CN104032572A - Hydrophilic modification method for polyester fiber by using sodium alginate - Google Patents

Hydrophilic modification method for polyester fiber by using sodium alginate Download PDF

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Publication number
CN104032572A
CN104032572A CN201410165075.5A CN201410165075A CN104032572A CN 104032572 A CN104032572 A CN 104032572A CN 201410165075 A CN201410165075 A CN 201410165075A CN 104032572 A CN104032572 A CN 104032572A
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sodium alginate
polyster fibre
polyester fiber
mass fraction
reaction
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CN104032572B (en
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黄良辉
姚翔
潘恒祥
孟静
徐卫林
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Wuhan Textile University
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Wuhan Textile University
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Abstract

The invention provides a hydrophilic modification method for a polyester fiber by using sodium alginate, which belongs to the technical field of high polymer. The method comprises the following steps: stirring and pretreating the polyester fiber by using a sodium hydroxide solution with a mass fraction of 3 to 10% in a reaction container at a temperature of 70 to 90 DEG C for 1 h, wherein a solid-liquid ratio is 1: 50, then carrying out flushing with water after completion of a reaction and carrying out drying; and preparing a sodium alginate solution with a mass fraction of 1 to 4%, standing the sodium alginate solution at a temperature of 4 DEG C for 1 h, allowing sodium alginate to expand after sufficient water absorption, placing the sodium alginate solution in the reaction container, adding the dried polyester fiber into the reaction container, carrying out mechanical stirring at normal temperature for 1 to 2 h, adding a calcium chloride solution with a mass fraction of 2% during stirring and after completion of a reaction, successively carrying out flushing with water and then drying at 70 DEG C for 1 h. According to determination results, the contact angle of the modified polyester fiber is less than 10 to 60 DEG, hydrophilicity of the polyester fiber and products thereof are greatly improved, and the modified polyester fiber can be extensively applied to fields like papermaking with renewable resources, clothes, decoration, the industry and the agriculture.

Description

The hydrophilic modification method of a kind of sodium alginate to polyster fibre
Technical field
The present invention relates to a kind of method of polyster fibre modification, relate in particular to the method for a kind of sodium alginate to polyster fibre hydrophilic modifying, belong to technical field of macromolecules.
Background technology
Polyster fibre is the one of polyester fiber, claim again POLYESTER, it is fiber-forming polymer---the polyethylene terephthalate making through esterification or ester exchange and polycondensation reaction taking poly terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol as raw material, the fiber of making through spinning and post processing.Having many uses of polyster fibre, in a large number for the manufacture of goods in clothing and industry.
Many physics of polyster fibre, chemical property are better than natural fabric, as high in intensity, excellent wear resistance, its goods again not yielding, do not crease easily, well-pressed, and cheap.But polyster fibre is because interior molecules is arranged closely, the intermolecular hydrophilic-structure that lacks, thereby regain is very little, and moisture pick-up properties is poor, and gas permeability is bad, and dyeability is poor, and pilling resistance is poor.Therefore the hydrophilicity that improves polyster fibre is the vital task of polyster fibre modification.
Hydrophilic modifying research for polyster fibre mainly contains two aspects: the one, and physical modification method and chemical modification, the former is physical blending, the latter uses the method for chemical graft or block to change the molecular chain structure of polyster fibre; The 2nd, to the surface dressing of fiber or fabric.
