CN101435119B - Preparation of modified polyacrylonitrile fibre - Google Patents
Preparation of modified polyacrylonitrile fibre Download PDFInfo
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- CN101435119B CN101435119B CN2008101542435A CN200810154243A CN101435119B CN 101435119 B CN101435119 B CN 101435119B CN 2008101542435 A CN2008101542435 A CN 2008101542435A CN 200810154243 A CN200810154243 A CN 200810154243A CN 101435119 B CN101435119 B CN 101435119B
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Abstract
The invention relates to a preparation method of a modified polyacrylonitrile fiber, comprising the steps of: 1. blending starch and polyacrylonitrile according to the mass ratio of (5 to 50) : (95 to 50), dissolving the mixture in dimethyl sulfoxide solvent with the mass of 3 to 5 times of the total mass of the starch and the polyacrylonitrile, and stirring and evenly mixing at the temperature of 40 to 80 DEG C for 3 to 8h to prepare blending spinning solution; or firstly dissolving the starch and the polyacrylonitrile in own solvent respectively, then blending according to the mass ratio (5 to 50) : (95 to 50), and stirring and evenly mixing at the temperature of 40 to 80 DEG C for 3 to 8h to prepare the blending spinning solution; the starch solvent is dimethyl sulfoxide and the polyacrylonitrile solvent is one of dimethyl formamide and dimethyl acetamide, or mixture of a plurality of dimethyl formamide, dimethyl acetamide and dimethyl sulfoxide according to an arbitrary proportion; and 2. spinning the blending spinning solution according to a conventional solution wet spinning method to prepare the modified polyacrylonitrile fiber.
Description
Technical field
The present invention relates to the chemical fibre manufacturing technology, be specially a kind of method of utilizing the solvent spinning technology to prepare the starch blending modified acrylic fibre.
Background technology
The used raw material major part of macromolecule material product derives from petrochemicals.Because the restriction of petroleum resources, be badly in need of new environmentally friendly, the degradable of exploitation or can partly substitute the raw material of petroleum base polymer.Starch resource is abundant, and is cheap, degradable and renewable.Simultaneously, characteristics such as starch has gel strength height that suction back forms, moisture-holding capacity is big, the anti-mildew ability is strong, biodegradable, therefore developing the new Application Areas of starch has important economic value and realistic meaning.
Polyacrylonitrile fibre is a kind of important weaving composite fibre materials, have many premium properties,, light resistance good as mechanical property given prominence to, and weatherability, heat-resisting, anti-mould and anti-common chemical reagent etc., but because in the big molecule of polyacrylonitrile-CN base hydrophily is poor, the fibre made from polyacrylonitrile fibre easily produces static and easily contamination, has limited it and has used widely.The research of relevant polyacrylonitrile fibre hydrophilic modifying has some reports.For example, Xiao Changfa etc. are monomer with acrylonitrile, methyl methacrylate, with the N hydroxymethyl acrylamide is latent crosslinker, and wet spinning is shaped after the polymerisation in solution, the crosslinked and basic hydrolysis processing through the back, make hydrophilic polymerized acrylonitrile fiber (Xiao Changfa etc. with tridimensional network feature, hydrophilic polymerized acrylonitrile fiber, textile journal, 2007,28 (8), 12-14).This method is to realize the hydrophiling of fiber, technical process more complicated by synthetic and last handling process; Gao Yue etc. adopt the amide-type hydrophilic monomer to the acrylic fabric graft modification, its hydroscopicity and water retention rate all have more significantly and improve (Gao Yue etc., the research of graft modification acrylic fabric hydrophilicity, synthetic fiber industry, 2007,30 (3), 45-46).This method is by chemical method Manufactured fiber to be carried out the big molecule graft reaction in surface, thereby forms hydrophilically modified layer at fiber surface, the technical process more complicated, and need the organic wastewater that contains that produces in the grafting modifying process is handled; Xiao Changfa etc. are according to synthetic polymer blend interface phase separation principle, prepare modified acrylic fibre with loose structure, it has higher suction and water retention characteristic (Xiao Changfa etc., the microcellular structure of copolymerized acrylonitrile/acetyl cellulose blend fiber, the using polymer magazine, 1990,41,439-444, Xiao Changfa, Liu Zhaofeng, MicrovoidFormation of Acrylic Copolymer/Cellulose Acetate Blend Fibers, Journal of Applied Polymer Science, 1990,41,439-444).This method belongs to physical modification, contain the suction-operated that a large amount of microcellular structures are realized fiber liquid towards moisture in the fiber by making, but owing to still lack hydrophilic chemical group in the fiber, the fiber after the modification is still relatively poor to the adsorption capacity of gaseous state moisture, does not change substantially as hydroscopicity.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that a kind of preparation method of modified acrylic fibre is provided.This preparation method utilizes renewable and degradable natural polymer child resource starch to do modifier, it is extensive to have raw material sources, and technical process is easy to characteristics such as commercial scale enforcement, and prepared modified acrylic fibre has hydrophilicity preferably, can partly degrade characteristics such as mechanical property is better.
