CN103603086B - The preparation method of environment-friendlyultra-soft ultra-soft polyester fiber - Google Patents
The preparation method of environment-friendlyultra-soft ultra-soft polyester fiber Download PDFInfo
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Abstract
The invention provides a kind of production method of environment-friendlyultra-soft ultra-soft polyester fiber.This production method comprises in the polyester material generation structure being joined by modified organic silicon and formed by aromatic acid and aliphatic dihydroxy alcohol, carries out in-situ polymerization and obtains organosilicon polyester composite; Spinning process is carried out to organosilicon polyester composite, obtained polyester fiber.The polyester fiber obtained according to method provided by the invention has submissive and smooth characteristic, without the need to carrying out soft Final finishing to fabric, considerably reduces the discharge that dyeing and finishing adds organic wastewater in man-hour.
Description
Technical field
The present invention relates to textile fiber technology field, in particular to a kind of production method of environment-friendlyultra-soft ultra-soft polyester fiber.
Background technology
In recent years, people require more and more higher to the comfortableness of garment material, health, security and the feature of environmental protection etc.When people purchase textiles or clothes, what first judge is eyes, is then sense of touch.Certainly, can not underestimate tempting feel, it has become a quality index, also becomes main sales aid.
Polyester fiber is the most important components of synthetic fiber, because its excellent physical and chemical performance is widely used in textile garment field.In order to increase pliability and the comfort level of polyester fiber garment material, usually at present in the dyeing and finishing process of garment material, soft treatment is carried out to polyester fiber.The process of this soft treatment is: immersed by fabric in the solution containing softener, soak a period of time, namely obtain soft polyester fiber garment material after oven dry.Silicone softening agent has excellent flexibility, is a kind of widely used softener material.The bond energy of Si-O key is more much higher than the bond energy (356kJ/mol) of C-C key, and reach 452.2kJ/mol, this makes siloxanes have good heat endurance and ageing-resistant performance.Si-O-Si bond angle is very large, easily rotates between Si and O, and make main chain section become soft, the surface energy of adding siloxane group is very low, impels silica chain when film forming to surface migration.Through the fabric of organosilicon process, there is soft smooth, the plentiful feature such as flexible, be applicable to the arrangement of different textiles (natural fabric, synthetic fiber, blend fibre etc.).
The mixture that silicone softening agent is made up of materials such as active material (modified organic silicon), surfactant, water, preservative agents.All active materials have a general character part: they are water insoluble.In order to the active material and water that make softener dissolve each other, need in mixed solution, add surfactant and other auxiliary agent, form the aqueous solution by emulsification.Fabric is after soft treatment, and a small amount of softener and whole auxiliary agents all will fall as discharge of wastewater.Therefore, a large amount of organic wastewater discharges can be produced in the dyeing and finishing process of polyester fiber garment material, more and more serious pollution is also caused to the water environment gone from bad to worse.Especially terylene is owing to lacking active group, and molecules align is tight, and smooth surface, relatively cotton fiber is low for the adsorbance of softener, and washability is also poor, and therefore in sewage, organic emission amount is larger.The adsorption percentage of usual silicone softening agent on fabric, 43% ~ 66%, has the organosilicon of 0.5% ~ 4% to be adsorbed on wall, and the organosilicon of 32% ~ 54% is residual to be discharged in the solution.
Polyoxyethylene nonylphenol ether (NPE) is often used as surfactant in textile manufacturing, is discharged in environment and can resolves into rapidly nonyl phenol (NP).Nonyl phenol (NP) is a kind of generally acknowledged environmental hormone, and it can simulate estrogen, has an impact to the sexual development of biology, and the endocrine that interference is biological, to reproductive system, there is toxicity.Meanwhile, nonyl phenol (NP) is constantly accumulated in vivo by food chain, therefore there are some researches show, even if the concentration of discharge is very low, also has harmfulness.