But the hydrophilic finishing agent using can not fundamentally change the water-wet behavior of polyster fibre and goods thereof, to be subject to the restriction of service condition toward contact in surface dressing.The mostly principle based on physical blending of method of at present common processing, certain material blend spinning by adulterating in melt spinning liquid with water-wet behavior reaches the object of hydrophilic modifying.Japanese patent application publication No. JP S5766123A, publication date is April 22 nineteen eighty-two, denomination of invention is Preparation of modified polyester fiber.This application case discloses a kind of method of physical modification terylene.This application case adopts a kind of cellulose of modification, under the effect of carrier module, joins in molten polyester, to obtain stable hydrophily, and can not damage the mechanical performance that it has.The method of this modification is set about from raw material, similarly method is well applied in factory's practice is produced, most of modified polyester fibre and goods thereof are all to obtain by the method for physical blending on the market at present, such as Cationic Dyeable Pet, amination modified terylene etc.The angle of producing from raw material, physical blending be a kind of with low cost, produce method of modifying efficiently, but for the hydrophilic modifying of existing polyster fibre and goods thereof, the mostly principle based on chemical reaction, generates new hydrophilic radical by the original surface chemical structure of destruction PET fiber and reaches modification object.
For example, a, honeycomb capillary modified polyester fibre, have good moisture absorption, wet transmitting performance by the microcellular structure Cationic Dyeable Pet fiber that dodges quick-fried processing, and this is inseparable with the internal structure of fiber; Foot point is not the surface wettability that the crystallisation of growing nonparasitically upon another plant that ultimate strength and fracture toughness are less than ordinary polyester fiber .b, polyester fiber improves fiber, the employing crystallisation of growing nonparasitically upon another plant improves the surface and interface performance of PET fiber, forefathers' result of study shows, resin forms and crosses after crystal at fiber surface, and the interface bond strength of fiber and resin obviously strengthens.Therefore, can use grow nonparasitically upon another plant crystallisation PET fiber surface grow nonparasitically upon another plant one deck polarity or with the polymer of other resin thermodynamic compatibility, finally reach the object of improving PET fiber surface performance.C, the improvement of lipase treatment to fabrics of polyester hydrophilicity, lipase has certain denudation to polyster fibre fiber surface, and it is more coarse that fiber surface becomes, and its hydrophily significantly improves.
China Patent Publication No. CN 101367912A, publication date is on February 18th, 2009, denomination of invention is modified dacron having excellent hydrophilic and antistatic property and preparation method thereof, this application case discloses a kind of functional ion liquid modified polyester fibre and preparation method thereof, adopt one to contain 1, the ionic liquid of 3-bis-(2-methoxyl group-2-oxygen ethyl) glyoxaline structure, react with polyster fibre fiber and goods under certain condition, and change the structure of polyster fibre fiber and goods, make it have certain hydrophily.This method effect is obvious, but operation is succinct not, and reactant is on the high side, partially complicated, is unfavorable for heavy industrialization application.China Patent Publication No. CN 101935952B, on January 4 2012 publication date, denomination of invention is a kind of method of dacron bio-modification.This application case discloses a kind of method of enzyme modified dacron.In order to open the ester bond in the large molecule of PET, thereby produce appropriate hydroxyl and carboxyl, improve the hydrophily of fabric, antistatic behaviour, the performances such as pilling, this patent adopts the terylene monomer that contains phenyl ring as inducer, and induction stosterone produces oxidizing ferment modified dacron fabric from hair monad.But the method step is various, conditional request is too high, and the particularly condition harshness of bacterial classification cultivation and Induction Process, is not suitable for heavy industrialization application.European Patent Publication No EP 0548452A1, publication date is on June 30th, 1993, denomination of invention is Hydrophilic silicone-modified polyester resin and fibers and films made there from.This application case discloses a kind of preparation method of hydrophilic polyester fibers.This application case adopts a kind of aromatic dicarboxylic acid and the polysiloxane polyether copolymer esterification that contains dihydroxylic alcohols, and on organosilicon segment, contain hydrophilic group, consequent organosilicon modified polyester, has good hydrophily, is especially applicable to manufacturing hydrophilic fibre and film.The method of this modification is to introduce a kind of segment with hydrophilic radical, but course of reaction is still comparatively complicated, and the hydrophilic modifying of the polyester fiber of inapplicable structural integrity.
Summary of the invention
For the poor problem of above-mentioned polyster fibre hydrophilicity, the object of the present invention is to provide the method for a kind of sodium alginate to polyster fibre hydrophilic modifying.