The technical scheme that the present invention solve the technical problem is: design a kind of preparation method of modified acrylic fibre, this preparation method's technical process is:
1. be that 5～50: 95～50 ratio blend is dissolved in the dimethyl sulfoxide solvent that accounts for 3～5 times of starch and polyacrylonitrile gross masses simultaneously with the starch of intensive drying and polyacrylonitrile in mass ratio, stir 3～8h down at 40～80 ℃ and be mixed, be prepared into starch/polyacrylonitrile blended spinning solution; Perhaps the starch of intensive drying and polyacrylonitrile are dissolved in respectively earlier in the solvent separately, and then are after 5～50: 95～50 the ratio blend, to stir 3～8h down at 40～80 ℃ and be mixed in mass ratio, be prepared into starch/polyacrylonitrile blended spinning solution; The solvent of described starch is a dimethyl sulfoxide (DMSO), and the solvent of described polyacrylonitrile is a kind of in dimethyl formamide and the dimethylacetylamide, perhaps is the mixture of more than one arbitrary proportions in dimethyl formamide, dimethylacetylamide and the dimethyl sulfoxide (DMSO);
2. with the solution wet spinning method spinning routinely of described starch/polyacrylonitrile blended spinning solution, promptly make modified acrylic fibre; Spinning temperature is 40～80 ℃, and coagulating bath is the mixed liquor of water and solvent, and solvent is dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO), and solvent quality content is 10～70%, and coagulation bath temperature is 20～50 ℃.
Compared with prior art, the starch modifying agent that the preparation method of modified acrylic fibre of the present invention adopts has the raw polymer wide material sources, cost is low, the technology maturation of employed solution wet spinning method own, need not to add other special installation, technical process is easy to commercial scale and implements, and the gained fiber has characteristics such as good hydrophilicity and part degradability.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment.
The preparation method of modified acrylic fibre of the present invention (abbreviation preparation method) is dissolved in starch and polyacrylonitrile in the appropriate solvent by proper proportion earlier, prepare uniform starch/polyacrylonitrile blended spinning solution, adopt the spinning of solution wet spinning method then, make the starch conversion polyacrylonitrile fibre.Specific embodiments comprises two kinds: scheme one is:
(1) starch and the polyacrylonitrile with intensive drying is (5～50) in mass ratio: the ratio blend of (95～50), be dissolved in simultaneously in the dimethyl sulfoxide solvent that accounts for 3～5 times of starch and polyacrylonitrile gross masses, stir 3～8h down at 40～80 ℃ and mix, be prepared into starch/polyacrylonitrile blended spinning solution;
(2) with the solution wet spinning method spinning routinely of described starch/polyacrylonitrile blended spinning solution, make the starch conversion polyacrylonitrile fibre, spinning temperature is 40～80 ℃, coagulation bath composition is the mixed liquor of water and solvent, coagulation bath temperature is 20～50 ℃, described solvent is dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO), and solvent quality content is 10～70%.
