CN104499086A - Preparation method of polyoxymethylene crude fiber for toughening concrete - Google Patents
Preparation method of polyoxymethylene crude fiber for toughening concrete Download PDFInfo
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Abstract
The invention relates to a preparation method of a polyoxymethylene crude fiber for toughening concrete. The method comprises the following steps: (1) mixing polyoxymethylene resin, a modified nano filler, a water-soluble polymer pore-foaming agent and a high-performance fiber in a high-speed mixer, extruding and pelletizing, so as to obtain modified POM aggregates; and (2) spinning the modified POM aggregates in a twin-screw extruder, directly feeding to a cooling bath to cool and mold, washing in a hot water bath, removing a water-soluble polymer, carrying out hot stretching, carrying out secondary stretching after drying, carrying out heat setting, and finally cutting into staple fibers, so as to prepare polyoxymethylene crude fiber the surface of which has micropores, with the equivalent diameter being 0.1-1mm, the tensile strength being greater than or equal to 600MPa and the tensile modulus being greater than or equal to 6.5GPa. Nanoparticle-enhanced and fiber-enhanced synergistic reinforcing effects are adopted, so that the high-performance polyoxymethylene crude fiber is prepared by virtue of general crude fiber equipment.
Description
Technical field
The present invention relates to a kind of preparation method of polyoxymethylene fiber, especially for the coarse-fibred preparation method of the polyoxymethylene that concrete is toughness reinforcing.
Background technology
Concrete is one of most important construction material, current forward high-performance, functionalization, high-durability future development.Concrete exists that tensile strength is low, poor toughness and the shortcoming such as easy to crack, causes concrete structure ftractureing lower than under Ultimate Loads, works service life and endurance quality are reduced.In cement-base composite material, mix synthetic fiber can improve its fragility, suppress its early-age plastic to ftracture, improve its cracking resistance, impervious, the performance such as toughness, antifatigue and shock resistance.
Synthetic fiber can divide the fortifying fibre of the reinforcement of concrete according to diameter, can be divided into the fine fibre of diameter < 0.1mm and the crude fibre of diameter >=0.1mm.Fine fibre due to its diameter little, the easy conglomeration when concrete-agitating, volume is low, only effective to concrete early stage cracking resistance, and limited to the performance improvement such as concrete cracking resistance, toughness, flexural tensile strength, impact resistance after sclerosis.Crude fibre can improve concrete anti-dry shrinkage and cracking and toughness, is a kind of concrete activeness and quietness material, obtains application in fields such as gunite concrete, concrete road surface, bridge floor and industry ground slab, airfield runway and parking lots.
At present, the crude fibre of the reinforcement of concrete is mainly polypropylene (PP) crude fibre.Polyoxymethylene is the engineering plastics being better than PP in a kind of strand containing ehter bond, mechanical property, the cementitiousness of itself and cement-based material is better than PP, and cost of material is lower than PP, if can be prepared into crude fibre, alternative PP crude fibre application, reduces crude fibre Cost of Concrete.At present, the relevant report of polyoxymethylene fiber is mainly as follows: WO-2008001924, CN1715464A are by introducing Third monomer unit, and the flexible chain controlling polyoxymethylene is greater than 30s, prepares fiber by melt spinning; At controlled working process aspect, as CN1555430A, CN102011201A, CN101792938A adopt the technique of multistage slow cooling-quenching, carry out heating slow cooling after spinnerets is left to as-spun fibre, adopt the drawing process of steam under pressure simultaneously, the fiber of preparation high strength.But for the exploitation of spinning-grade raw material, mainly from converging angle, technical requirement is high, core technology grasp by external several big companies, cost of material is higher, is difficult to carry out large-scale industrialization and applies.The complex process of multistage slow cooling-quenching, needs to carry out slow cooling-quenching transformation to spinning equipment, carries out high drafting, and mainly for the preparation of the fine fibre of high-strength and high-modulus.