Discuss as can be seen from above, the discharge of silicone softening agent has serious harm to environment, and this problem causes extensive concern in the industry.Such as, the Chinese invention patent being CN102031578A at application publication number discloses a kind of manufacture method of organic-silicon-modified hydrophilic special-shaped polyester fiber.This manufacture method adopts the organic silicon polyether silicone oil containing hydrophilic radical to replace conventional polyether, by the reactive group in organic silicon polyether silicone oil and the incompatible synthesizing organo-silicon modified poly ester of monomer generation copolymerization; Again organic-silicon-modified hydrophilic polyesters section melting, spinning are formed polyester fiber.Although the method to some extent solves soft agent emission problem, the polyester fiber fabric that the method is produced still need be carried out soft treatment and just can be obtained soft smooth feel in dyeing and finishing processing.
Summary of the invention
In order to reduce organic wastewater discharge capacity that polyester fiber fabric produces in dyeing and finishing process and simplify production process, the invention provides a kind of production method of environmental protection polyester fiber.Modified organic silicon material is added polymeric system when polyester synthesizes by this production method, carries out in-situ polymerization, forms organosilicon polyester complex fiber material.Silicone segments moves to polymer surfaces because surface energy is low, makes polyester fiber have submissive and smooth characteristic, carrying out soft Final finishing man-hour, considerably reducing the discharge that dyeing and finishing adds large amount of organic waste water in man-hour without the need to adding in dyeing and finishing fabric.
The preparation method of environment-friendlyultra-soft ultra-soft polyester fiber provided by the invention comprises the following steps: joined by modified organic silicon in the polyester material generation structure formed by aromatic acid and aliphatic dihydroxy alcohol, carries out in-situ polymerization and obtains organosilicon polyester composite; Then spinning process is carried out to organosilicon polyester composite and can obtain environment-friendlyultra-soft ultra-soft polyester fiber.
In detailed description of the invention provided by the invention, this preparation method comprises the following steps: step S1, aromatic acid and aliphatic dihydroxy alcohol generation esterification, generates esterification products; Step S2, adds modified organic silicon in esterification products, under reaction temperature and pressure, and esterification products generation polycondensation reaction, described modified organic silicon and polycondensation product carry out in-situ polymerization, obtain organosilicon polyester composite; Step S3, carries out spinning process to organosilicon polyester composite, forms polyester fiber.
Further, above-mentioned steps S1 comprises: the ratio by aromatic acid and aliphatic dihydroxy alcohol with mol ratio being 1:1.1-1.8, in esterification device esterification occurs after mixing with catalyst and stabilizing agent.
Preferably, aromatic acid is selected from terephthalic acid (TPA), M-phthalic acid, 1, one or more in 3-M-phthalic acid binaryglycol ester-5 sodium sulfonate, carboxyethyl (phenyl) phosphoric acid, cyclic phosphate ester derivant, hydroxy benzenes oxygen phosphorus acrylic acid, 2-carboxyethyl (phenyl) hypophosphorous acid, more preferably, aromatic acid is terephthalic acid (TPA).
Preferably, aliphatic dihydroxy alcohol is selected from ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, 1, one or more in 2 butanediols, Isosorbide-5-Nitrae butanediol, pentanediol, hexylene glycol, neopentyl glycol, PTMEG, and more preferably, aliphatic dihydroxy alcohol is ethylene glycol.
Preferably, above-mentioned catalyst is selected from the one in Titanium series catalyst, antimony-based catalyst, or two kinds of compounds formed; Stabilizing agent be selected from triphenyl phosphite, trimethyl phosphate, phosphoric acid, irganox1010, irganox259, irganox1330, irganoxB900 one or more.
Further, the reaction temperature of above-mentioned esterification is 240-270 DEG C.
Further, above-mentioned steps S2 comprises: step S21, is mixed by modified organic silicon with Organic Alcohol, obtains modified organic silicon mixed liquor; Step S22, joins in esterification products by modified organic silicon mixed liquor; Step S23, under reaction temperature and pressure, esterification products generation polycondensation reaction, modified organic silicon and polycondensation product carry out in-situ polymerization simultaneously, obtain organosilicon polyester composite.
