CN102277643B - Elastic composite polyvinyl alcohol fiber and preparation method thereof - Google Patents
Elastic composite polyvinyl alcohol fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to elastic composite polyvinyl alcohol fiber and a preparation method thereof, belonging to the technical field of spinning. In the elastic composite polyvinyl alcohol fiber, polyvinyl alcohol is a continuous phase and aqueous polyurethane is a dispersed phase; and the elastic composite polyvinyl alcohol fiber comprises the following components by weight percent: 50-95% of polyvinyl alcohol and 5-50% of aqueous polyurethane. The elastic composite polyvinyl alcohol fiber is formed by blending and spinning of polyvinyl alcohol solution and aqueous polyurethane solution, and the polyvinyl alcohol solution and the aqueous polyurethane solution are further convenient to prepare. The preparation method is simple in process, special equipment is not required, the operation control is convenient, the industrial production is easy to realize, the elastic elongation rate of the elastic composite polyvinyl alcohol fiber prepared by the method can achieve 40-120%, the elastic recovery rate can achieve 80-95%, diverse products can be realized and the range of applications is wide.
Description
Technical field
The present invention relates to a kind of elastic composite vinal that forms by poly-vinyl alcohol solution and the spinning of aqueous polyurethane solution blending and preparation method thereof, belong to textile technology field.
Background technology
Nineteen twenty-four, the Hermann and the Haehnel of Germany synthesize polyvinyl alcohol, and process fiber with its aqueous solution through dry spinning.Over nearly 100 years; The production process and the technology of vinal are constantly improved; The vinal of different mechanical properties emerges in large numbers gradually, as: high strength poly vinyl alcohol fiber, high strength high modulus polyvinyl alcohol fiber, protein modified polyvinyl alcohol fabric, cracking resistance vinal fiber or the like.Got into since the eighties in last century; Functional fibre causes people's strong interest gradually, and for example: the various functional polyvinyl alcohol fibers of high absorption polyvinyl alcohol fibre, conductive polyvinyl alcohol fiber, bio-medical vinal, flame-proof polyethelene alcohol fibre, hollow vinal, conductive polyvinyl alcohol fiber, anti electromagnetic wave vinal or the like are developed.
The vinal face shaping is near cotton, but intensity and ABRASION RESISTANCE all are superior to cotton, the cotton with 50/50/dimension BLENDED FABRIC, and its strength ratio pure cotton fabric is high by 60%, and ABRASION RESISTANCE can improve 50%～100%.Vinal density is lighter by 20% than cotton approximately, can be woven into the fabric of more same thickness with the fiber of same weight.The hydroscopicity of vinal under standard conditions is 4.5%～5.0%, in several big synthetic fiber kinds, comes out at the top.Because poor thermal conductivity, vinal has good warmth retention property, and in addition, vinal also has well corrosion-resistant and sunlight resistance.
The hot water resistance of vinal is relatively poor, and temperature will take place significantly to shrink and distortion above 110～115 ℃ under hygrometric state, and the elasticity of vinal is not as other synthetic fiber such as polyester; Its fabric is well-pressed inadequately, in the process of taking, is prone to take place wrinkle, therefore; Vinal is mainly used in and cotton blending, is made into various cotton-spinning fabrics, in addition; Also can with other fiber blend or pure spinning, weave all kinds of woven or knitted fabrics.The performance of polyvinyl alcohol filament yarn and outward appearance and natural silk are closely similar, can weave the silks and satins dress material.But, because of its poor flexibility, easy dyeing not, and be difficult to do high-grade dress material, weaving is taken and is restricted.
At present, in the research document and patent of China and foreign countries, do not find the relevant report of relevant elastic polyethylene alcohol fiber.
