CN103290505B - Method for preparing high-strength high-modulus polyvinyl alcohol fibers - Google Patents
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Abstract
The invention relates to a method for preparing high-strength high-modulus polyvinyl alcohol fibers. The method comprises the following steps of: mixing 10-40 parts by weight of poly-hydroxymethyl compounds with 30-70 parts by weight of water to obtain a mixture serving as a composite modifier; then evenly mixing the composite modifier with 0.01-5 parts by weight of inorganic alkali compounds and 100 parts by weight of polyvinyl alcohol with polymerization degree of 1700-2600 and alcoholysis degree of 88-99% in a high-speed mixer to obtain modified polyvinyl alcohol; then spinning on a melt spinning machine to prepare nascent polyvinyl alcohol fibers; finally implementing cold drawing, drying, multi-stage hot drawing and hot shaping. The method needs neither solvents nor coagulators for wet spinning, thereby being simple in technology and free from pollution; a screw rod with a unique structure is not required; industrial production is easy to realize. The prepared fibers are high in fiber strength and high in modulus and can be used for cement toughening anti-cracking materials, geotextile and tire cords; the prepared fibers also can be used as reinforcing materials for plastics and rubber.
Description
Technical field
The present invention relates to a kind of preparation method of vinal, particularly adopt general purpose grade polyvinyl alcohol to prepare the method for high strength high modulus polyvinyl alcohol fiber.
Background technology
The features such as high strength and high modus polymer fiber is important high performance polymer material, has excellent mechanical property, acid-alkali-corrosive-resisting, lightweight are the important foundation materials supporting high-tech industry development.High-strength high-modulus polyethylene alcohol (PVA) fiber is as the one of high-performance polymer fiber, have high strength, high-modulus, good dispersion, acid and alkali-resistance, wear-resistant, with the advantage such as the compatibility of substrate interface is good, be widely used as the toughness reinforcing cracking-resistant material of cement, geotextiles, tire cord and the reinforcing material as plastics and rubber.Therefore, develop high strength high modulus polyvinyl alcohol fiber and there is good development prospect.
Because polyvinyl alcohol is crystalline polymer, have polyhydroxy structure, molecule is interior and intermolecular hydrogen bonding effect is strong, fusing point and decomposition temperature are too close, melting Sum decomposition occurs simultaneously, directly cannot carry out melt-processed, and therefore traditional vinal adopts wet spinning preparation.During fiberizing there is two-way mass transfer in coagulating agent and solvent, and the normal dia of fiber, at about 15 μm, cannot prepare the coarse denier fiber that diameter is larger; And fibre section is kidney type, have obvious skin-core structure, cannot carry out super drawing, TENSILE STRENGTH is only 500-700MPa, cannot meet the requirement of high-strength and high-modulus.
In order to improve the strength and modulus of vinal, overcoming conventional wet spinning cross section uneven, the problem that draw ratio is low, having carried out large quantifier elimination both at home and abroad.Add the crosslinking agent such as boric acid or borax and PVA molecule forms cross-linked gel structure as added boron crosslinking spinning (ZL981013643, JPH10-046428), overcome the problem of PVA intermolecular too much entanglement when conventional wet spinning is solidified, be conducive to improving total draw ratio and intensity; The method that dry-wet spinning (Ye Guangdou " polyvinyl communication " the 4th phase in 1998, JPH07-207521) adopts high temperature spinning and low temperature solidifying phase to combine, the as-spun fibre stretching strand is obtained after low temperature coagulating bath, reduce the intermolecular entanglement of PVA, improve the posterior drawing of fiber, and then improve the strength and modulus of fiber; Gel spinning (JP1987-90308, CN1092120A) makes intermeshing molecule unfold solution in a solvent to twine, highly swelling frozen glue body as-spun fibre is obtained after spinning, reduce secondary valency power and the entanglement of interchain, can be used for the spinning of ultra-high molecular weight polyethylene alcohol, reduce macromolecular chain end defect by improving molecular weight, as-spun fibre can super drawing after extraction; Polyvinyl acetate (PVAc) directly alcoholization spinning process (Ye Guangdou " synthetic fiber industry " the 3rd phase in 1998) is by PVAc direct fabrics, in spinning bath, alcoholysis becomes PVA fiber, the hydroxy number of hydrogen bond action is formed when reducing spinning, obtain the as-spun fibre that degree of crystallinity is lower, improve spinning speed and draw ratio.But above-described spinning process is all based on solution-polymerized SBR, still needs solvent and coagulating agent, complex process, and the discharge of solvent, coagulating agent etc. easily produces pollution.