Preferably, above-mentioned modified organic silicon is selected from one or more in organic silicon modified by polyether, polyester resin change properties of organic silicon and polyether polyester modified organic silicon; More preferably, the polyethers in organic silicon modified by polyether comprises polyglycol ether, polytetramethylene glycol ether, polypropylene glycol ether or copolyether; Polyester in polyester resin change properties of organic silicon comprises poly adipate succinic acid ester, polyethylene glycol adipate, polycaprolactone, polyethylene terephthalate, polybutylene terephthalate (PBT).
Preferably, the addition of modified organic silicon is the 0.1-10wt% of described polyester material generation structure gross weight, and more preferably, the addition of modified organic silicon is 0.5-3wt%.
Further, the polycondensation reaction in step S23 comprises: be 240 DEG C-275 DEG C in reaction temperature, and reaction pressure is under the condition of 5000-1000Pa, carries out prepolymerization reaction; And be 280 DEG C-300 DEG C in reaction temperature, reaction pressure is under the condition of 1000-100Pa, carries out whole polycondensation reaction.
Further, the inherent viscosity of the organosilicon composite copolymerization ester material that step S2 obtains is 0.5-1.2dl/g, and preferably this inherent viscosity is 0.6-0.7dl/g.
Further, above-mentioned organosilicon composite copolymerization ester material can the specification of processing fiber be 0.5-50dtex.
As can be seen from above technical scheme, the production method of polyester fiber provided by the invention, by adding modified organic silicon material when polyester synthesizes, carries out in-situ polymerization, forms organosilicon polyester complex fiber material.Polyethers in modified organic silicon or polyester compatible and fixing with polymeric system in the polymer, move to polymer surfaces because organosilicon chain surface energy is low, make polyester fiber have submissive and smooth characteristic.By the production method of polyester fiber provided by the invention without the need to carrying out soft Final finishing to fabric, not only simplifying technological process and also considerably reducing dyeing and finishing and add the discharge of wastewater of man-hour containing large amount of organic.
Accompanying drawing explanation
The accompanying drawing forming a part of the present invention is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the environment-friendlyultra-soft ultra-soft polyester fiber preparation method schematic flow sheet that the embodiment of the invention provides.
Detailed description of the invention
Hereinafter also describe the present invention in detail with reference to accompanying drawing in conjunction with the embodiments.It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.
From background technology, in existing polyester fiber fabric and blended yarn woven fabric soft treatment technique thereof, have organic waste water too much, the technical problem of complex production process.The present inventor studies for the problems referred to above, creatively proposes to carry out in-situ polymerization by adding modified organic silicon material when polyester synthesizes, and forms organosilicon polyester complex fiber material.Specifically, the preparation method of this environment-friendlyultra-soft ultra-soft polyester fiber comprises the following steps: joined by modified organic silicon in the polyester material generation structure formed by aromatic acid and aliphatic dihydroxy alcohol, carries out in-situ polymerization and obtains organosilicon polyester composite; Then spinning process is carried out to organosilicon polyester composite and can obtain environment-friendlyultra-soft ultra-soft polyester fiber.Here the modified organic silicon of indication refers to the modified organic silicon had with polyester fiber consistent part and organosilicon chain part, such as, and organic silicon polyether, organosilicon polyester or organic silicon polyether ester.Due to part compatible with polyester fiber in modified organic silicon (such as, polyethers or polyester) can compatible and fixing with polymeric system in the polymer, and organosilicon chain surface energy is low and move to polymer surfaces, make, by its obtained polyester fiber, there is submissive and smooth characteristic.
Here it should be noted that, the reaction that the polyester material generation structure formed by aromatic acid and aliphatic dihydroxy alcohol occurs comprises esterification and polycondensation reaction, modified organic silicon can add reaction system when esterification occurs and in pulping process, also reaction system can be added before polycondensation reaction after esterification, depending on producing equipment, such as, continuous polymerization unit adds the form and aspect being more conducive to having obtained after adopting esterification.
The polyester fiber obtained according to the method described above has submissive and smooth characteristic, carries out soft treatment, considerably reduce the discharge that dyeing and finishing adds a large amount of organic wastewater in man-hour without the need to the fabric of processing is added softener in dyeing and finishing processing.
