CN102776597B - High-strength and high-modulus polyvinyl alcohol fiber and melt spinning method of high-strength and high-modulus polyvinyl alcohol fiber - Google Patents
High-strength and high-modulus polyvinyl alcohol fiber and melt spinning method of high-strength and high-modulus polyvinyl alcohol fiber Download PDFInfo
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Abstract
The invention relates to a high-strength and high-modulus polyvinyl alcohol fiber and a melt spinning method of the high-strength and high-modulus polyvinyl alcohol fiber. The method comprises the following steps that polyvinyl alcohol, water and polyatomic alcohol are subjected to full swelling after being uniformly mixed; the polyvinyl alcohol subjected to the full swelling is added into a double-screw-rod extruding machine and is then subjected to full fusion to be extruded, and melt fine flows form a primary fiber after air blowing cooling; and the prepared primary fiber is subjected to the drying by a hot air drying oven, multistage stretching and tense heat setting to form the polyvinyl alcohol fiber. The preparation method of the prepared polyvinyl alcohol fiber has the advantage that through the hydrogen bond compounding among water molecules, polyatomic alcohol and polyvinyl alcohol molecules, the melt spinning and the high-power stretching of the polyvinyl alcohol are realized. The polyvinyl alcohol fiber prepared by the preparation method has the advantages of fiber degree controllability, high strength and high modulus, and can be widely applied to the field of civil engineering concrete.
Description
Technical field
The present invention relates to a kind of high strength high modulus polyvinyl alcohol fiber and melt spinning method thereof, the preparation method who particularly relates to a kind of high strength high modulus polyvinyl alcohol fiber for civil engineering, the specifically melt-spinning preparation method of a kind of high-strength high-modulus polyethylene alcohol (PVA) coarse denier fiber.
Background technology
In order to improve, concrete tensile property is poor, performance of resisting cracking and the shortcoming such as ductility is poor, to admixture synthetic fiber in concrete, to improve the research of concrete performance, develops quite rapidly.At present research is more polypropylene fibre, polyethylene fiber, nylon fiber, polyester fiber, carbon fiber, aramid fiber, vinal etc.Wherein with polypropylene monofilament fiber because of its cheap, chemical corrosion resistance high, and source more extensively thereby is at present comparatively being widely applied again on the market, but the hydrophobicity that its defect is polypropylene itself can not form more firmly bond stress with cement matrix material; Polyethylene fiber, thus nylon fiber and polyester fiber are because the enhancing toughening effect to cement concrete is not outstanding, corrosion-resistant and the defect of the aspect such as weatherability makes its application exist limitation; Carbon fiber and aramid fiber are owing to itself having the feature of high-strength and high-modulus amount, can obviously give performances such as strengthening concrete anti-impact, resistance to compression and anticracking, but there is defect in the production technology due to carbon fiber and aramid fiber, use cost is high, is therefore seldom utilizing on the market carbon fiber and aramid fiber to be applied to concrete enhancing field; The price of vinal is low, density is little, cohesive force is high, good dispersion, be easy to stir; Compare with other synthetic fiber, vinal good hydrophilic property, elastic modelling quantity are high, and have high-specific surface area, good with cement concrete compatibility, are applicable to the cement of various grades, strengthen successful.In addition, its light resistance and alkali resistance might as well, there is good chemical stability, add consumption little (consumption be only asbestos 1/5), and be acknowledged as the material of the most rising replacement asbestos, therefore more next and extensive in concrete application and research to polyvinyl alcohol at present.
Because polyvinyl alcohol is crystalline polymer, in molecule, contain great amount of hydroxy group, can form in a large amount of molecules and intermolecular hydrogen bonding, make its fusing point up to 220～240 ℃, but its decomposition temperature is very low, 160 ℃ start the etherificate of dewatering, 200 ℃ start to decompose, are difficult to melt-processed.Therefore polyvinyl alcohol (PVA) fiber of market is owing to adopting wet-formed technique, but the two-way mass transport process of wet spinning makes vinal structure inhomogeneous, cross section is kidney-shaped, there is obvious skin-core structure, cannot bear super drawing, and can not reach the thick dawn standard of the fortifying fibre that civil engineering uses, cause the dispersiveness of fiber in concrete and strengthen effect bad.