At present, adopting melt spinning to prepare vinal also has some to report, mainly comprises copolymerization melt spinning, blend melt spinning and plasticizing melt spinning.Wherein copolymerization melt spinning carries out modification, complex process for the chemical constitution of polyvinyl alcohol, and there is the problem of blend and polyvinyl alcohol compatibility in blend melt spinning, Small molecular plasticizer modified polyvinylalcohol is normally selected in plasticizing melt spinning, if CN1786302A is by adding Small molecular nitrogen-containing compound, hydrophilic polymer assistant, water and polyvinyl alcohol form intermolecular hydrogen bonding effect and carry out melt spinning, but it is of a great variety to there is micromolecule additive, extraction is complicated, the shortcoming that cost is higher, such as CN102776597A again, CN102797050A, CN102776598A adopts water, amides compound, polyalcohols etc. are as plasticiser, but water content used in whole system is higher, need melt spinning in the water-vapor sealed-type double-screw extruder that it is special, high to the requirement of equipment, spinning can not be carried out on the apparatus for melt spinning of routine, not there is universality.
Summary of the invention
Object of the present invention solves the deficiencies in the prior art, provides a kind of method utilizing conventional apparatus for melt spinning to prepare high strength high modulus polyvinyl alcohol fiber, makes that technique is simple, cost is low, and does not produce environment and pollute.
Technical scheme
A preparation method for high strength high modulus polyvinyl alcohol fiber, comprises the steps:
(1) many for 10-40 part methylol compounds are mixed with 30-70 part water, as composite modifier, then mix in high-speed mixer with 0.01-5 part inorganic alkaline compound and 100 parts of polyvinyl alcohol, obtain modified polyvinylalcohol;
(2) modified polyvinylalcohol prepared by step (1) is carried out spinning on melt spinning machine, prepare polyvinyl alcohol as-spun fibre;
(3) as-spun fibre prepared by step (2) is carried out cold stretch;
(4) fiber after step (3) cold stretch is carried out drying;
(5) step (4) dried fiber is carried out Multi-stage heat stretching, finally fiber is carried out HEAT SETTING, to obtain final product.
In step (1), the degree of polymerization of described polyvinyl alcohol is 1700-2600, and alcoholysis degree is 88-99%.
Above number is parts by weight.
In step (1), described many methylol compounds are selected from three (methylol) aminomethane, three (methylol) methylglycine, trimethylolethane, trimethylolpropane, two (trihydroxy methyl) propane, 1, the mixture of one or more arbitrary proportions in 3-dihydroxyacetone (DHA), 2,2-dihydromethyl propionic acids or dimethylolpropionic acid.Many methylol compounds and water and polyvinyl alcohol form hydrogen bond action, destroy the crystalline texture of polyvinyl alcohol, reduce its fusing point.
In step (1), described inorganic alkaline compound is selected from the mixture of one or more arbitrary proportions in NaOH, calcium hydroxide, calcium oxide, magnesium hydroxide or aluminium oxide.Inorganic alkaline compound plays acidic absorbent effect, suppresses the acid catalyzed decomposition of polyvinyl alcohol, improves decomposition temperature, thus realize melt spinning and the super drawing of polyvinyl alcohol.
In step (2), spinning temperature is 140-180 DEG C, and spinneret temperature is 105-135 DEG C.
In step (3), the temperature of cold stretch is 20-25 DEG C, and draw ratio is 2-4 times.
In step (4), baking temperature is 100-140 DEG C, and the time is 3-10min.Dry object destroys the hydrogen bond that many methylol compounds and water formed with polyvinyl alcohol, and the removal many methylol compounds of part and water, to improve the multiple of subsequent step hot-stretch.
In step (5), the temperature that Multi-stage heat stretches is 150-230 DEG C, and draw ratio is 2-10 times.