In CN103435964A, other additives such as polyformaldehyde 80-100 part, carbon fiber 12-18 part, polytetrafluoroethylene (PTFE) 1-5 part, nano imvite 2-5 part are extruded preparation and increase wear-resisting enhancing POM pellet, the composition such as CN102993626A polyformaldehyde, glass fibre, polyurethane, compound flame retardant, antioxidant, formaldehyde absorbent, coupling agent has prepared the fire-retardant POM of enhancing.As can be seen from these patents, interpolation CNT, glass fibre can strengthen POM, but these patents are all adopt single enhancement method, strengthen limited efficiency, and constituent species is various, use mainly as engineering plastics, do not relate to the Synthesis and applications of fiber, more do not relate to the polyoxymethylene crude fibre that concrete is toughness reinforcing.
Summary of the invention
Instant invention overcomes deficiency of the prior art, be to provide the toughness reinforcing polyoxymethylene of a kind of concrete coarse-fibred preparation method, which employs nano particle to strengthen and fibre-reinforced synergistic enhancing effect, under lower draw ratio, prepare the coarse-fibred preparation method of the toughness reinforcing polyoxymethylene of concrete with general crude fibre equipment.
Concrete technical scheme of the present invention is as follows:
The coarse-fibred preparation method of a kind of toughness reinforcing polyoxymethylene of concrete, comprises the steps:
(1) extruding pelletization after polyoxymethylene resin, modified Nano filling, water-soluble polymer pore-foaming agent, high-performance fiber being mixed in homogenizer, obtains modification POM pellet;
(2) modification POM pellet is directly entered cooling forming in cooling bath after spinning in double screw extruder, then carry out washing removing water-soluble polymer in hot water bath while, carry out hot-stretch; Then carry out succeeding stretch after drying, then carry out HEAT SETTING, final cutting becomes staple fibre, and preparing fiber equivalent diameter is 0.1-1mm, and the polyoxymethylene crude fibre of micropore is contained on the surface of TENSILE STRENGTH >=600MPa, stretch modulus >=6.5GPa.
Above-mentioned in hot water bath, carry out washing removing water-soluble polymer while to carry out hot-stretch be carry out in the hot water bath that 6m is long, control washing time >=3.6s; To ensure the dissolving of water-soluble polymer pore-foaming agent.
Selected by the processing fluidity of polyoxymethylene resin, the mean molecule quantity of polyoxymethylene resin is too high or too low all cannot be processed into fiber; The mean molecule quantity of preferred described polyoxymethylene resin is 20000-50000, and melt index is 6-10g/10min.
Described modified Nano filling is selected from the one in CNT, nano-cellulose whisker, Graphene; The addition of modified Nano filling accounts for the 0.1-1.5% of polyoxymethylene resin quality.Described modified Nano filling has higher strength and modulus, can be used for improving the intensity of fiber.
Described modified Nano filling is through surface carboxylicization process, and concrete treatment step is as follows: with glacial acetic acid diluting modification Nano filling to flowable turbid liquid, the mass fraction of modified Nano filling is 10%; Then (quality of sulfuric acid is 5% of modified Nano filling quality slowly to drip the mixed liquor of sulfuric acid, glacial acetic acid and acetic anhydride while stirring, the quality of glacial acetic acid is 5 times of modified Nano filling quality, and the quality of acetic anhydride is 30% of modified Nano filling quality); After dropwising, under agitation reactant is warming up to 45 DEG C from room temperature with the speed of 1 DEG C/min, reacts 30 min, product is successively with ethanol and acetone washing, and suction filtration, drying obtains the modified Nano filling of surface carboxylicization process.
Described water-soluble polymer pore-foaming agent is selected from the blend of a kind of in polyethylene glycol oxide, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone or two kinds; The addition of described water-soluble polymer pore-foaming agent accounts for the 0.5%-3% of polyoxymethylene resin quality., water-soluble polymer pore-foaming agent dissolves in a water bath, and the fiber surface made produces hole, increases the surface roughness of fiber, increases the cementitiousness of fiber and matrix.
Described high-performance fiber is selected from the one in aramid fiber, carbon fiber, polyphenylene sulfide fibre, polyparaphenylene's benzo-dioxazole fiber; Its addition accounts for the 5-20% of polyoxymethylene resin quality, and the length of high-performance fiber is 1-3mm.The intensity of above-mentioned high-performance fiber and fusing point, higher than polyoxymethylene, ensure to exist with fibers form when melting, can improve the strength and modulus of polyoxymethylene.
In step (1), in homogenizer, mixing temperature is 80-100 DEG C, and incorporation time is 3-8min; When ensureing to mix, not conglomeration again.