Dimethyl sulfoxide solvent described in this scheme is the cosolvent of starch and polyacrylonitrile, so starch and polyacrylonitrile can use the solvent dmso solution jointly, is prepared into uniform starch/polyacrylonitrile blended spinning solution.This is a kind of terse and process efficiently.But also have the miscible method of another kind of starch and polyacrylonitrile in the total design of the present invention, promptly scheme two is:
(1) with after the starch intensive drying, join in the dimethyl sulfoxide solvent that accounts for 3～5 times of starch qualities, stir 3～8h down at 40～80 ℃ and mix, make starch solution;
(2) with after the polyacrylonitrile resin intensive drying, join in the solvent that accounts for 3～5 times of polyacrylonitrile resin quality, stirring 3～8h at 40～80 ℃ mixes, make polyacrylonitrile solution, the solvent of described polyacrylonitrile is a kind of in dimethyl formamide and the dimethylacetylamide, perhaps is the mixture of more than one arbitrary proportions in dimethyl formamide, dimethylacetylamide and the dimethyl sulfoxide (DMSO);
(3) with described starch solution and polyacrylonitrile solution in mass ratio (5～50): the ratio blend of (95～50), stir 3～8h at 40～80 ℃ and mix, make starch/polyacrylonitrile blended spinning solution;
(4) with described starch/polyacrylonitrile blended spinning solution routinely after the defoaming method vacuum defoamation of solution wet spinning, utilize the wet-spinning frame spinning technique, after coagulating bath is solidified, make the starch conversion polyacrylonitrile fibre, spinning temperature is 40～80 ℃, and coagulating bath is the mixed liquor of water and solvent, and solvent is dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO), solvent quality content is 10～70%, and coagulation bath temperature is 20～50 ℃.
Starch of the present invention can only be dissolved in dimethyl sulfoxide (DMSO), and described polyacrylonitrile solvent not only can be a dimethyl sulfoxide (DMSO), and can be dimethyl formamide or dimethylacetylamide.Polyacrylonitrile not only can be dissolved in any in dimethyl sulfoxide (DMSO), dimethyl formamide or three kinds of solvents of dimethylacetylamide, and can be dissolved in the mixed solvent that any one above solvent arbitrary proportion is formed in this three kinds of solvents.Therefore, preparation method of the present invention is not only can starch and polyacrylonitrile is molten altogether by described mass ratio blend, be prepared into uniform starch/polyacrylonitrile blended spinning solution, and blend again after starch and polyacrylonitrile can being mixed by described mass ratio Dan Rong, be prepared into uniform starch/polyacrylonitrile blended spinning solution.The former is comparatively terse, and technology is simple; Latter's better adaptability, and neither need increase equipment and change technological parameter, be convenient to industrialization and select to implement.
Test shows that the mass ratio of described starch of preparation method of the present invention (solution) and polyacrylonitrile (solution) is (10～30): when (90～70), effect is comparatively desirable; The solvent quality content of described coagulating bath is that 30～50% o'clock effects are better.
Preparation method's of the present invention main raw material is polyacrylonitrile and starch.Polyacrylonitrile is conventional fibre-forming polymer, and starch is renewable and degradable hydrophilic natural macromolecule.Starch source is in the carbon dioxide of the Nature and the photosynthesis of water, still getting back to the Nature with the form of carbon dioxide and water after the degraded, is the pollution-free green natural macromolecular material, and the product fiber is not had physics damage or chemical damage, simultaneously harmless, environmentally friendly.Starch of the present invention is native starch, and the starch that embodiment uses is pea starch, also can use wheaten starch, potato starch or starch from sweet potato etc., no specific limited.
The described spinning process of preparation method of the present invention is undertaken by conventional soln wet spinning technology, and process conditions such as spinning, deaeration, curing are basic identical with existing preparation polyacrylonitrile fibre.
Further feature of the present invention is, above-mentioned gained fiber is stretched 2～4 times in 50～90 ℃ of water-baths, then can make the better starch conversion polyacrylonitrile fibre of mechanical property (hereinafter to be referred as fiber).The gained fiber can improve the macromolecular degree of orientation of fiber effectively after suitable stretch processing, improve the mechanical property of fiber, satisfies the requirement of fibrous woven or processing such as non-woven.The after-drawing multiple should be suitable, and draw ratio is low excessively, and drawing effect is not obvious; Draw ratio is too high, then can make the fiber itself fracture, runs counter to desire.General draw ratio is 2～5 times, and draw ratio is 2～4 times preferably.
The present invention does not address part and is applicable to prior art.
Further describe the present invention with specific embodiment below.Embodiment is just to further explanation of the present invention, and it does not limit the protection domain of claim of the present invention.
Embodiment 1
Take by weighing dried powdered starch and conventional fibre grade polypropylene nitrile resin respectively, starch is placed dimethyl sulfoxide solvent, polyacrylonitrile resin is dissolved in the dimethylacetylamide, respectively at 65 ℃ of following stirring and dissolving 6h, make mass content and be all 22% starch solution and polyacrylonitrile solution,, and continue to stir fusion 5h down and mix at 65 ℃ then with two kinds of solution blendings, make uniform co-blended spinning solution, the mass ratio of starch and polyacrylonitrile is 30/70.Under same temperature, make co-blended spinning solution for vacuum deaeration 1h after, adopt conventional soln wet spinning technology spinning technique, make starch conversion polyacrylonitrile as-spun fibre; Used coagulating bath is 50% the dimethylacetylamide aqueous solution; With the fully washing in water of gained as-spun fibre, remove contained solvent after, at 60 ℃ of following dry 1h, promptly get the product fiber.