Now, the illustrative embodiments according to the application is described with reference to the accompanying drawings in more detail.But these illustrative embodiments can be implemented by multiple different form, and should not be interpreted as being only limited to embodiment set forth herein.Should be understood that, there is provided these embodiments be in order to make the application open thorough and complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art, in the accompanying drawings, for the sake of clarity, expand the thickness in layer and region, and use the device that identical Reference numeral represents identical, thus will omit description of them.
Fig. 1 shows the environment-friendlyultra-soft ultra-soft polyester fiber preparation method schematic flow sheet that the embodiment of the invention provides.
As shown in Figure 1, first implementation step S1, aromatic acid and aliphatic dihydroxy alcohol generation esterification, generate esterification products; S2, adds modified organic silicon in esterification products, the polyester material generation structure generation polycondensation reaction of then aromatic acid and aliphatic dihydroxy alcohol formation, and modified organic silicon and polycondensation product carry out in-situ polymerization, obtain organosilicon polyester composite; Last implementation step S3, carries out spinning process to organosilicon polyester composite, thus forms polyester fiber.As can be seen from above step, the present invention, by in-situ polymerization, adds organosilicon modifier and synthesizes organic silicon polyether composite, make the polyester fiber obtained have submissive and smooth characteristic in process of polyester synthesizing.The fabric produced by polyester fiber provided by the invention is without the need to carrying out soft Final finishing to fabric, and fabric just has soft and smooth characteristic, not only simplifies technological process and also considerably reduces dyeing and finishing and add the discharge of wastewater that man-hour contains large amount of organic.
For each step, the concrete technology flow process of each step will be elaborated below.
For step S1, aromatic acid and aliphatic dihydroxy alcohol generation esterification generate esterification products.In concrete mode provided by the present invention, this step comprises: be that aromatic acid and aliphatic dihydroxy alcohol, catalyst and the stabilizing agent of 1:1.1-1.8 mixes by mol ratio, then add in esterification device, at 240 DEG C-270 DEG C, carry out esterification; Preferably, controlled by esterification yield >=85%, this is conducive to the carrying out of polycondensation reaction and obtains suitable molecular weight and the composite polyester resin of molecular weight distribution thereof.
Preferably, the aromatic acid adopted is selected from terephthalic acid (TPA), M-phthalic acid, 1, one or more in 3-M-phthalic acid binaryglycol ester-5 sodium sulfonate, carboxyethyl (phenyl) phosphoric acid, cyclic phosphate ester derivant, hydroxy benzenes oxygen phosphorus acrylic acid, 2-carboxyethyl (phenyl) hypophosphorous acid, wherein more preferably terephthalic acid (TPA).
Preferably, the aliphatic dihydroxy alcohol of employing is selected from ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, 1, one or more in 2 butanediols, Isosorbide-5-Nitrae butanediol, pentanediol, hexylene glycol, neopentyl glycol, PTMEG, more preferably ethylene glycol.
Preferably, the catalyst of employing is selected from the compound of one or both compositions in Titanium series catalyst (such as titanate esters), acetate type catalyst (as antimony acetate); The stabilizing agent adopted is selected from triphenyl phosphite, trimethyl phosphate, phosphoric acid, irganox1010(tetra-[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] quaternary amyl alcohol ester), the two [3-(3 of irganox259(hexylene glycol, 5-di-tert-butyl-hydroxy phenyl) propionic ester), irganox1330(1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene), one or more in irganoxB900.More preferably antimony acetate.