Summary of the invention
To above-mentioned existing problems, the objective of the invention is to overcome above-mentioned defective, a kind of elastic composite vinal and preparation method thereof is provided, for the technical solution that satisfies the object of the invention is:
A kind of elastic composite vinal, polyvinyl alcohol is a continuous phase in the elastic composite vinal, and aqueous polyurethane is a decentralized photo, and the mass percent of each component is in the elastic composite vinal:
Polyvinyl alcohol 50～95%
Aqueous polyurethane 5～50%.
The degree of polymerization of said polyvinyl alcohol is 1700～2000.
The number-average molecular weight of said aqueous polyurethane is 2000～200000.
The elastic composite vinal is formed by poly-vinyl alcohol solution and the spinning of aqueous polyurethane solution blending, and the preparation method adopts following steps:
The spinning solution preparation of A polyvinyl alcohol water solution and aqueous polyurethane solution
With solid content is 10～20% polyvinyl alcohol water solution and the solid content aqueous polyurethane solution that is 10-60% by following mass percent: polyvinyl alcohol water solution 33～99.1%; The ratio of aqueous polyurethane solution 0.9～67% is put into mixer and is stirred, and whipping temp is 85-95 ℃; Mixing time is 2～8 hours; The rotating speed of mixer is 200-2000 rev/min, forms spinning solution, and is subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, 95～98 ℃ of insulations, deaeration 6～8 hours.
The spinning of C spinning solution
To 95～98 ℃ of insulations, irritate pressure regulation through pressure regulation through the spinning solution after the deaeration of B step, the control spinning speed is 10～30m/min, and spinning technology parameter is respectively: spinning temperature is 95-98 ℃, Na in the coagulating bath
2SO
4Concentration be 400～420g/L solution, coagulation bath temperature is 43～45 ℃, draw ratio be 2-5 doubly, heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 30～40g/L, sulfuric acid 310～400g/L, sodium sulphate 150～220g/L.The hydroformylation temperature is 60～70 ℃, and the acetalation time is 20～60min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.
Owing to adopted above technical scheme, the present invention has the following advantages:
Because polyurethane fiber is a kind of highly elastic fiber, its elongation at break is greater than 400%, and the elastic restoration ratio during deformation 300% is more than 95%, and superior elasticity makes polyurethane fiber in preparation rubber-like clothing, bring into play very big effect.The present invention is matrix material with the polyvinyl alcohol; With the aqueous polyurethane is the elastic return point; Reach the mass percent of each component in the elastic composite vinal through the mass percent of adjusting two kinds of solution; Through mixer aqueous polyurethane solution and poly-vinyl alcohol solution are carried out blend, rely on mixer that aqueous polyurethane is cut into decentralized photo, be dispersed in uniformly in the continuous phase of poly-vinyl alcohol solution.It is that packing material, polyvinyl alcohol are the elastic composite vinal of base material that the method for employing wet spinning can prepare with the aqueous polyurethane; In spinning process; The parameter of coagulating bath, stretching, typing changes the degree of crystallinity and the degree of orientation that can regulate the elastic composite vinal; The adjustment structure obtains different flexible elastic composite vinals.When this fiber receives force-extension, the elongation of fiber axial direction, diametric(al) is dwindled.When external force is removed; Because the elasticity of aqueous polyurethane itself and and matrix material between interaction force; The elastic composite vinal has elasticity recovery; In addition, polyurethane aqueous polyurethane can not be damaged in polyvinyl alcohol water solution and coagulating bath, himself structure of preservation that can be intact.
Original production equipment of the preparation vinylon capable of using of fiber, and technology is simple, and equipment requirements is low, and convenient operation and control is easy to realize suitability for industrialized production.The elastic extension of the elastic composite vinal that is prepared by this method can reach 10%-140%, and elastic recovery rate can reach 80-95%, and fiber product is various, is widely used.
The specific embodiment
A kind of elastic composite vinal, polyvinyl alcohol is a continuous phase in the elastic composite vinal, and aqueous polyurethane is a decentralized photo, and the mass percent of each component is in the elastic composite vinal:
Polyvinyl alcohol 50～95%
Aqueous polyurethane 5～50%.