Through room temperature condition test down, the fracture strength of gained fiber is 0.196cN/dtex, and saturated suction (distilled water) amount is 3.12 (gg-1 fibers); Fiber is got into bed and to be embedded in the nature soil after 1 week, and fiber quality reduces 7.3%, and intensity keeps 43.7%; Fiber is got into bed and to be embedded in the nature soil after 1 month, and fiber quality reduces 15.2%, and intensity keeps 13.7%.
Embodiment 2 (comparative example)
Dried conventional fibre grade polypropylene nitrile resin is placed dimethylacetamide solvent, make the solution of mass content 22% at 65 ℃ of following stirring and dissolving 5h, the condition of pressing embodiment 1 is made the polyacrylonitrile fibre of non-modified behind deaeration, spinning technique.After tested, its fracture strength is 0.589cN/dtex, saturated water adsorptive value 0.84 (gg-1 fiber); Fiber is got into bed and to be embedded in the nature soil after 1 week, and fiber quality reduces 0.13%, and intensity keeps 93.7%; Fiber is got into bed and to be embedded in the nature soil after 1 month, and fiber quality reduces 1.2%, and intensity keeps 83.3%.Compare with the result of embodiment 1, the intensity of polyacrylonitrile fibre is higher, but water absorption and degradable performance are relatively poor.
Embodiment 3
In the method for embodiment 1, change the solvent of polyacrylonitrile into dimethyl formamide, the mass concentration of starch solution and polyacrylonitrile solution changes 26% into, starch in the blend solution/polyacrylonitrile mass ratio changes 20/80 into, melting temperature changes 70 ℃ into, other condition is constant, and then the fracture strength of gained fiber is 0.289cN/dtex, and saturated water adsorptive value is 2.24 (gg-1 fibers); Fiber is got into bed and to be embedded in the nature soil after 1 week, and fiber quality reduces 6.4%, and intensity keeps 49.3%; Fiber is got into bed and to be embedded in the nature soil after 1 month, and fiber quality reduces 13.3%, and intensity keeps 19.4%.With comparing of embodiment 1, the polymer concentration in the present embodiment increases, and has improved the mechanical property of fiber, and along with contents of starch reduces, the water absorption of fiber and rate of mass reduction are along with decreasing.
Embodiment 4
In the method for embodiment 1, polyacrylonitrile is dissolved in the mixed solvent of being made up of by 1: 1 volume ratio dimethyl sulfoxide (DMSO) and dimethylacetylamide, starch/polyacrylonitrile mass ratio changes 10/90 into, other condition is constant, the fracture strength of gained fiber is 0.351cN/dtex, and saturated water adsorptive value is 1.89 (gg-1 fibers); Fiber is got into bed and to be embedded in the nature soil after 1 week, and fiber quality reduces 5.6%, and intensity keeps 54.7%; Fiber is got into bed and to be embedded in the nature soil after 1 month, and fiber quality reduces 8.2%, and intensity keeps 39.3%.Compare with the result of embodiment 1, along with content of starch further reduces, the water absorption of fiber and rate of mass reduction also further reduce thereupon.
Embodiment 5
In the method for embodiment 1, change the solvent of polyacrylonitrile into dimethyl sulfoxide (DMSO), be starch and polyacrylonitrile blendedly be dissolved in the dimethyl sulfoxide solvent simultaneously, starch/polyacrylonitrile mass ratio changes 5/95 into, other condition is constant, the fracture strength of gained fiber is 0.413cN/dtex, and saturated water adsorptive value is 1.26 (gg-1 fibers); Fiber is got into bed and to be embedded in the nature soil after 1 week, and fiber quality reduces 3.0%, and intensity keeps 73.3%; Fiber is got into bed and to be embedded in the nature soil after 1 month, and fiber quality reduces 4.2%, and intensity keeps 63.4%.By the result of embodiment 1,3-5 as seen, dimethyl sulfoxide (DMSO), dimethyl formamide are or/and dimethylacetylamide is the good solvent of polyacrylonitrile, no matter use wherein one or more, performance to last gained fiber does not have influence substantially, illustrates that content of starch is unique factor of decision product fiber water absorption and rate of mass reduction.