After completing steps S1, implementation step S2, adds modified organic silicon in described esterification products, mix, under reaction temperature and pressure, described esterification products generation polycondensation reaction, modified organic silicon and polycondensation product carry out in-situ polymerization, obtain organosilicon polyester composite.In detailed description of the invention provided by the invention, this step comprises:
Step S21, mixes modified organic silicon with Organic Alcohol, obtains modified organic silicon mixed liquor.Wherein, the volume fraction of modified organic silicon in modified organic silicon mixed liquor is 20-80%;
Step S22, joins in esterification products by modified organic silicon mixed liquor, and wherein modified organic silicon accounts for the 0.1-10wt% of polyester material generation structure gross weight, is preferably 0.5-3wt%; In practical operation, the addition of modified organic silicon can the composite resin (polymer) that generates of aromatic acid and aliphatic dihydroxy alcohol reaction be also weight basis, with 0.1-10wt%, the ratio being preferably 0.5-3wt% joins in polyester material generation structure.
Step S23, under reaction temperature and pressure, esterification products generation polycondensation reaction, modified organic silicon and polycondensation product carry out in-situ polymerization simultaneously, obtain organosilicon polyester composite.The reaction temperature of this indication and pressure are temperature and pressure conventional in polyester material preparation process, and such as, temperature can between 200 DEG C to 300 DEG C, and pressure between 100Pa to 5000Pa, just can repeat no more at this.
Preferably, above-mentioned polycondensation reaction comprises following process: be 240 DEG C-275 DEG C in reaction temperature, and reaction pressure is carry out prepolymerization reaction under the condition of 5000-1000Pa; Then, be 280 DEG C-300 DEG C in reaction temperature, reaction pressure is under the condition of 1000-100Pa, carries out whole polycondensation reaction.
Preferably, above-mentioned modified organic silicon is selected from one or more in organic silicon modified by polyether, polyester resin change properties of organic silicon and polyether polyester modified organic silicon; The polyethers of above-mentioned organic silicon modified by polyether comprises polyglycol ether, polytetramethylene glycol ether, polypropylene glycol ether or copolyether; Polyester in above-mentioned polyester resin change properties of organic silicon comprises poly adipate succinic acid ester, polyethylene glycol adipate, polycaprolactone, polyethylene terephthalate, polybutylene terephthalate (PBT).Polyester or organic silicon modified by polyether is selected to be have good compatibility for obtaining with polymeric system.
After completing steps S2, just can obtain organosilicon polyester composite.Then conveniently spinning process technique carries out mode processing to organosilicon polyester composite, can obtain polyester fiber provided by the present invention, also just completes the enforcement of step S3.Because the spinning process technique that the present invention adopts is routine techniques means, just repeat no more at this.Preferably, when the inherent viscosity of the organosilicon polyester composite that step S2 generates is 0.5-1.2dl/g, when being more preferably 0.6-0.7dl/g, just can carry out spinning process to complex polyester, form polyester fiber.The line density of the polyester fiber obtained is 0.5-50dtex, and has submissive and smooth characteristic.
The production method of polyester fiber provided by the present invention will be further illustrated below with specific embodiment.
Embodiment 1
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.1 by mol ratio, catalyst acetic acid antimony and stabilizing agent triphenyl phosphite join mixing device, add esterifier and carry out esterification after mixing.When esterification yield reaches 90%, the polyglycol ether modified organic silicon be blended in ethylene glycol is added reactor, wherein the volume fraction of polyglycol ether modified organic silicon in mixed liquor is 20%, and the addition of organic silicon modified by polyether is the 1wt% of polyester material generation structure gross weight.Carry out prepolymerization reaction after mixing, reaction temperature is 240 DEG C, and pressure is 900Pa, carries out prepolymerization reaction when esterification yield reaches 85%, and carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 280 DEG C, and pressure is 200Pa.When inherent viscosity is 0.6dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.
Embodiment 2
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.1 by mol ratio, catalyst acetic acid antimony and stabilizing agent triphenyl phosphite add mixing device, add esterifier after mixing and carry out esterification, when esterification yield reaches more than 90%, the poly adipate succinic acid ester modified silicon be blended in ethylene glycol is added system, wherein the volume fraction of poly adipate succinic acid ester modified silicon in mixed liquor is 40%, the 2wt% of the composite resin gross weight that the addition of poly adipate succinic acid ester modified silicon generates with terephthalic acid (TPA) and glycol reaction.Carry out prepolymerization reaction after mixing, reaction temperature is 255 DEG C, and pressure is 900Pa.Carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 290 DEG C, and pressure is 150Pa.When inherent viscosity is 0.6dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.