To achieve these goals, the present invention is achieved through the following technical solutions:
The method of a kind of sodium alginate to polyster fibre hydrophilic modifying; the sodium hydroxide solution that it is 3-10% that described method of modifying refers to polyster fibre mass fraction stirs preliminary treatment 1h under 70-90 DEG C of condition in stirred vessel; mechanical agitation speed is 200-400 rev/min; the solid-to-liquid ratio of polyster fibre and sodium hydroxide solution is 1:50, and preliminary treatment finishes rear water and rinses and be dried; Configuration quality mark is the sodium alginate soln of 1-4%, mechanical agitation speed is 200-400 rev/min, at the temperature of 4 DEG C, leave standstill 1 hour, make the abundant imbibition of sodium alginate, be placed in again reaction vessel, to adding dried polyster fibre in reaction vessel, mechanical agitation 1h-2h under normal temperature, mechanical agitation speed is 200-400 rev/min, in whipping process, then to add mass fraction be 2% calcium chloride solution, after sodium alginate finishes the graft reaction of polyster fibre, through rinsing and being dried, make the polyster fibre after hydrophilic modifying under 70 DEG C of conditions.
Owing to having adopted above technical scheme, with the method comparison of existing polyster fibre hydrophilic modifying, the present invention has the following advantages:
1, inventing related raw material is ordinary hydrogen sodium oxide molybdena AR, calcium chloride AR, sodium alginate AR, ordinary polyester fiber, and raw material sources are simple, and consumption is little.
2, in invention, related reaction condition gentleness is controlled, and if the temperature of polyster fibre alkali treatment is 70-90 DEG C, mechanical agitation speed is 100-400 rev/min, and the graft reaction of polyster fibre just can carry out at normal temperatures, and technological process is simple, easy to operate.
3, in invention, related graft reaction is to be connected and to fetch realization with terylene surface texture with carboxyl by the hydroxyl in sodium alginate, sodium alginate itself is a kind of biotinylated biomolecule avirulence material, there is higher hydrophily and biocompatibility, do not contain poisonous organic solvent.
4, gained modified polyester fibre of the present invention adopts infrared spectrum to characterize: the infrared spectrogram of the polyster fibre that Fig. 1 is sodium alginate-modified front and back, in figure, 2 is in the infrared spectrogram of ordinary polyester fiber, the vibration absorption peak that is C=O at 1719cm-1, 1577cm-1, 1505cm-1 is the vibration absorption peak of phenyl ring, and can find out by the polyster fibre infrared waves spectrogram after sodium alginate-modified shown in 1 in figure, except above wave number has the absworption peak of corresponding functional group, can see the characteristic peak that has all occurred sodium alginate in publishing picture,-COOH base peak (1606cm -1), C-O base peak (1035cm -1).In spectrum, there is equally the hydrophilic hydroxyl (3500-3300cm of functional group -1).From analyzing above, on sodium alginate PET fiber surface graft crosslinking after treatment hydrophilic radical hydroxyl and carboxyl, and in former Structure of PET Fiber exist more than absworption peak.
5, gained modified polyester fibre of the present invention adopts the assay method test of contact angle: the polyster fibre of above-mentioned preparation is ground, makes sheet, measure with CA-A type contact angle instrument, test result is shown in Fig. 2.Along with the content of sodium alginate in modified polyester fibre increases, the contact angle of modified polyester fibre diminishes gradually, owing to having introduced the oh group in sodium alginate on polyster fibre segment, make the polyster fibre after modification obviously show good hydrophily, after measured, the contact angle of modified polyester fibre prepared by the present invention is below 10-60 degree, and hydrophilic effect is stable.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the polyster fibre before and after modification.