In step (2), the temperature of cooling bath is-60 DEG C ~-20 DEG C, and the distance of cooling bath liquid level and Screw Extrusion mouth mould is 2-10mm; Fiber is cooled fast.
Described cooling bath is the mixture of a kind of or two kinds of arbitrary proportions in ethanol, ethylene glycol; Temperature for controlled cooling model bath is-60 DEG C ~-20 DEG C.
In step (2), the draft temperature carrying out hot-stretch in hot water bath is 80-95 DEG C, and draw ratio is 2-4 times; Succeeding stretch carries out in oven heat, and draft temperature is 140-170 DEG C, and draw ratio is 1.2-2 times; Ensure the abundant stretching of fiber, ensure final fibrous mechanical property.
In step (2), baking temperature is 100-130 DEG C, and drying time is 20s-40s; Heat setting temperature is 158 DEG C-163 DEG C, and the time is 20-50s.
Polyoxymethylene resin-made standby one-tenth fiber equivalent diameter is 0.1-1mm by the present invention, and the polyoxymethylene crude fibre of micropore is contained on the surface of TENSILE STRENGTH >=600MPa, stretch modulus >=6.5GPa, and is applied to concrete field, has enriched coarse-fibred kind.Have employed nano particle to strengthen and fibre-reinforced synergistic enhancing effect, under lower draw ratio, high performance polyoxymethylene crude fibre has been prepared with general crude fibre equipment, dissolved water soluble polymer in water-bath stretch slot, increasing the roughness of fiber surface, decreasing the impression process in crude fibre preparation, without the need to transforming equipment, technique is simple, and cost is low.
specific implementation method
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 after having read content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
When " fiber equivalent diameter " of the present invention refers to that fibre section is non-circular, the circular cross section diameter conversed by the principle that sectional area is equal.
In embodiment, the mean molecule quantity of described polyoxymethylene resin is 20000-50000, and melt index is 6-10g/10min.
embodiment 1
The polyvinylpyrrolidone of the CNT of the polyoxymethylene resin of 1000g, the carboxylated process of 1g, 50g carbon fiber (length of fiber is 1-3mm), 5g is put into high-speed mixer, stop stirring after mixer being warming up to 80 DEG C of stirring 8min, after material cooling, in screw extruder, extruding pelletization obtains modification POM pellet, the melting in double screw extruder of modification POM pellet is entered cooling forming in the ethanol cooling bath of-20 DEG C after die extrusion, the distance of cooling bath liquid level and extrusion neck ring mold is 2mm, the silk of cooling is imported in 95 DEG C of water-baths while carrying out washing removing water-soluble polymer and carry out 3 times of stretchings, washing time is 4s, after 120 DEG C of oven heat drying process 20s, carry out succeeding stretch entering in 140 DEG C of oven heats, draw ratio is 1.5 times, then HEAT SETTING 50s in the oven heat of 158 DEG C, finally by the crude fibre rolling of preparation, the short crude fibre being cut into different length.The key property of its fiber is in table 1.
embodiment 2
The polyethylene glycol oxide of the nano-cellulose whisker of the polyoxymethylene resin of 1000g, the carboxylated process of 15g, 200g polyparaphenylene benzo-dioxazole fiber (length of fiber is 1-3mm), 10g is put into high-speed mixer, stop stirring after mixer being warming up to 90 DEG C of stirring 5min, after material cooling, in screw extruder, extruding pelletization obtains modification POM pellet, the melting in double screw extruder of modification POM pellet is entered after die extrusion cooling forming in the glycol-cooled bath of-60 DEG C, the distance of cooling bath liquid level and extrusion neck ring mold is 5mm, the silk of cooling is imported in 95 DEG C of water-baths while carrying out washing removing water-soluble polymer and carry out 4 times of stretchings, washing time is 3.6s, after 120 DEG C of oven heat drying process 40s, carry out succeeding stretch entering in 160 DEG C of oven heats, draw ratio is 1.2 times, then shape 30s in 163 DEG C of oven heats, finally by the crude fibre rolling of preparation, the short crude fibre being cut into different length.The key property of its fiber is in table 1.