Embodiment 3
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.2 by mol ratio, catalyst acetic acid antimony and stabilizing agent triphenyl phosphite add mixing device, add esterifier after mixing and carry out esterification, when esterification yield reaches more than 85%, the poly adipate succinic acid ester modified silicon be blended in ethylene glycol is added system, wherein the volume fraction of poly adipate succinic acid ester modified silicon in mixed liquor is 40%, and polyester organic silicon modified by polyether adds in reaction system with the 3wt% of the composite resin gross weight that terephthalic acid (TPA) and glycol reaction generate.Carry out prepolymerization reaction after mixing, reaction temperature is 255 DEG C, and pressure is 900Pa.Carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 290 DEG C, and pressure is 150Pa.When inherent viscosity is 0.6dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.
Embodiment 4
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.1 by mol ratio, catalyst acetic acid antimony and stabilizing agent triphenyl phosphite add mixing device, add esterifier after mixing and carry out esterification, when esterification yield reaches more than 93%, the polytetramethylene glycol ether modified organic silicon be blended in ethylene glycol and polyethylene glycol adipate modified organic silicon are added system by the mixed proportion of 1:1, and modified organic silicon content accounts for 5% of polyester material generation structure gross weight.Carry out prepolymerization reaction after mixing, reaction temperature is 255 DEG C, and pressure is 900Pa.Carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 290 DEG C, and pressure is 150Pa.When inherent viscosity is 0.6dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.
Embodiment 5
Be terephthalic acid (TPA) and the butanediol of 1:1.8 by mol ratio, catalyst Ti acid esters and stabilizing agent irganox1010 add blender, enter after mixing and carry out esterification at esterifier, reaction temperature is 230 DEG C, pressure is: 78kpa, reaction esterification yield reaches more than 97%, and the polytetramethylene glycol ether modified organic silicon be blended in butanediol is added system, and polytetramethylene glycol ether modified organic silicon content accounts for the 3wt% of polyester material generation structure gross weight.Carry out prepolymerization reaction after mixing, reaction temperature is 240 DEG C, and pressure is 1200kpa, and after reaction certain hour, carry out whole polycondensation reaction, reaction temperature is 245 degree, and pressure is 140pa.When inherent viscosity is 1.0dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.
Embodiment 6
Be terephthalic acid (TPA) and 1.3 propylene glycol of 1:1.8 by mol ratio, catalyst Ti acid esters and stabilizing agent irganox1010 add mixing device, add esterification device after mixing and carry out esterification, after esterification yield reaches 96%, the polypropylene glycol ether modified organic silicon be blended in propylene glycol is added system, and polypropylene glycol ether modified organic silicon content adds in reaction system with the 0.5wt% of the composite resin gross weight that terephthalic acid (TPA) and the reaction of 1.3 propylene glycol generate.Carry out prepolymerization reaction after mixing, reaction temperature is 250 DEG C, and pressure is 3000pa.Carry out the poly-reaction of final minification after precondensation terminates, reaction temperature is 260 DEG C, and pressure is 100pa.When inherent viscosity is 1.1dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.
Embodiment 7
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.1 by mol ratio, catalyst acetic acid antimony and stabilizing agent triphenyl phosphite add mixing device, add esterifier after mixing and carry out esterification, when esterification yield reaches more than 90%, by the polypropylene glycol ether modified silicon be blended in propylene glycol and account for 1 of total acid mol ratio 3%, 3-M-phthalic acid binaryglycol ester-5 sodium sulfonate adds system, and polypropylene glycol ether modified silicon adds with the 2wt% of the composite resin gross weight that terephthalic acid (TPA) and glycol reaction generate.Carry out prepolymerization reaction after mixing, reaction temperature is 255 DEG C, and pressure is 900Pa.Carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 290 DEG C, and pressure is 100Pa. when to work as inherent viscosity be 0.6dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.The fiber of spinning has cationic-dyeable performance.