The variety of problems occurring in order to solve wet spinning, improve intensity and the modulus and the thick dawn of realizing polyvinyl alcohol of vinal, both at home and abroad based on having made large quantity research in wet production mode: dry-wet spinning (Hu Shao Hua < < polyvinyl communication > > the 1st phase in 1997, JPH07-207521), boron crosslinking spinning (ZL981013643, JPH10-046428), gel spinning (JP1987-90308, JP1989-77614, CN1092120A) etc. method is prepared the PVA as-spun fibre of even structure, and be aided with region and stretch, multistage Ultra-Drawing etc., prepare high-quality vinal.But said method based on wet production, still has defect realizing aspect the thick dawn due to all, and great majority adopt high polymerization degree PVA, and additive is complicated, needs follow-up extraction process, and production cost is high, and environmental pollution is large.
Because fiberizing in melt spinning only relates to the cooling of polymer melt, thing forms variation, only has the variation of geometry and physical state, and technological process is short, three-waste free pollution, and it is high to spin speed, is a kind of efficient mode of production.And shrink during melt-spinning fiber moulding littlely, fibre section uniformity is high, can impose super drawing, thereby improves fibre property.If realize the melt spinning of PVA, what will solve that wet spinning exists cannot production high-performance coarse denier fiber and operation and the pollution problem such as desolvation, has the features such as simple, efficient, economy, environmental protection.Therefore in order to realize the thick dawn of vinal, melt spinning research at polyvinyl alcohol also has certain achievement in research: Chinese patent CN101899722A carries out swelling by water to polyvinyl alcohol, after dissolving by single screw rod, extrude, through freezing liquid, solidify formation vinal, but exist through coagulating bath, become silk to make the technological process of production long, the shortcoming that cost is larger; It is CN1786302A " a kind of method of preparing high performance polyvinyl alcohel fiber " that plasticizing melt spinning coarse denier fiber refers to the disclosed Granted publication of Chinese invention patent number, by adding little molecular modification agent and polyvinyl alcohol, form intermolecular composite and carry out melt spinning, but exist micromolecule additive of a great variety, extraction is complicated, the shortcoming that cost is higher.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of water and polyalcohol to carry out the method that plasticizing melt spinning technique is prepared vinal.The production technology of the method is simple, and environmental pollution is little, and production cost is low.Adopt that vinal prepared by the method has advantages of that fiber number is controlled, high strength, high-modulus, can be widely used in civil engineering concrete field.
In order to solve technical problem recited above, the present invention takes following technical scheme:
The invention provides a kind of high strength high modulus polyvinyl alcohol fiber and melt spinning method thereof, specifically comprise the following steps:
And a melt spinning method, it is characterized in that comprising the following steps:
(1) swelling;
Raw material is pva powder or pellet, take water as plasticizer, adds amides compound, fully swelling; Wherein polyvinyl alcohol polymerizable raw material degree is 800～2600, and alcoholysis degree is 60%～99%, and the weight ratio of polyvinyl alcohol, water and polyalcohol is 1: 0.3～1.5: 0.05～0.2;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 0.1～2mm from aperture, melt thread obtains polyvinyl alcohol as-spun fibre through quenching; Wherein each district's temperature of screw rod is: 80～170 ℃ of 70～120 ℃ of feed zones, 90～170 ℃ of compression sections and metering sections, and 90～170 ℃ of filament spinning component temperature, 80～150 ℃ of spinnerets temperature, nascent silk spinning speed is 10～200m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 80～180 ℃ through temperature is dried, carrying out 1～3 grade of stretching, is at 110～220 ℃, to carry out nervous HEAT SETTING to make vinal in temperature; Vinal fracture strength >=the 8cN/dtex obtaining, fiber number >=10D, reach >=25GPa of modulus.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, described polyalcohol comprises glycerine, trihydroxy methyl ethane, pentaerythrite, xylitol or sorbic alcohol.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, described abundant swelling is carried out swelling 40min～4h at 20～60 ℃ after referring to abundant mixing.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, described screw extruder is water vapor seal type double screw extruder.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, the twin-screw screwing element of described water vapor seal type double screw extruder has at least tri-kinds of screwing element I, screwing element II and screwing element III to combine; Combination at least comprises: be followed successively by least one circulation of screwing element I, screwing element II and screwing element III, and after described circulation, meet screwing element I again; Or combination comprises screwing element I, connect afterwards at least one circulation of screwing element II and screwing element III, and after described circulation, meet again screwing element I.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, described screwing element I, screwing element II and screwing element III meet following relation: h