Fig. 2 is the tendency chart that the contact angle of the polyster fibre after modification changes with sodium alginate concentration.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further details, sees accompanying drawing
The method of a kind of sodium alginate to polyster fibre hydrophilic modifying, described method refers to first carries out NaOH preliminary treatment to polyster fibre, accurately take a certain amount of sodium hydrate solid, add deionized water to be mixed with the sodium hydroxide solution that mass fraction is 3-10%, again the sodium hydroxide solution preparing is put into stirred vessel, then polyster fibre is immersed in the solution in stirred vessel, under 70-90 DEG C of condition, in stirred vessel, stir preliminary treatment 1h, mechanical agitation speed is 100-400 rev/min, the solid-to-liquid ratio of polyster fibre and sodium hydroxide solution is 1:50, after reaction finishes, polyster fibre is taken out, water rinses and remains in PET fiber surface and inner sodium hydroxide solution, after rinsing well, put into baking oven inner drying, accurately take a certain amount of sodium alginate solid, add deionized water to be mixed with at normal temperatures the sodium alginate soln that mass fraction is 1-4%, this process will fully stir so that sodium alginate solute is uniformly distributed in solution, then be placed on and at the temperature of 4 DEG C, leave standstill 1h, make the abundant imbibition of sodium alginate, obtain the thick solution of sodium alginate, take the calcium chloride solid of certain mass, adding deionized water to be mixed with mass fraction is 2% calcium chloride solution, and fully stirring is that calcium chloride solute is uniformly distributed in solution, dried polyster fibre is taken out, be immersed in the reaction vessel that fills sodium alginate soln, mechanical agitation at normal temperatures, the calcium chloride solution preparing is joined in reaction vessel simultaneously, continue mechanical agitation 1-2h, in course of reaction, make reaction vessel keep sealing, after reaction finishes, polyster fibre is taken out, water rinses to remove the calcium chloride solution of PET fiber surface remnants, uncrosslinked sodium alginate soln, and other impurity, after rinsing well, put into again baking oven dry 1h under 70 DEG C of conditions, be dried rear taking-up, it is exactly the polyster fibre after hydrophilic modifying, in order to characterize the crosslinked sodium alginate monomer of having gone up of PET fiber surface, the polyster fibre after hydrophilic modifying and unmodified polyster fibre are analyzed with infrared waves spectrometer, obtain corresponding infrared waves spectrogram, to observe the chemical group of PET fiber surface, in order to test the hydrophily of the polyster fibre after modification, then it is carried out to the test of contact angle, polyster fibre after the modification of above-mentioned preparation is ground, makes sheet, measure with CA-A type contact angle instrument.
Specific embodiment
embodiment 1
1, accurately take 3g sodium hydrate solid, adding 97ml water to be mixed with mass fraction is 3% sodium hydroxide solution, and contain in stirred vessel, then container is added to 2g polyster fibre, under 70 DEG C of conditions, stir preliminary treatment 1h in reaction vessel, mechanical agitation speed is 200 revs/min, and the solid-to-liquid ratio of polyster fibre and reaction solution is 1:50, after reaction finishes, water rinses and is dried polyster fibre.
2, accurately take 4g sodium alginate solid, adding 96ml deionized water to be mixed with mass fraction is 4% sodium alginate soln, fully stir, mechanical agitation speed is 200 revs/min, place it in again and at the temperature of 4 DEG C, leave standstill 1h, make the abundant imbibition of sodium alginate, obtain the thick solution of sodium alginate.
3, accurately take 2g calcium chloride solid, adding 98ml deionized water to be mixed with mass fraction is that 2% calcium chloride solution is for subsequent use, the polyster fibre of above-mentioned processing is put into and filled the reaction vessel that mass fraction is 4% sodium alginate soln, stir process 1h under normal temperature, mechanical agitation speed is 200 revs/min, in whipping process, add 2% calcium chloride solution.
4, after reaction finishes, be dried and rinse reactant, obtain the polyster fibre after hydrophilic modifying.