In step (5), heat setting temperature is 200-230 DEG C, and the time is 0.5-3min.
Compared with prior art, tool has the following advantages in the present invention:
1. the present invention adopts many methylol compounds and water and polyvinyl alcohol to form hydrogen bond action, destroys the crystalline texture of polyvinyl alcohol, reduces its fusing point; Inorganic alkaline compound, as acidic absorbent, suppresses the acid catalyzed decomposition of polyvinyl alcohol, improves decomposition temperature, finally realizes melt spinning and the super drawing of polyvinyl alcohol.
2. without the need to solvent and coagulating agent, pollution-free, technique is simple, is easy to suitability for industrialized production; To screw rod without particular/special requirement, conventional melt spinning equipment can realize.
3. adopt general purpose grade polyvinyl alcohol on the melt spinning machine of routine, prepare the high strength high modulus polyvinyl alcohol fiber of different cross section shape, different fiber number, solve the problem that conventional wet lay spinning cannot prepare coarse denier fiber.
4. adopt the fibre strength prepared of the inventive method and modulus high, TENSILE STRENGTH >=1150MPa, modulus >=30GPa, can be used for the toughness reinforcing cracking-resistant material of cement, geotextiles, tire cord and the reinforcing material as plastics and rubber.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
100g tri-(methylol) aminomethane is mixed with 600g water, as composite modifier, represent that the degree of polymerization of polyvinyl alcohol is 1700 with 30g magnesium hydroxide and 1000g PVAC polyvinylalcohol 1799(note: PVA1799 again, alcoholysis degree is 99%) mix in high-speed mixer, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 140 DEG C, spinneret temperature is 115 DEG C, as-spun fibre is stretched at 25 DEG C after 3 times and enter dry 10min in 100 DEG C of drying boxes, then at 150 DEG C, 175 DEG C, 3 grades of hot-stretchs 3.3 times are carried out at 200 DEG C, finally by 210 DEG C of HEAT SETTING 1.5min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 2
400g trimethylolpropane is mixed with 700g water, as composite modifier, mix in high-speed mixer with 50g calcium hydroxide and 1000g polyvinyl alcohol (PVA2499) again, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 160 DEG C, spinneret temperature is 125 DEG C, as-spun fibre is stretched at 20 DEG C after 2 times and enter dry 8min in 120 DEG C of drying boxes, then at 150 DEG C, 180 DEG C, 220 DEG C are carried out 3 grades of hot-stretchs 7 times, through 220 DEG C of HEAT SETTING 0.5min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 3
By 300g1, 3-dihydroxyacetone (DHA) mixes with 300g water, as composite modifier, mix in high-speed mixer with 5g calcium hydroxide and 1000g polyvinyl alcohol (PVA1788) again, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 145 DEG C, spinneret temperature is 105 DEG C, as-spun fibre is stretched at 25 DEG C after 2 times and enter dry 4min in 120 DEG C of drying boxes, then at 150 DEG C, 175 DEG C, 195 DEG C are carried out 3 grades of hot-stretchs 10 times, through 220 DEG C of HEAT SETTING 3min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 4
150g tri-(methylol) methylglycine is mixed with 450g water, as composite modifier, mix in high-speed mixer with the aluminium oxide of 0.1g and 1000g polyvinyl alcohol (PVA1799) again, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 150 DEG C, spinneret temperature is 120 DEG C, as-spun fibre is stretched at 25 DEG C after 3 times and enter dry 3min in 140 DEG C of drying boxes, then at 150 DEG C, 180 DEG C, 210 DEG C are carried out 3 grades of hot-stretchs 6.7 times, through 215 DEG C of HEAT SETTING 1.5min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 5
300g dimethylolpropionic acid is mixed with 600g water, as composite modifier, mix in high-speed mixer with 40g calcium oxide and 1000g polyvinyl alcohol (PVA2699) again, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out spinning at melt spinning machine and prepares as-spun fibre, spinning temperature is 180 DEG C, spinneret temperature is 135 DEG C, as-spun fibre is stretched at 25 DEG C after 4 times and enter dry 6min in 140 DEG C of drying boxes, then at 150 DEG C, 180 DEG C, 200 DEG C, 230 DEG C are carried out 4 grades of hot-stretchs 2 times, through 230 DEG C of HEAT SETTING 0.5min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 6