The degree of polymerization of said polyvinyl alcohol is 1700～2000.
The number-average molecular weight of said aqueous polyurethane is 2000～200000.
A kind of preparation method of elastic composite vinal, the elastic composite vinal is formed by poly-vinyl alcohol solution and the spinning of aqueous polyurethane solution blending, and the preparation method adopts following steps:
The spinning solution preparation of A polyvinyl alcohol water solution and aqueous polyurethane solution
Take by weighing the degree of polymerization and be 1700～2000 polyvinyl alcohol and join in the deionized water, soaking at room temperature 60min makes polyvinyl alcohol abundant swelling in water; After be warmed up to 85-95 ℃, stirred 2～8 hours, the rotating speed of mixer is 200-2000 rev/min; Let polyvinyl alcohol fully dissolve, process solid content and be 10～20% polyvinyl alcohol water solution, according to following mass percent: polyvinyl alcohol water solution 33～99.1%; The ratio of aqueous polyurethane solution 0.9～67% is 10-60% with solid content, and number-average molecular weight is that 20000～350000 aqueous polyurethane solution is put into above-mentioned polyvinyl alcohol water solution and stirred; Whipping temp is 85-95 ℃, and mixing time is 2～8 hours, and the rotating speed of mixer is 200-2000 rev/min; Let polyurethane solutions be dispersed in uniformly in the polyvinyl alcohol water solution, form spinning solution, subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation,, filtrating is squeezed in the deaeration still to remove micro-undissolved swelling body and mechanical admixture, 95～98 ℃ of insulations, normal pressure standing and defoaming 6～8 hours.
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, 95～98 ℃ of insulations, irritate pressure regulation through pressure regulation, control spinning speed is 10～30m/min, make contain polyvinyl alcohol be 50～95% and aqueous polyurethane be 5～50% elastic composite vinal.Spinning technique comprises: spinnerets, coagulating bath, stretching, typing.Spinning technology parameter is respectively: spinning temperature is 95-98 ℃, Na in the coagulating bath
2SO
4Concentration be 400～420g/L solution, coagulation bath temperature is 43～45 ℃, draw ratio be 2-5 doubly, heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 30～40g/L, sulfuric acid 310～400g/L, sodium sulphate 150～220g/L.The hydroformylation temperature is 60～70 ℃, and the acetalation time is 20～60min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.
Below in conjunction with specific embodiment the preparation method of elastic composite elastomer of the present invention is done and to describe in further detail:
Embodiment 1 is by above-mentioned preparation method
The spinning solution preparation of A poly-vinyl alcohol solution and aqueous polyurethane solution
Take by weighing the degree of polymerization and be 1700 polyvinyl alcohol 100g and add in the 900g deionized water, soaking at room temperature 60min, after be warmed up to 95 ℃ and stirred 3 hours; The rotating speed of mixer is 200 rev/mins, processes mass percent and be 10% polyvinyl alcohol water solution, and taking by weighing the 1000g solid content is 10%; Number-average molecular weight is 200000 aqueous polyurethane solution; Join in the above-mentioned polyvinyl alcohol water solution that makes, fully mix 120min at 95 ℃ and obtain mixed solution, subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, be incubated at 95～98 ℃ standing and defoaming 6 hours.
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, insulation is irritated pressure regulation at 95～98 ℃ through pressure regulation, and the control spinning speed is 10m/min, and spinning technology parameter is respectively: spinning temperature is 95-98 ℃, and coagulating bath is the Na of 400g/L
2SO
4The aqueous solution, coagulation bath temperature are 43 ℃, and draw ratio is 2 times, and heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 30g/L, sulfuric acid 310g/L, sodium sulphate 150g/L.The hydroformylation temperature is 60 ℃, and the acetalation time is 20min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.Wherein, polyvinyl alcohol accounts for quality of fiber percentage 50%, and aqueous polyurethane accounts for quality of fiber percentage 50%.