embodiment 3
The polyethylene glycol of the nano-cellulose whisker of the polyoxymethylene resin of 1000g, the carboxylated process of 10g, 100g polyphenylene sulfide fibre (length of fiber is 1-3mm), 30g is put into high-speed mixer, stop stirring after mixer being warming up to 100 DEG C of stirring 4min, after material cooling, in screw extruder, extruding pelletization obtains modification POM pellet, the melting in double screw extruder of modification POM pellet is entered after die extrusion (volume ratio of ethanol and ethylene glycol is 1:1) cooling forming in the ethanol of-30 DEG C and glycol-cooled bath, the distance of cooling bath liquid level and extrusion neck ring mold is 10mm, the silk of cooling is imported in 90 DEG C of water-baths while carrying out washing removing water-soluble polymer and carry out 2 times of stretchings, washing time is 7.2s, after 120 DEG C of oven heat drying process 30s, carry out succeeding stretch entering in 160 DEG C of oven heats, draw ratio is 2 times, then shape 20s in 163 DEG C of oven heats, finally by the crude fibre rolling of preparation, the short crude fibre being cut into different length.The key property of its fiber is in table 1.
embodiment 4
The polyvinyl alcohol of the CNT of the polyoxymethylene resin of 1000g, the carboxylated process of 5g, 200g polyparaphenylene benzo-dioxazole fiber (length of fiber is 1-3mm), 10g is put into high-speed mixer, stop stirring after mixer being warming up to 90 DEG C of stirring 5min, after material cooling, in screw extruder, extruding pelletization obtains modification POM pellet, the melting in double screw extruder of modification POM pellet is entered after die extrusion (volume ratio of ethanol and ethylene glycol is 3:1) cooling forming in the ethanol of-40 DEG C and glycol-cooled bath, the distance of cooling bath liquid level and extrusion neck ring mold is 8mm, the silk of cooling is imported in 95 DEG C of water-baths while carrying out washing removing water-soluble polymer and carry out 4 times of stretchings, washing time is 4.2s, after 120 DEG C of oven heat drying process 20s, carry out succeeding stretch entering in 170 DEG C of oven heats, draw ratio is 2 times, then shape 30s in 160 DEG C of oven heats, finally by the crude fibre rolling of preparation, the short crude fibre being cut into different length.The key property of its fiber is in table 1.
embodiment 5
The polyethylene glycol of the CNT of the polyoxymethylene resin of 1000g, the carboxylated process of 10g, 100g polyparaphenylene benzo-dioxazole fiber (length of fiber is 1-3mm), 20g is put into high-speed mixer, stop stirring after mixer being warming up to 100 DEG C of stirring 6min, after material cooling, in screw extruder, extruding pelletization obtains modification POM pellet, the melting in double screw extruder of modification POM pellet is entered after die extrusion ethanol and the middle cooling forming of glycol-cooled bath (volume ratio of ethanol and ethylene glycol is 1:5) of-60 DEG C, the distance of cooling bath liquid level and extrusion neck ring mold is 5mm, the silk of cooling is imported in 80 DEG C of water-baths while carrying out washing removing water-soluble polymer and carry out 3 times of stretchings, washing time is 5.6s, after 120 DEG C of oven heat drying process 25s, carry out succeeding stretch entering in 170 DEG C of oven heats, draw ratio is 1.5 times, then shape 20s in 162 DEG C of oven heats, finally by the crude fibre rolling of preparation, the short crude fibre being cut into different length.The key property of its fiber is in table 1.
embodiment 6
The polyethylene glycol oxide of the nano-cellulose of the polyoxymethylene resin of 1000g, the carboxylated process of 15g, 100g aramid fiber (length of fiber is 1-3mm), 10g is put into high-speed mixer, stop stirring after mixer being warming up to 100 DEG C of stirring 5min, after material cooling, in screw extruder, extruding pelletization obtains modification POM pellet, the melting in double screw extruder of modification POM pellet is entered after die extrusion (volume ratio of ethanol and ethylene glycol is 2:3) cooling forming in the ethanol of-60 DEG C and glycol-cooled bath, the distance of cooling bath liquid level and extrusion neck ring mold is 6mm, the silk of cooling is imported in 85 DEG C of water-baths while carrying out washing removing water-soluble polymer and carry out 3.5 times of stretchings, washing time is 3.6s, after 120 DEG C of oven heat drying process 35s, carry out succeeding stretch entering in 170 DEG C of oven heats, draw ratio is 2 times, then shape 40s in 160 DEG C of oven heats, finally by the crude fibre rolling of preparation, the short crude fibre being cut into different length.The key property of its fiber is in table 1.