2s
2< h
1s
1< h
3s
3; D '
3< D '
1< D '
2; Wherein said h
1for the spiral groove depth of screwing element I, S
1for the flight pitch of screwing element I, D '
1screw rod root footpath for screwing element I; h
2for the spiral groove depth of screwing element II, S
2for the flight pitch of screwing element II, D '
2screw rod root footpath for screwing element II; h
3for the spiral groove depth of screwing element III, S
3the flight pitch of screwing element III, D '
3screw rod root footpath for screwing element III.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, described screw flight element important technological parameters is as follows:
Screwing element I
Screw rod root footpath D
01>=15mm, spiral groove depth h
1>=15mm, flight pitch S
1>=10mm, spiral shell rib width B
1>=10mm;
Wherein, 0.3D
01≤ h
1≤ 0.6D
01, B
1≤ S
1;
Screwing element II
Screw rod root footpath D
02>=20mm, spiral groove depth h
2>=10mm, flight pitch S
2>=5mm, spiral shell rib width B
2>=5mm;
Wherein, 0.1D
02≤ h
2≤ 0.3D
02, B
2≤ S
2;
Screwing element III
Screw rod root footpath D
03>=10mm, spiral groove depth h
3>=20mm, flight pitch S
3>=10mm, spiral shell rib width: B
3>=10mm;
Wherein, 0.6D
03≤ h
3≤ 2D
03, B
3≤ S
3.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, the mode of described quenching is lateral blowing, ring blowing or center ring blowing quench.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, 1～3 grade of described stretching is respectively: while adopting 1 grade to stretch, carry out 5～10 times of draw ratios at 150～190 ℃; While adopting 2 grades to stretch, carry out respectively at 120～150 ℃ and 150～200 ℃, total draw ratio is 8～15 times; While adopting 3 grades to stretch, carry out respectively at 90～120 ℃, 120～170 ℃ and 170～220 ℃, total draw ratio is 10～20 times.
Nervous HEAT SETTING as above refers under tension force effect carries out nervous HEAT SETTING by the fiber after described drawn at 110～220 ℃, heat-setting time 0.2～6 minute.Fiber is heat-treated, eliminate stress, the strain of in vinal, accumulating, make size, the processing technology of form stable.
A kind of high strength high modulus polyvinyl alcohol fiber as above and melt spinning method thereof, the vinal finally making is cut into certain length according to different needs, general staple fiber ppd is 5mm～50mm, and the polyvinyl alcohol staple fibre making can be used as enhancing toughening material and is widely used in civil engineering.
Beneficial effect:
The present invention prepares the vinal of high-strength and high-modulus by melt spinning method, have the following advantages: by adding water and polyalcohol, carry out melt spinning and the super drawing that plasticising realizes polyvinyl alcohol, without ultra-high molecular weight polyethylene alcohol, from general purpose grade polyvinyl alcohol, prepare high-performance fiber, do not need coagulating bath, only by unidirectional mass transfer, remove the plasticizer water of polyvinyl alcohol, regulation and control vinal forms, hydrogen bond and oriented crystalline structure are prepared high performance polyvinyl alcohel fiber, fiber is through super-dry, many times stretch and the nervous HEAT SETTING of high temperature after, obtain high strength, the fiber of modulus, make up the defect of prior art and commercially available prod, meet civil engineering for concrete toughness reinforcing, cracking resistances etc. need, and technique is simple, economical, environmental protection, be easy to realize suitability for industrialized production.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 800, alcoholysis degree 60%, take water as plasticizer, after fully mixing, at 20 ℃, carries out swelling 4h; The weight ratio of polyvinyl alcohol, water and glycerine is 1: 0.3: 0.05;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds double screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 0.1mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 80 ℃ of 70 ℃ of feed zones, 90 ℃ of compression sections and metering sections, and 90 ℃ of filament spinning component temperature, 80 ℃ of spinnerets temperature, nascent silk spinning speed is 10m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 80 ℃ through temperature is dried, at 150 ℃, carry out 1 grade of stretching, 5 times of draw ratios, are at 110 ℃, to carry out nervous HEAT SETTING within 0.2 minute, to make the vinal that fiber number is 10D in temperature; The vinal fracture strength 8cN/dtex obtaining, modulus reaches 25GPa.