5, the hydrophilicity of modified polyester fibre test: the assay method that adopts contact angle, the polyster fibre of above-mentioned preparation is ground, makes sheet, measure with CA-A type contact angle instrument, the contact angle of modified polyester fibre prepared by the present invention is below 55 degree.
embodiment 2
1, accurately take 5g sodium hydrate solid, adding 95ml water to be mixed with mass fraction is 5% sodium hydroxide solution, and contain in stirred vessel, then container is added to 2g polyster fibre, under 80 DEG C of conditions, stir preliminary treatment 1h in reaction vessel, mechanical agitation speed is 300 revs/min, and the solid-to-liquid ratio of polyster fibre and reaction solution is 1:50, after reaction finishes, water rinses and is dried polyster fibre.
2, accurately take 3g sodium alginate solid, adding 97ml deionized water to be mixed with mass fraction is 3% sodium alginate soln, fully stir, mechanical agitation speed is 300 revs/min, place it in again and at the temperature of 4 DEG C, leave standstill 1h, make the abundant imbibition of sodium alginate, obtain the thick solution of sodium alginate.
3, accurately take 2g calcium chloride solid, adding 98ml deionized water to be mixed with mass fraction is that 2% calcium chloride solution is for subsequent use, the polyster fibre of above-mentioned processing is put into and filled the reaction vessel that mass fraction is 3% sodium alginate soln, stir process 1.5h under normal temperature, mechanical agitation speed is in 300 revs/min of whipping process, adds 2% calcium chloride.
4, after reaction finishes, be dried and rinse reactant, obtain the polyster fibre after hydrophilic modifying.
5, the hydrophilicity of modified polyester fibre test: the assay method that adopts contact angle, the polyster fibre of above-mentioned preparation is ground, makes sheet, measure with CA-A type contact angle instrument, the contact angle of modified polyester fibre prepared by the present invention is below 25 degree.
embodiment 3
1, accurately take 10g sodium hydrate solid, adding 90ml water to be mixed with mass fraction is 10% sodium hydroxide solution, and contain in stirred vessel, then container is added to 2g polyster fibre, under 90 DEG C of conditions, stir preliminary treatment 1h in reaction vessel, mechanical agitation speed is 400 revs/min, and the solid-to-liquid ratio of polyster fibre and reaction solution is 1:50, after reaction finishes, water rinses and is dried polyster fibre.
2, accurately take 2g sodium alginate solid, adding 98ml deionized water to be mixed with mass fraction is 2% sodium alginate soln, fully stir, mechanical agitation speed is 400 revs/min, place it in again and at the temperature of 4 DEG C, leave standstill 1h, make the abundant imbibition of sodium alginate, obtain the thick solution of sodium alginate.
3, accurately take 2g calcium chloride solid, adding 98ml deionized water to be mixed with mass fraction is that 2% calcium chloride solution is for subsequent use, the polyster fibre of above-mentioned processing is put into and filled the reaction vessel that mass fraction is 2% sodium alginate soln, stir process 2h under normal temperature, mechanical agitation speed is 400 revs/min, in whipping process, add 2% calcium chloride.
4, after reaction finishes, be dried and rinse reactant, obtain the polyster fibre after hydrophilic modifying.
5, the hydrophilicity of modified polyester fibre test: the assay method that adopts contact angle, the polyster fibre of above-mentioned preparation is ground, makes sheet, measure with CA-A type contact angle instrument, the contact angle of modified polyester fibre prepared by the present invention is below 10 degree.