Through measuring, the elastic extension of elastic composite vinal can reach 130%, and elastic recovery rate can reach 93%.Embodiment 2 is by above-mentioned preparation method
The blend solution preparation of A poly-vinyl alcohol solution and aqueous polyurethane solution
Take by weighing average degree of polymerization and be 1800 polyvinyl alcohol 100g and add in the 900g deionized water, soaking at room temperature 60min, after be warmed up to 95 ℃ and stirred 3 hours, the rotating speed of mixer is 2000 rev/mins, processes mass percent and be 10% polyvinyl alcohol water solution.Taking by weighing the 167g solid content is 60%, and number-average molecular weight is 2000 aqueous polyurethane solution, joins in the above-mentioned polyvinyl alcohol water solution that makes, and fully mixes 120min at 90 ℃ and obtains mixed solution, subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, be incubated at 95～98 ℃ deaeration 7 hours.
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, insulation is irritated pressure regulation at 95～98 ℃ through pressure regulation, and the control spinning speed is 20m/min, and spinning technology parameter is respectively: spinning temperature is 95-98 ℃, and coagulating bath is the Na of 400g/L
2SO
4The aqueous solution, coagulation bath temperature are 43 ℃, and draw ratio is 3 times, and heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 36g/L, sulfuric acid 390g/L, sodium sulphate 180g/L.The hydroformylation temperature is 60 ℃, and the acetalation time is 30min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.Wherein, polyvinyl alcohol accounts for 50% of fiber, and aqueous polyurethane accounts for 50% of fiber.
Through measuring, the elastic extension of elastic composite vinal can reach 140%, and elastic recovery rate can reach 95%.
Embodiment 3 is by above-mentioned preparation method
The blend solution preparation of A poly-vinyl alcohol solution and aqueous polyurethane solution
Take by weighing average degree of polymerization and be 1900 polyvinyl alcohol 180g and add in the 820g deionized water, soaking at room temperature 60min, after be warmed up to 95 ℃ and stirred 3 hours, the rotating speed of mixer is 1200 rev/mins, processes mass percent and be 18% polyvinyl alcohol water solution.Taking by weighing the 300g solid content is 40%, and number-average molecular weight is 50000 aqueous polyurethane solution, joins in the above-mentioned polyvinyl alcohol water solution that makes, and fully mixes 120min at 95 ℃ and obtains mixed solution, subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, be incubated at 95～98 ℃ deaeration 8 hours.
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, insulation is irritated pressure regulation at 95～98 ℃ through pressure regulation, and the control spinning speed is 30m/min, and spinning technology parameter is respectively: spinning temperature is 95-98 ℃, and coagulating bath is the Na of 400g/L
2SO
4The aqueous solution, coagulation bath temperature are 45 ℃, and draw ratio is 4 times, and heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 38g/L, sulfuric acid 375g/L, sodium sulphate 200g/L.The hydroformylation temperature is 68 ℃, and the acetalation time is 45min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.Wherein, polyvinyl alcohol accounts for 67% of fiber, and aqueous polyurethane accounts for 33% of fiber.
Through measuring, the elastic extension of elastic composite vinal can reach 90%, and elastic recovery rate can reach 90%.
Embodiment 4 is by above-mentioned preparation method
The blend solution preparation of A poly-vinyl alcohol solution and aqueous polyurethane solution
Take by weighing average degree of polymerization and be 1800 polyvinyl alcohol 2000g and add in the 8000g deionized water, soaking at room temperature 60min, after be warmed up to 95 ℃ and stirred 3 hours, the rotating speed of mixer is 1600 rev/mins, processes mass percent and be 15% polyvinyl alcohol water solution.Taking by weighing the 333g solid content is 60%, and number-average molecular weight is 3000 aqueous polyurethane solution, joins in the above-mentioned polyvinyl alcohol water solution that makes, and fully mixes 120min at 95 ℃ and obtains mixed solution, subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, be incubated at 95～98 ℃ deaeration 8 hours.