Embodiment 2
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 2600, alcoholysis degree 99%, take water as plasticizer, after fully mixing, at 60 ℃, carries out swelling 40min; The weight ratio of polyvinyl alcohol, water and trihydroxy methyl ethane is 1: 1.5: 0.2;
(2) melt spinning;
The good polyvinyl alcohol of swelling is added to water vapor seal type double screw extruder, the combination of the twin-screw screwing element of described water vapor seal type double screw extruder is followed successively by two circulations of screwing element I, screwing element II and screwing element III, and after described circulation, meets screwing element I again; The important technological parameters of the screwing element of water vapor seal type double screw extruder is: in screwing element I, and screw rod root footpath D
01=15mm, spiral groove depth h
1=15mm, flight pitch S
1=10mm, spiral shell rib width B
1=10mm, 0.3D
01=h
1=0.6D
01, B
1=S
1; In screwing element II, screw rod root footpath D
02=20mm, spiral groove depth h
2=10mm, flight pitch S
2=5mm, spiral shell rib width B
2=5mm, 0.1D
02=h
2=0.3D
02, B
2=S
2; In screwing element III, screw rod root footpath D
03=10mm, spiral groove depth h
3=20mm, flight pitch S
3=10mm, spiral shell rib width: B
3=10mm, 0.6D
03=h
3=2D
03, B
3=S
3, fully after melting, through spraying filament spinning component the spinnerets that is 2mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 170 ℃ of 120 ℃ of feed zones, 170 ℃ of compression sections and metering sections, and 170 ℃ of filament spinning component temperature, 150 ℃ of spinnerets temperature, nascent silk spinning speed is 200m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 180 ℃ through temperature is dried, at 190 ℃, carry out 1 grade of stretching, 10 times of draw ratios, are at 220 ℃, to carry out nervous HEAT SETTING within 6 minutes, to make the vinal that fiber number is 1900D in temperature; The vinal fracture strength 12cN/dtex obtaining, modulus reaches 26GPa.
The vinal finally making is cut into certain length according to different needs, and general staple fiber ppd is 5mm, and the polyvinyl alcohol staple fibre making can be used as enhancing toughening material and is widely used in civil engineering.
Embodiment 3
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 1700, alcoholysis degree 99%, take water as plasticizer, after fully mixing, at 45 ℃, carries out swelling 2h; The weight ratio of polyvinyl alcohol, water and pentaerythrite is 1: 1: 0.11;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds double screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 0.5mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 150 ℃ of 80 ℃ of feed zones, 120 ℃ of compression sections and metering sections, and 150 ℃ of filament spinning component temperature, 140 ℃ of spinnerets temperature, nascent silk spinning speed is 60m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 150 ℃ through temperature is dried, at 170 ℃, carry out 1 grade of stretching, 7 times of draw ratios, are at 180 ℃, to carry out nervous HEAT SETTING within 3 minutes, to make the vinal that fiber number is 370D in temperature; The vinal fracture strength 12.5cN/dtex obtaining, modulus reaches 28GPa.
Embodiment 4
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 1700, alcoholysis degree 88%, take water as plasticizer, after fully mixing, at 40 ℃, carries out swelling 3h; The weight ratio of polyvinyl alcohol, water and xylitol is 1: 0.8: 0.09;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds double screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 1mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 160 ℃ of 80 ℃ of feed zones, 125 ℃ of compression sections and metering sections, and 155 ℃ of filament spinning component temperature, 150 ℃ of spinnerets temperature, nascent silk spinning speed is 100m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 160 ℃ through temperature is dried, at 120 ℃ and 150 ℃, carry out 2 grades of stretchings respectively, total draw ratio is 8 times, in temperature, is at 170 ℃, to carry out nervous HEAT SETTING within 2.5 minutes, to make the vinal that fiber number is 400D; The vinal fracture strength 13cN/dtex obtaining, modulus reaches 27GPa.
The vinal finally making is cut into certain length according to different needs, and general staple fiber ppd is 50mm, and the polyvinyl alcohol staple fibre making can be used as enhancing toughening material and is widely used in civil engineering.