200g trimethylolethane is mixed with 300g water, as composite modifier, mix in high-speed mixer with 50g NaOH and 1000g polyvinyl alcohol (PVA2099) again, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 155 DEG C, spinneret temperature is 120 DEG C, as-spun fibre is stretched at 20 DEG C after 2.5 times and enter dry 5min in 120 DEG C of drying boxes, then at 150 DEG C, 170 DEG C, 190 DEG C, 210 DEG C, 220 DEG C are carried out 5 grades of hot-stretchs 7.2 times, through 225 DEG C of HEAT SETTING 1min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 7
By 250g trimethylolpropane, 50g1, 3-dihydroxymethyl acetone mixes with 300g water, as composite modifier, mix in high-speed mixer with 30g magnesium hydroxide and 1000g polyvinyl alcohol (PVA1799) again, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 155 DEG C, spinneret temperature is 120 DEG C, as-spun fibre is stretched at 25 DEG C after 3 times and enter dry 3min in 140 DEG C of drying boxes, then at 150 DEG C, 180 DEG C, 210 DEG C are carried out 3 grades of hot-stretchs 6.7 times, through 220 DEG C of HEAT SETTING 1min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 8
300g trihydroxy methyl (amino) methane is mixed with 500g water, as composite modifier, mix in high-speed mixer with 0.1g NaOH and 1000g polyvinyl alcohol (PVA1799:PVA1788=9:1) again, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 150 DEG C, spinneret temperature is 115 DEG C, as-spun fibre is stretched at 25 DEG C after 2.5 times and enter dry 6min in 120 DEG C of drying boxes, then at 150 DEG C, 180 DEG C, 210 DEG C are carried out 3 grades of hot-stretchs 7.2 times, through 220 DEG C of HEAT SETTING 0.5min, obtain high strength high modulus polyvinyl alcohol fiber.
Embodiment 9
300g trihydroxy methyl (amino) methane is mixed with 500g water, as composite modifier, again with 5g NaOH, 10g magnesium hydroxide and 1000g polyvinyl alcohol (PVA2099) mix in high-speed mixer, obtain modified polyvinylalcohol, modified polyvinylalcohol is carried out on melt spinning machine spinning and prepare as-spun fibre, spinning temperature is 150 DEG C, spinneret temperature is 115 DEG C, as-spun fibre is stretched at 25 DEG C after 2.5 times and enter dry 4min in 130 DEG C of drying boxes, then at 150 DEG C, 180 DEG C, 210 DEG C are carried out 3 grades of hot-stretchs 7.2 times, through 220 DEG C of HEAT SETTING 0.5min, obtain high strength high modulus polyvinyl alcohol fiber.
Performance test:
Vinal obtained for embodiment is carried out the test of fiber number, TENSILE STRENGTH and modulus, TENSILE STRENGTH and
The method of testing of modulus is with reference to standard GB/T/T19975-2005, and test result sees the following form:
As can be seen from the test result of upper table, the fibre strength adopting the inventive method to prepare and the high (TENSILE STRENGTH >=1150MPa of modulus, modulus >=30GPa), can be used for the toughness reinforcing cracking-resistant material of cement, geotextiles, tire cord and the reinforcing material as plastics and rubber.
Claims (7)
1. a preparation method for high strength high modulus polyvinyl alcohol fiber, is characterized in that, comprises the steps:
(1) many for 10-40 part methylol compounds are mixed with 30-70 part water, as composite modifier, then mix in high-speed mixer with 0.01-5 part inorganic alkaline compound and 100 parts of polyvinyl alcohol, obtain modified polyvinylalcohol;
(2) modified polyvinylalcohol prepared by step (1) is carried out spinning on melt spinning machine, prepare polyvinyl alcohol as-spun fibre;
(3) as-spun fibre prepared by step (2) is carried out cold stretch;
(4) fiber after step (3) cold stretch is carried out drying;
(5) step (4) dried fiber is carried out Multi-stage heat stretching, finally fiber is carried out HEAT SETTING, to obtain final product;
In step (1), the degree of polymerization of described polyvinyl alcohol is 1700-2600, and alcoholysis degree is 88-99%;
In step (3), the temperature of cold stretch is 20-25 DEG C, and draw ratio is 2-4 times;
Above number is weight portion.