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, insulation is irritated pressure regulation at 95～98 ℃ through pressure regulation, and the control spinning speed is 30m/min, and spinning technology parameter is respectively: spinning temperature is 95-98 ℃, and coagulating bath is the Na of 430g/L
2SO
4The aqueous solution, coagulation bath temperature are 45 ℃, and draw ratio is 4 times, and heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 38g/L, sulfuric acid 360g/L, sodium sulphate 190g/L.The hydroformylation temperature is 60C, and the acetalation time is 30min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.Wherein, polyvinyl alcohol accounts for 91% of fiber, and aqueous polyurethane accounts for 9% of fiber.
Through measuring, the elastic extension of elastic composite vinal can reach 70%, and elastic recovery rate can reach 93%.
Embodiment 5 is by above-mentioned preparation method
The blend solution preparation of A poly-vinyl alcohol solution and aqueous polyurethane solution
Take by weighing average degree of polymerization and be 1800 polyvinyl alcohol 950g and add in the 8550g deionized water, soaking at room temperature 60min, after be warmed up to 95 ℃ and stirred 3 hours, the rotating speed of mixer is 1500 rev/mins, processes mass percent and be 10% polyvinyl alcohol water solution.Taking by weighing the 500g solid content is 10%, and number-average molecular weight is 80000 aqueous polyurethane solution, joins in the polyvinyl alcohol water solution that makes, and fully mixes 120min at 90 ℃ and obtains mixed solution, subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, be incubated at 95～98 ℃ deaeration 6～8 hours.
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, insulation is irritated pressure regulation at 95～98 ℃ through pressure regulation, and the control spinning speed is 20m/min.Spinning technology parameter is respectively: spinning temperature is 95-98 ℃, and coagulating bath is the Na of 420g/L
2SO
4The aqueous solution, coagulation bath temperature are 45 ℃, and draw ratio is 4 times, and heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 35g/L, sulfuric acid 350g/L, sodium sulphate 170g/L.The hydroformylation temperature is 65 ℃, and the acetalation time is 40min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.Wherein, polyvinyl alcohol accounts for 95% of fiber, and aqueous polyurethane accounts for 5% of fiber.Through measuring, the elastic extension of elastic composite vinal can reach 40%, and elastic recovery rate can reach 80%.
Embodiment 6 is by above-mentioned preparation method
The blend solution preparation of A poly-vinyl alcohol solution and aqueous polyurethane solution
Take by weighing average degree of polymerization and be 2000 polyvinyl alcohol 1900g and add in the 8100g deionized water, soaking at room temperature 60min, after be warmed up to 95 ℃ and stirred 3 hours, the rotating speed of mixer is 1500 rev/mins, processes the polyvinyl alcohol water solution of mass percent 20%.Taking by weighing the 400g solid content is 50%, and number-average molecular weight is 8000 aqueous polyurethane solution, joins in the above-mentioned polyvinyl alcohol water solution that makes, and fully mixes 120min at 95 ℃ and obtains mixed solution, subsequent use.
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, be incubated at 95～98 ℃ deaeration 6～8 hours.
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, insulation is irritated pressure regulation at 95～98 ℃ through pressure regulation, and the control spinning speed is 30m/min, and spinning technology parameter is respectively: spinning temperature is 95-98 ℃, and coagulating bath is the Na of 420g/L
2SO
4Concentration, coagulation bath temperature are 45 ℃, and draw ratio is 5 times, and heat setting temperature is 200 ℃.
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation.Hydroformylation is bathed and is formed: formaldehyde 40g/L, sulfuric acid 400g/L, sodium sulphate 220g/L.The hydroformylation temperature is 70 ℃, and the acetalation time is 60min.Through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out supervisor of bathing, promptly make the elastic composite vinal.Wherein, polyvinyl alcohol accounts for 90% of fiber, and aqueous polyurethane accounts for 10% of fiber.