Embodiment 5
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 2400, alcoholysis degree 99%, take water as plasticizer, after fully mixing, at 50 ℃, carries out swelling 50min; The weight ratio of polyvinyl alcohol, water and sorbierite is 1: 0.8: 0.12;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds double screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 1.2mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 160 ℃ of 100 ℃ of feed zones, 150 ℃ of compression sections and metering sections, and 160 ℃ of filament spinning component temperature, 140 ℃ of spinnerets temperature, nascent silk spinning speed is 75m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 160 ℃ through temperature is dried, at 150 ℃ and 200 ℃, carry out 2 grades of stretchings respectively, total draw ratio is 15 times, in temperature, is at 200 ℃, to carry out nervous HEAT SETTING within 2.3 minutes, to make the vinal that fiber number is 410D; The vinal fracture strength 13.5cN/dtex obtaining, modulus reaches 30GPa.
The vinal finally making is cut into certain length according to different needs, and general staple fiber ppd is 20mm, and the polyvinyl alcohol staple fibre making can be used as enhancing toughening material and is widely used in civil engineering.
Embodiment 6
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 1700, alcoholysis degree 99%, take water as plasticizer, after fully mixing, at 30 ℃, carries out swelling 3h; The weight ratio of polyvinyl alcohol, water and glycerine is 1: 0.9: 0.15;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds double screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 0.8mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 170 ℃ of 105 ℃ of feed zones, 140 ℃ of compression sections and metering sections, and 170 ℃ of filament spinning component temperature, 150 ℃ of spinnerets temperature, nascent silk spinning speed is 40m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 170 ℃ through temperature is dried, at 130 ℃ and 180 ℃, carry out 2 grades of stretchings respectively, total draw ratio is 10 times, in temperature, is at 150 ℃, to carry out nervous HEAT SETTING within 5 minutes, to make the vinal that fiber number is 800D; The vinal fracture strength 13.2cN/dtex obtaining, modulus reaches 29.5GPa.
Embodiment 7
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 2600, alcoholysis degree 88%, take water as plasticizer, after fully mixing, at 35 ℃, carries out swelling 3.5h; The weight ratio of polyvinyl alcohol, water and xylitol is 1: 0.9: 0.18;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds double screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 0.4mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 130 ℃ of 100 ℃ of feed zones, 110 ℃ of compression sections and metering sections, and 140 ℃ of filament spinning component temperature, 140 ℃ of spinnerets temperature, nascent silk spinning speed is 55m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 100 ℃ through temperature is dried, at 90 ℃, 120 ℃ and 170 ℃, carry out 3 grades of stretchings respectively, total draw ratio is 10 times, in temperature, is at 170 ℃, to carry out nervous HEAT SETTING within 3 minutes, to make the vinal that fiber number is 1100D; The vinal fracture strength 14cN/dtex obtaining, modulus reaches 31GPa.
Embodiment 8
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 2400, alcoholysis degree 99%, take water as plasticizer, after fully mixing, at 60 ℃, carries out swelling 1min; The weight ratio of polyvinyl alcohol, water and pentaerythrite is 1: 1.2: 0.05;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds double screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 1.5mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 150 ℃ of 100 ℃ of feed zones, 120 ℃ of compression sections and metering sections, and 160 ℃ of filament spinning component temperature, 140 ℃ of spinnerets temperature, nascent silk spinning speed is 80m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 100 ℃ through temperature is dried, at 110 ℃, 150 ℃ and 200 ℃, carry out 3 grades of stretchings respectively, total draw ratio is 17 times, in temperature, is at 180 ℃, to carry out nervous HEAT SETTING within 3 minutes, to make the vinal that fiber number is 110D; The vinal fracture strength 12cN/dtex obtaining, modulus reaches 35GPa.
The vinal finally making is cut into certain length according to different needs, and general staple fiber ppd is 35mm, and the polyvinyl alcohol staple fibre making can be used as enhancing toughening material and is widely used in civil engineering.