Fiber key property prepared by table 1 embodiment
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Diameter (mm) | 0.55 | 0.4 | 1 | 0.1 | 0.75 | 0.25 |
| Tensile strength (MPa) | 625 | 784 | 600 | 886 | 620 | 806 |
| Elastic modelling quantity (GPa) | 7.2 | 8.0 | 6.5 | 9.5 | 6.8 | 8.6 |
The method of testing of tensile strength described in table 1 and elastic modelling quantity is with reference to standard GB/T/T19975-2005).
Claims (10)
1. the coarse-fibred preparation method of the toughness reinforcing polyoxymethylene of concrete, is characterized in that comprising the steps:
(1) extruding pelletization after polyoxymethylene resin, modified Nano filling, water-soluble polymer pore-foaming agent, high-performance fiber being mixed in homogenizer, obtains modification POM pellet;
(2) modification POM pellet is directly entered cooling forming in cooling bath after spinning in double screw extruder, then carry out washing removing water-soluble polymer in hot water bath while, carry out hot-stretch; Then carry out succeeding stretch after drying, then carry out HEAT SETTING, final cutting becomes staple fibre, and preparing fiber equivalent diameter is 0.1-1mm, and the polyoxymethylene crude fibre of micropore is contained on the surface of TENSILE STRENGTH >=600MPa, stretch modulus >=6.5GPa.
2. preparation method according to claim 1, it is characterized in that the mean molecule quantity of described polyoxymethylene resin is 20000-50000, melt index is 6-10g/10min.
3. preparation method according to claim 1, is characterized in that described modified Nano filling is selected from the one in CNT, nano-cellulose whisker, Graphene; The addition of modified Nano filling accounts for the 0.1-1.5% of polyoxymethylene resin quality.
4. preparation method according to claim 3, is characterized in that described modified Nano filling is through surface carboxylicization process.
5. preparation method according to claim 1, is characterized in that described water-soluble polymer pore-foaming agent is selected from the blend of a kind of in polyethylene glycol oxide, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone or two kinds; The addition of described water-soluble polymer pore-foaming agent accounts for the 0.5%-3% of polyoxymethylene resin quality.
6. preparation method according to claim 1, is characterized in that described high-performance fiber is selected from the one in aramid fiber, carbon fiber, polyphenylene sulfide fibre, polyparaphenylene's benzo-dioxazole fiber; Its addition accounts for the 5-20% of polyoxymethylene resin quality, and the length of high-performance fiber is 1-3mm.
7. the preparation method according to any one of claim 1 to 6, it is characterized in that, in step (1), in homogenizer, mixing temperature is 80-100 DEG C, incorporation time is 3-8min.
8. the preparation method according to any one of claim 1 to 6, is characterized in that in step (2), and the temperature of cooling bath is-60 DEG C ~-20 DEG C, and the distance of cooling bath liquid level and Screw Extrusion mouth mould is 2-10mm.
9. preparation method according to claim 8, is characterized in that described cooling bath is the mixture of a kind of or two kinds of arbitrary proportions in ethanol, ethylene glycol.
10. the preparation method according to any one of claim 1 to 6, is characterized in that in step (2), and the draft temperature carrying out hot-stretch in hot water bath is 80-95 DEG C, and draw ratio is 2-4 times; Succeeding stretch carries out in oven heat, and draft temperature is 140-170 DEG C, and draw ratio is 1.2-2 times; Baking temperature is 100-130 DEG C, and drying time is 20s-40s.
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| CN107586373A (en) * | 2017-10-18 | 2018-01-16 | 江苏苏博特新材料股份有限公司 | A kind of crystal property adjustable spinning polyoxymethylene resin and its spinning process |
| CN107938019A (en) * | 2017-10-16 | 2018-04-20 | 唐山开滦化工科技有限公司 | A kind of one-step shaping preparation method of polyformaldehyde fibre |
| US20210387911A1 (en) * | 2018-10-31 | 2021-12-16 | Adfil N.V. | Fiber for concrete reinforcement |
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