Embodiment 8
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.1 by mol ratio, catalyst acetic acid antimony and stabilizing agent triphenyl phosphite add mixing device, add esterifier after mixing and carry out esterification, when esterification yield reaches more than 90%, the polyglycol ether modified organic silicon be blended in ethylene glycol and the polyglycol ether accounting for gross weight 8% are added system, and the addition of polyglycol ether modified organic silicon is the 0.5wt% of the composite resin gross weight that terephthalic acid (TPA) and glycol reaction generate.Carry out prepolymerization reaction after mixing, reaction temperature is 255 DEG C, and pressure is 900Pa.Carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 290 DEG C, and pressure is 180Pa.When inherent viscosity is 0.9dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.The fiber of spinning has hydrophilicity.
Embodiment 9
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.1 by mol ratio, catalyst acetic acid antimony and stabilizing agent irganox1010 add mixing device, add esterifier after mixing and carry out esterification, when esterification yield reaches more than 90%, by the polytetramethylene glycol ether modified organic silicon be blended in butanediol, account for gross weight 5% polyglycol ether and account for 1 of total acid molal quantity 3%, 3-ethylene isophthalate-5 sodium sulfonate adds system, and the addition of polytetramethylene glycol ether modified organic silicon is the 1wt% of the composite resin gross weight that terephthalic acid (TPA) and glycol reaction generate.Carry out prepolymerization reaction after mixing, reaction temperature is 255 DEG C, and pressure is 900Pa.Carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 290 DEG C, and pressure is 240Pa.When inherent viscosity is 0.6dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.The fiber of spinning has dyeing at normal pressure performance.
Embodiment 10
Be terephthalic acid (TPA) and the ethylene glycol of 1:1.1 by mol ratio, catalyst acetic acid antimony and stabilizing agent triphenyl phosphite add mixing device, add esterifier after mixing and carry out esterification, when esterification yield reaches more than 90%, by the polyglycol ether modified organic silicon be blended in ethylene glycol and CEPA(2-carboxyethyl (phenyl) hypophosphorous acid accounting for total acid mol ratio 5%) add system, the addition of polyglycol ether modified organic silicon is the 2wt% of the composite resin gross weight that terephthalic acid (TPA) and glycol reaction generate.Carry out prepolymerization reaction after mixing, reaction temperature is 255 DEG C, and pressure is 900Pa.Carry out the poly-reaction of final minification after prepolymerization reaction terminates, reaction temperature is 290 DEG C, and pressure is 100Pa.When inherent viscosity is 0.7dl/g, discharging, extrude, pelletizing obtains composite polyester resin.Resin forms fibrous material through spinning process.The fiber of spinning has fire resistance, and limited oxygen index reaches more than 30.
The original position organosilicon complex polyester of embodiment 1,2,7 and 9 is carried out spinning process respectively, process fiber dimensious be 100D 72F drafted fibre, by TENSILE STRENGTH and the elongation at break of the obtained fiber of tensometer test, test result asks for an interview table 1.As can be seen from Table 1, the polyester fiber prepared according to method provided by the invention has very high TENSILE STRENGTH and elongation at break, and its numerical value is suitable with same specification ordinary polyester fiber, and this shows that obtained polyester fiber has good toughness and flexibility.In addition, obtained polyester fiber has the softness and smooth characteristic that ordinary polyester fiber do not have, without the need to carrying out soft treatment in dyeing and finishing processing.
Table 1
| Spin fast m min | TENSILE STRENGTH cN/dtex | Elongation at break % | |
| Embodiment 1 | 3000 | 4.13 | 29.63 |
| Embodiment 2 | 3000 | 3.89 | 24.12 |
| Embodiment 7 | 3000 | 3.94 | 26.82 |
| Embodiment 9 | 3000 | 4.09 | 35.33 |
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
1. carry out in-situ polymerization by adding modified organic silicon material when polyester synthesizes, make the polyethers in organosilicon or polyester compatible and fixing with polymeric system in the polymer, the surface energy of organosilicon chain is low and move to polymer surfaces, thus causes polyester fiber to have submissive and smooth characteristic.