Embodiment 9
And a melt spinning method, comprise the following steps:
(1) swelling;
Raw material is pva powder or the pellet of the degree of polymerization 2400, alcoholysis degree 88%, take water as plasticizer, after fully mixing, at 60 ℃, carries out swelling 50min; The weight ratio of polyvinyl alcohol, water and glycerine is 1: 0.7: 0.1;
(2) melt spinning;
The good polyvinyl alcohol of swelling is added to water vapor seal type double screw extruder, the combination of the twin-screw screwing element of described water vapor seal type double screw extruder is screwing element I, connect afterwards two circulations of screwing element II and screwing element III, and after described circulation, meet again screwing element I; The important technological parameters of the screwing element of water vapor seal type double screw extruder is: in screwing element I, and screw rod root footpath D
01=19mm, spiral groove depth h
1=16mm, flight pitch S
1=11mm, spiral shell rib width B
1=11mm, 0.3D
01< h
1< 0.6D
01, B
1< S
1; In screwing element II, screw rod root footpath D
02=25mm, spiral groove depth h
2=11mm, flight pitch S
2=6mm, spiral shell rib width B
2=6mm, 0.1D
02< h
2< 0.3D
02, B
2< S
2; In screwing element III, screw rod root footpath D
03=11mm, spiral groove depth h
3=24mm, flight pitch S
3=11mm, spiral shell rib width: B
3=11mm, 0.6D
03< h
3< 2D
03, B
3< S
3, fully after melting, through spraying filament spinning component the spinnerets that is 1mm from aperture, melt thread is through the cooling polyvinyl alcohol as-spun fibre that obtains of lateral blowing; Wherein each district's temperature of screw rod is: 160 ℃ of 100 ℃ of feed zones, 150 ℃ of compression sections and metering sections, and 170 ℃ of filament spinning component temperature, 150 ℃ of spinnerets temperature, nascent silk spinning speed is 100m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 150 ℃ through temperature is dried, at 120 ℃, 170 ℃ and 220 ℃, carry out 3 grades of stretchings respectively, total draw ratio is 20 times, in temperature, is at 200 ℃, to carry out nervous HEAT SETTING within 0.5 minute, to make the vinal that fiber number is 1250D; The vinal fracture strength 13.1cN/dtex obtaining, modulus reaches 32GPa.
The vinal finally making is cut into certain length according to different needs, and general staple fiber ppd is 40mm, and the polyvinyl alcohol staple fibre making can be used as enhancing toughening material and is widely used in civil engineering.
Claims (10)
1. a melt spinning method for high strength high modulus polyvinyl alcohol fiber, is characterized in that comprising the following steps:
(1) swelling;
Raw material is pva powder or pellet, take water as plasticizer, adds polyalcohol; Wherein polyvinyl alcohol polymerizable raw material degree is 800～2600, and alcoholysis degree is 60%～99%, and the weight ratio of polyvinyl alcohol, water and polyalcohol is 1:0.3～1.5:0.05～0.2;
(2) melt spinning;
The polyvinyl alcohol that swelling is good adds screw extruder, and fully after melting, through spraying filament spinning component the spinnerets that is 0.1～2mm from aperture, melt thread obtains polyvinyl alcohol as-spun fibre through quenching; Wherein each district's temperature of screw rod is: 80～170 ℃ of 70～120 ℃ of feed zones, 90～170 ℃ of compression sections and metering sections, and 90～170 ℃ of filament spinning component temperature, 80～150 ℃ of spinnerets temperature, nascent silk spinning speed is 10～200m/min;
(3) dry drawing and setting;
After the hot-air oven that the polyvinyl alcohol as-spun fibre that upper step is made is 80～180 ℃ through temperature is dried, carrying out 1～3 grade of stretching, is at 110～220 ℃, to carry out nervous HEAT SETTING to make vinal in temperature; Vinal fracture strength >=the 8cN/dtex obtaining, fiber number >=10D, modulus >=25GPa.
2. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 1, is characterized in that, described polyalcohol is glycerine, trihydroxy methyl ethane, pentaerythrite, xylitol or sorbic alcohol.
3. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 1, is characterized in that, described swelling is carried out swelling 40min～4h at 20～60 ℃ after referring to abundant mixing.
4. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 1, is characterized in that, described screw extruder is water vapor seal type double screw extruder.
5. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 4, it is characterized in that, the twin-screw screwing element of described water vapor seal type double screw extruder has at least three kinds of screwing element I, screwing element II and screwing element III to combine; Combination comprises screwing element I, connects afterwards at least one circulation of screwing element II and screwing element III, and after described circulation, connects screwing element I again;
Described screwing element I, screwing element II and screwing element III meet following relation: h
2s
2< h
1s
1< h
3s
3; D '
3< D '
1< D '
2; Wherein said h
1for the spiral groove depth of screwing element I, S
1for the flight pitch of screwing element I, D '
1screw rod root footpath for screwing element I; h
2for the spiral groove depth of screwing element II, S
2for the flight pitch of screwing element II, D '
2screw rod root footpath for screwing element II; h
3for the spiral groove depth of screwing element III, S
3the flight pitch of screwing element III, D '
3screw rod root footpath for screwing element III.
6. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 5, is characterized in that, described screwing element important technological parameters is as follows:
Screwing element I
Screw rod root footpath D
01>=15mm, spiral groove depth h
1>=15mm, flight pitch S
1>=10mm, spiral shell rib width B
1>=10mm;
Wherein, 0.3D
01≤ h
1≤ 0.6D
01, B
1≤ S
1;
Screwing element II
Screw rod root footpath D
02>=20mm, spiral groove depth h
2>=10mm, flight pitch S
2>=5mm, spiral shell rib width B
2>=5mm;
Wherein, 0.1D
02≤ h
2≤ 0.3D
02, B
2≤ S
2;
Screwing element III
Screw rod root footpath D
03>=10mm, spiral groove depth h
3>=20mm, flight pitch S
3>=10mm, spiral shell rib width B
3>=10mm;
Wherein, 0.6D
03≤ h
3≤ 2D
03, B
3≤ S
3.
7. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 1, is characterized in that, the mode of described quenching is lateral blowing, ring blowing or center ring blowing quench.
8. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 1, is characterized in that, 1～3 grade of described stretching is respectively: while adopting 1 grade to stretch, carry out 5～10 times of draw ratios at 150～190 ℃; While adopting 2 grades to stretch, carry out respectively at 120～150 ℃ and 150～200 ℃, total draw ratio is 8～15 times; While adopting 3 grades to stretch, carry out respectively at 90～120 ℃, 120～170 ℃ and 170～220 ℃, total draw ratio is 10～20 times.
9. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 1, it is characterized in that, described nervous HEAT SETTING refers under tension force effect carries out HEAT SETTING by the fiber after described drawn at 110～220 ℃, heat-setting time 0.2～6 minute.
10. the melt spinning method of a kind of high strength high modulus polyvinyl alcohol fiber according to claim 1, it is characterized in that, the vinal finally making is cut into certain length according to different needs, staple fiber ppd is 5mm～50mm, and the polyvinyl alcohol staple fibre making can be used as enhancing toughening material and is widely used in civil engineering.
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| CN103290505B (en) * | 2013-05-09 | 2015-02-25 | 江苏苏博特新材料股份有限公司 | Method for preparing high-strength high-modulus polyvinyl alcohol fibers |
| CN103409837B (en) * | 2013-08-02 | 2015-10-28 | 东华大学 | The method of water-soluble polyvinyl alcohol fibers prepared by a kind of melt spinning |
| CN103436977B (en) * | 2013-08-28 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Flame-retardant melt-spun high-strength high-modulus polyvinyl alcohol fiber and preparation method thereof |
| CN103436978B (en) * | 2013-08-28 | 2015-08-26 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of high strength high modulus polyvinyl alcohol fiber of surface micropore |
| CN107287675A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工集团公司 | A kind of vinal and preparation method thereof |
| CN106222885B (en) * | 2016-07-23 | 2018-08-31 | 大连天马可溶制品有限公司 | A kind of preparation method of the water-soluble non-woven cloth based on polyvinyl alcohol and polyethylene glycol oxide |
| CN110205696B (en) * | 2019-07-15 | 2021-12-07 | 安徽皖维高新材料股份有限公司 | Method for preparing polyvinyl alcohol coarse denier fiber by melt spinning |
| CN113062004A (en) * | 2021-05-13 | 2021-07-02 | 永安市宝华林实业发展有限公司 | Method for preparing polyvinyl alcohol fiber by semi-molten wet method |
| CN113480751B (en) * | 2021-07-15 | 2022-08-09 | 江南大学 | Spinnable polyvinyl alcohol master batch for sea-island fiber and preparation method thereof |
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