Through measuring, the elastic extension of elastic composite vinal can reach 70%, and elastic recovery rate can reach 93%.
Claims (1)
1. the preparation method of an elastic composite vinal is characterized in that, the elastic composite vinal is formed by poly-vinyl alcohol solution and the spinning of aqueous polyurethane solution blending, and the preparation method adopts following steps:
The spinning solution preparation of A polyvinyl alcohol water solution and aqueous polyurethane solution
With solid content is 10～20% polyvinyl alcohol water solution and the solid content aqueous polyurethane solution that is 10-60% by following mass percent: polyvinyl alcohol water solution 33～99.1%; The ratio of aqueous polyurethane solution 0.9～67% is put into mixer and is stirred, and whipping temp is 85-95 ℃; Mixing time is 2～8 hours; The rotating speed of mixer is 100-2000 rev/min, forms spinning solution, and is subsequent use;
The deaeration of B spinning solution
To filter through twice through the spinning solution of A step preparation, squeeze in the deaeration still, 95～98 ℃ of insulations, deaeration 6～8 hours;
The spinning of C spinning solution
Will be through the spinning solution after the deaeration of B step, 95～98 ℃ of insulations, through the compensator pressure regulation, the control spinning speed is 10～30m/min, and spinning technology parameter is respectively: spinning temperature is 95-98 ℃, and coagulating bath is the Na of 400～420g/L
2SO
4The aqueous solution, coagulation bath temperature are 43～45 ℃, and draw ratio is 2-5 times, and heat setting temperature is 200 ℃;
D will get into the hydroformylation bath through the long filament of C step preparation and carry out acetalation; Hydroformylation is bathed and is formed: formaldehyde 30～40g/L, sulfuric acid 310～400g/L, sodium sulphate 150～220g/L; The hydroformylation temperature is 60～70 ℃; The acetalation time is 20～60min, through wet tow drawing-off, oven dry, dry heat drafting and HEAT SETTING, the cut-out program of bathing, promptly makes the elastic composite vinal.
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| CN102704035A (en) * | 2012-05-26 | 2012-10-03 | 东营市鸿信纺织有限公司 | Preparation method of polyvinyl alcohol composite fiber |
| CN105155003B (en) * | 2015-08-06 | 2017-10-20 | 武汉纺织大学 | A kind of preparation method of high-strength and high-modulus highly-elastic urethane fiber |
| CN110981344A (en) * | 2019-12-16 | 2020-04-10 | 深圳市龙岗大工业区混凝土有限公司 | Environment-friendly recycled concrete and preparation process thereof |
| CN116239337A (en) * | 2023-02-24 | 2023-06-09 | 中交第一公路勘察设计研究院有限公司 | Asphalt mixture with strong impact load resistance and preparation method thereof |
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| CA810579A (en) * | 1969-04-15 | Matsubayashi Kanji | Method of manufacturing polyvinyl alcohol fibres having high young's modulus | |
| CN101392412A (en) * | 2008-11-07 | 2009-03-25 | 湖南省湘维有限公司 | High strength vinylon and preparation method thereof |
| CN102080277A (en) * | 2010-12-09 | 2011-06-01 | 武汉纺织大学 | Compound elastic fiber and preparation method thereof |
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|---|---|---|---|---|
| CA810579A (en) * | 1969-04-15 | Matsubayashi Kanji | Method of manufacturing polyvinyl alcohol fibres having high young's modulus | |
| CN101392412A (en) * | 2008-11-07 | 2009-03-25 | 湖南省湘维有限公司 | High strength vinylon and preparation method thereof |
| CN102080277A (en) * | 2010-12-09 | 2011-06-01 | 武汉纺织大学 | Compound elastic fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 邹石龙等.热塑性聚氨酯/聚乙烯醇共混材料制备及性能.《化工新型材料(增刊)》.2007,第35卷(第3期),第63-66页. * |
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