Embodiment 6
In 60 ℃ of hot water, respectively embodiment 1 and embodiment 5 gained starch conversion polyacrylonitrile fibres are stretched 2.5 times, other condition is constant, and gained fiber test data is respectively: fracture strength 2.02 and 3.05cN/dtex, saturated water adsorptive value 2.98 and 1.19 (gg-1 fiber); Fiber is got into bed and to be embedded in the nature soil after 1 week, fiber quality reduces 6.7% and 2.89% respectively, and intensity keeps 49.9% and 77.3% respectively, and fiber is got into bed and to be embedded in the nature soil after 1 month, fiber quality reduces 14.3% and 4.02% respectively, and intensity keeps 15.6% and 61% respectively.Present embodiment is compared as can be known with the result of embodiment 1 and embodiment 5 respectively, by suitable stretch processing, can improve in the fiber big molecule effectively along the axial degree of orientation of fiber, thereby has improved the mechanical property of product fiber.
Claims (4)
1. the preparation method of a modified acrylic fibre, this preparation method's technical process is:
(1). is that 5～50: 95～50 ratio blend is dissolved in the dimethyl sulfoxide solvent that accounts for 3～5 times of starch and polyacrylonitrile gross masses simultaneously with the starch of intensive drying and polyacrylonitrile in mass ratio, stir 3～8h down at 40～80 ℃ and be mixed, be prepared into starch/polyacrylonitrile blended spinning solution; Perhaps the starch of intensive drying and polyacrylonitrile are dissolved in respectively earlier in the solvent separately, and then are after 5～50: 95～50 the ratio blend, to stir 3～8h down at 40～80 ℃ and be mixed in mass ratio, be prepared into starch/polyacrylonitrile blended spinning solution; The solvent of described starch is a dimethyl sulfoxide (DMSO), and the solvent of described polyacrylonitrile is a kind of in dimethyl formamide and the dimethylacetylamide, perhaps is the mixture of more than one arbitrary proportions in dimethyl formamide, dimethylacetylamide and the dimethyl sulfoxide (DMSO);
(2). with the solution wet spinning method spinning routinely of described starch/polyacrylonitrile blended spinning solution, promptly make modified acrylic fibre; Spinning temperature is 40～80 ℃, and coagulating bath is the mixed liquor of water and solvent, and solvent is dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO), and solvent quality content is 10～70%, and coagulation bath temperature is 20～50 ℃.
2. according to the preparation method of the described modified acrylic fibre of claim 1, the mass ratio that it is characterized in that described starch and polyacrylonitrile is 10～30: 90～70.
3. according to the preparation method of the described modified acrylic fibre of claim 1, the solvent quality content that it is characterized in that described coagulating bath is 30～50%.
4. according to the preparation method of claim 1,2 or 3 described modified acrylic fibres, it is characterized in that the gained modified acrylic fibre is stretched 2～4 times in 50～90 ℃ of water-baths.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102220660B (en) * | 2011-05-20 | 2013-04-17 | 大连工业大学 | Method for preparing high phase transition enthalpy phase transition temperature-adjusting fiber from hydrolysis products of waste acrylic yarn |
| CN103668491A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing anti-pilling acrylic fibers |
| CN103232581A (en) * | 2013-04-27 | 2013-08-07 | 诸城兴贸玉米开发有限公司 | Modified starch capable of resisting high temperature and resisting saturated salt |
| CN106702519A (en) * | 2017-01-09 | 2017-05-24 | 大连工业大学 | Polyacrylonitrile modified starch nano-fiber and preparation method thereof |
| CN107385564A (en) * | 2017-08-28 | 2017-11-24 | 德阳力久云智知识产权运营有限公司 | A kind of preparation method of starch base carbon fibre |
| CN110409013B (en) * | 2019-07-26 | 2021-09-28 | 大连工业大学 | Spinning process for preparing St-g-PAN fiber by wet method |
| CN114457448B (en) * | 2020-10-22 | 2023-08-11 | 中国石油化工股份有限公司 | Method for improving solubility of polyacrylonitrile with high molecular weight produced by dry method |
| CN115679709B (en) * | 2022-11-04 | 2023-10-03 | 苏州铂韬新材料科技有限公司 | Fiber wave-absorbing material |
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