Claims (1)

1. the sodium alginate method to polyster fibre hydrophilic modifying; it is characterized in that: the sodium hydroxide solution that is 3-10% by polyster fibre mass fraction stirs preliminary treatment 1h under 70-90 DEG C of condition in stirred vessel; mechanical agitation speed is 200-400 rev/min; the solid-to-liquid ratio of polyster fibre and sodium hydroxide solution is 1:50, and preliminary treatment finishes rear water and rinses and be dried; Configuration quality mark is the sodium alginate soln of 1-4%, mechanical agitation speed is 200-400 rev/min, at the temperature of 4 DEG C, leave standstill 1 hour, make the abundant imbibition of sodium alginate, be placed in again reaction vessel, to adding dried polyster fibre in reaction vessel, mechanical agitation 1h-2h under normal temperature, mechanical agitation speed is 200-400 rev/min, in whipping process, then to add mass fraction be 2% calcium chloride solution, after sodium alginate finishes the graft reaction of polyster fibre, through rinsing and being dried, make the polyster fibre after hydrophilic modifying under 70 DEG C of conditions.
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CN107519723A (en) * 2017-08-09 2017-12-29 浙江海洋大学 A kind of dusty material with hydrophilic and oleophobic property
CN107974831A (en) * 2016-10-24 2018-05-01 中国石油化工股份有限公司 Polypropylene non-woven fabric that a kind of calcium alginate is modified and preparation method thereof
WO2018102573A1 (en) * 2016-11-30 2018-06-07 The Research Foundation For The State University Of New York System and method for solar vapor evaporation and condensation
CN108396466A (en) * 2018-03-23 2018-08-14 福建省晋江市恒丰喷胶棉织造有限公司 A kind of Novel heat-preservation gum sprayed cotton and preparation method thereof
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CN110541304A (en) * 2019-08-02 2019-12-06 江苏涌金化纤有限公司 preparation method of single-sided hydrophilic modified polyester fabric
CN112626861A (en) * 2020-12-23 2021-04-09 山东汇高智慧纺织科技集团有限公司 Elastic multifunctional alginic acid composite fiber and preparation method thereof
CN112941699A (en) * 2021-01-28 2021-06-11 宁波共振服饰有限公司 Anti-pilling polyester sportswear fabric and preparation method thereof
CN114481614A (en) * 2021-12-29 2022-05-13 山东瑞礼健康科技有限公司 Seaweed polyester composite fiber and preparation method and application thereof

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CN105220456A (en) * 2015-10-22 2016-01-06 西安工程大学 A kind of preparation method of conductive dacron fibre
CN107974831A (en) * 2016-10-24 2018-05-01 中国石油化工股份有限公司 Polypropylene non-woven fabric that a kind of calcium alginate is modified and preparation method thereof
CN107974831B (en) * 2016-10-24 2020-12-18 中国石油化工股份有限公司 Calcium alginate modified polypropylene fiber non-woven fabric and preparation method thereof
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WO2018102573A1 (en) * 2016-11-30 2018-06-07 The Research Foundation For The State University Of New York System and method for solar vapor evaporation and condensation
CN107519723A (en) * 2017-08-09 2017-12-29 浙江海洋大学 A kind of dusty material with hydrophilic and oleophobic property
CN107519723B (en) * 2017-08-09 2020-08-14 浙江海洋大学 Powder material with hydrophilic oleophobic property
CN108396466A (en) * 2018-03-23 2018-08-14 福建省晋江市恒丰喷胶棉织造有限公司 A kind of Novel heat-preservation gum sprayed cotton and preparation method thereof
CN109235027A (en) * 2018-10-17 2019-01-18 江苏阳光股份有限公司 A kind of nano silver method for sorting of antibacterial wool fabric
CN110541304A (en) * 2019-08-02 2019-12-06 江苏涌金化纤有限公司 preparation method of single-sided hydrophilic modified polyester fabric
CN112626861A (en) * 2020-12-23 2021-04-09 山东汇高智慧纺织科技集团有限公司 Elastic multifunctional alginic acid composite fiber and preparation method thereof
CN112941699A (en) * 2021-01-28 2021-06-11 宁波共振服饰有限公司 Anti-pilling polyester sportswear fabric and preparation method thereof
CN114481614A (en) * 2021-12-29 2022-05-13 山东瑞礼健康科技有限公司 Seaweed polyester composite fiber and preparation method and application thereof

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