2. the preparation method of high strength high modulus polyvinyl alcohol fiber as claimed in claim 1, it is characterized in that, in step (1), described many methylol compounds are selected from three (methylol) aminomethane, three (methylol) methylglycine, trimethylolethane, trimethylolpropane, two (trihydroxy methyl) propane, 1, the mixture of one or more arbitrary proportions in 3-dihydroxyacetone (DHA), 2,2-dihydromethyl propionic acids or dimethylolpropionic acid.
3. the preparation method of high strength high modulus polyvinyl alcohol fiber as claimed in claim 1, it is characterized in that, in step (1), described inorganic alkaline compound is selected from the mixture of one or more arbitrary proportions in NaOH, calcium hydroxide, calcium oxide, magnesium hydroxide or aluminium oxide.
4. the preparation method of high strength high modulus polyvinyl alcohol fiber as claimed in claim 1, it is characterized in that, in step (2), spinning temperature is 140-180 DEG C, and spinneret temperature is 105-135 DEG C.
5. the preparation method of high strength high modulus polyvinyl alcohol fiber as claimed in claim 1, it is characterized in that, in step (4), baking temperature is 100-140 DEG C, and the time is 3-10min.
6. the preparation method of high strength high modulus polyvinyl alcohol fiber as claimed in claim 1, is characterized in that, in step (5), the temperature that Multi-stage heat stretches is 150-230 DEG C, and draw ratio is 2-10 times.
7. the preparation method of high strength high modulus polyvinyl alcohol fiber as claimed in claim 1, it is characterized in that, in step (5), heat setting temperature is 200-230 DEG C, and the time is 0.5-3min.
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| CN103981593B (en) * | 2014-05-28 | 2015-11-18 | 永安市宝华林实业发展有限公司 | A kind of preparation method of polyvinyl alcohol melt-spun superfine fibre |
| CN112226840B (en) * | 2020-08-04 | 2021-07-23 | 东华大学 | High-strength high-modulus PVA fiber and preparation method thereof |
| CN114875574B (en) * | 2022-05-23 | 2024-01-19 | 江南大学 | High-strength high-modulus polyvinyl alcohol fiber reinforced polylactic acid composite material and preparation method thereof |
| CN115403323B (en) * | 2022-10-09 | 2023-04-21 | 湖南融城环保科技有限公司 | Method for preparing high-strength concrete by using construction waste recycled aggregate |
Citations (4)
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|---|---|---|---|---|
| US6552123B1 (en) * | 1998-12-16 | 2003-04-22 | Kuraray Co., Ltd. | Thermoplastic polyvinyl alcohol fibers and method for producing them |
| CN1786302A (en) * | 2005-12-13 | 2006-06-14 | 中国石化集团四川维尼纶厂 | Method of preparing high performance polyvinyl alcohel fiber |
| CN101565513A (en) * | 2008-11-26 | 2009-10-28 | 轻工业塑料加工应用研究所 | Heat stabilizer for producing PVA product and method for producing PVA product |
| CN102776597A (en) * | 2012-03-22 | 2012-11-14 | 上海罗洋新材料科技有限公司 | High-strength and high-modulus polyvinyl alcohol fiber and melt spinning method of high-strength and high-modulus polyvinyl alcohol fiber |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6552123B1 (en) * | 1998-12-16 | 2003-04-22 | Kuraray Co., Ltd. | Thermoplastic polyvinyl alcohol fibers and method for producing them |
| CN1786302A (en) * | 2005-12-13 | 2006-06-14 | 中国石化集团四川维尼纶厂 | Method of preparing high performance polyvinyl alcohel fiber |
| CN101565513A (en) * | 2008-11-26 | 2009-10-28 | 轻工业塑料加工应用研究所 | Heat stabilizer for producing PVA product and method for producing PVA product |
| CN102776597A (en) * | 2012-03-22 | 2012-11-14 | 上海罗洋新材料科技有限公司 | High-strength and high-modulus polyvinyl alcohol fiber and melt spinning method of high-strength and high-modulus polyvinyl alcohol fiber |
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