liquid is prepared
At 20-40 DEG C, solvent and water are mixed according to weight ratio 20-80:20-80, stir, negative pressure deaeration, obtains core liquid;
(3) apply
Adopt hollow-fibre membrane spinning-drawing machine, after long fibre is put silk, to long fibre coating adhesion force promoter composition at 30-70 DEG C, then make two or more long fibres simultaneously by the coated preparation liquid of spinneret;
(4) gel, arrangement, drying
Enter coagulation bath after coating preparation liquid, coagulation bath temperature is 30-80 DEG C, after arrangement, drying, receive silk, obtains antipollution hollow fiber internal pressure and strengthens film.
5. preparation method according to claim 4, is characterized in that described masking resin is selected from Kynoar, polyvinyl chloride, polyether sulfone or polyacrylonitrile.
6. preparation method according to claim 4, is characterized in that described adhesion force promoter composition contains the adhesion promoter in weight ratio 30:60:10: solvent: ethanol.
7. preparation method according to claim 4, is characterized in that described adhesion promoter is PET adhesion promoter.
8. the antipollution hollow fiber internal pressure that the antipollution hollow fiber internal pressure enhancing film any one of claim 1-3 described in claim or the preparation method any one of claim 4-7 described in claim obtain strengthens the purposes of film in water treatment.
9. realize the spinneret of the preparation method any one of claim 4-8 described in claim, described spinneret comprises spinnerette body (11), be positioned at the preparation liquid import (12) of spinnerette body (11) side, the core liquid import (13) being positioned at spinnerette body (11) opposite side and the spinning being positioned at spinnerette body (11) bottom outlet (15), there are mutually isolated preparation liquid path (14) and core liquid path (16) in spinnerette body (11) middle part, preparation liquid path (14) exports (15) with preparation liquid import (12) with spinning and is communicated with, core liquid path (16) exports (15) with core liquid import (13) with spinning and is communicated with, it is characterized in that described spinnerette body (11) top also has two or more fiber paths (17), the end of fiber path (17) is communicated with preparation liquid path (14).
10. the spinning-drawing machine containing spinneret described in claim 9.
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| CN105233711A (en) * | 2015-10-31 | 2016-01-13 | 宁波欧梵卫浴有限公司 | Preparation method for water-purifying polysulfone hollow fiber membrane |
| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
| CN109023567A (en) * | 2018-08-10 | 2018-12-18 | 浙江三星特种纺织股份有限公司 | A kind of production equipment and process of pvc pipe type film wire |
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| CN109023567A (en) * | 2018-08-10 | 2018-12-18 | 浙江三星特种纺织股份有限公司 | A kind of production equipment and process of pvc pipe type film wire |
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|---|---|
| CN104474913B (en) | 2016-10-12 |
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