2. the polyester fiber obtained according to method provided by the invention has submissive and smooth characteristic, without the need to carrying out soft Final finishing to fabric, considerably reducing dyeing and finishing and adding the discharge of wastewater of man-hour containing large amount of organic.
These are only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. a preparation method for environment-friendlyultra-soft ultra-soft polyester fiber, is characterized in that, is joined by modified organic silicon in the polyester material generation structure formed by aromatic acid and aliphatic dihydroxy alcohol, carries out in-situ polymerization and obtains organosilicon polyester composite; Spinning process is carried out to described organosilicon polyester composite, obtained polyester fiber; Described modified organic silicon be selected from organic silicon modified by polyether, polyester resin change properties of organic silicon and polyether polyester modified organic silicon one or more.
2. preparation method according to claim 1, is characterized in that, described preparation method comprises the following steps:
Step S1, aromatic acid and aliphatic dihydroxy alcohol generation esterification, generate esterification products;
Step S2, adds modified organic silicon in described esterification products, under reaction temperature and pressure, and described esterification products generation polycondensation reaction, described modified organic silicon and polycondensation product carry out in-situ polymerization, obtain organosilicon polyester composite;
Step S3, carries out spinning process to described organosilicon polyester composite, obtained polyester fiber.
3. preparation method according to claim 1 and 2, it is characterized in that, described step S1 comprises: the ratio by described aromatic acid and aliphatic dihydroxy alcohol with mol ratio being 1:1.1-1.8, in esterification device esterification occurs after mixing with catalyst and stabilizing agent.
4. preparation method according to claim 3, is characterized in that, described aromatic acid is selected from terephthalic acid (TPA) or M-phthalic acid.
5. preparation method according to claim 3, is characterized in that, described aliphatic dihydroxy alcohol is selected from ethylene glycol, 1, ammediol, 1, one or more in 2-propylene glycol, 1,2-butanediol, BDO, pentanediol, hexylene glycol, neopentyl glycol, PTMEG.
6. preparation method according to claim 3, is characterized in that, described catalyst is selected from the one in Titanium series catalyst, antimony-based catalyst, or two kinds of compounds formed; Described stabilizing agent be selected from triphenyl phosphite, trimethyl phosphate, phosphoric acid, irganox1010, irganox259, irganox1330, irganoxB900 one or more.
7. preparation method according to claim 2, is characterized in that, the reaction temperature of described esterification is 240-270 DEG C.
8. preparation method according to claim 2, is characterized in that, described step S2 comprises,
Step S21, mixes described modified organic silicon with Organic Alcohol, obtains modified organic silicon mixed liquor;
Step S22, joins in described esterification products by described modified organic silicon mixed liquor;
Step S23, under reaction temperature and pressure, described esterification products generation polycondensation reaction, described modified organic silicon and polycondensation product carry out in-situ polymerization simultaneously, obtain described organosilicon polyester composite.
9. preparation method according to claim 1, is characterized in that, the polyethers in described organic silicon modified by polyether comprises polyglycol ether, polytetramethylene glycol ether, polypropylene glycol ether or copolyether.
10. preparation method according to claim 1, it is characterized in that, the polyester in described polyester resin change properties of organic silicon comprises poly adipate succinic acid ester, polyethylene glycol adipate, polycaprolactone, polyethylene terephthalate, polybutylene terephthalate (PBT).
11. preparation methods according to claim 1, is characterized in that, the addition of described modified organic silicon is the 0.1-10wt% of described polyester material generation structure gross weight
12. preparation methods according to claim 11, is characterized in that, the addition of described modified organic silicon is the 0.5-3wt% of described polyester material generation structure gross weight.
13. preparation methods according to claim 8, is characterized in that, the polycondensation reaction in described step S23 comprises:
Be 240 DEG C-275 DEG C in reaction temperature, reaction pressure is under the condition of 5000-1000Pa, carries out prepolymerization reaction; And
Be 280 DEG C-300 DEG C in reaction temperature, reaction pressure is under the condition of 1000-100Pa, carries out whole polycondensation reaction.
14. preparation methods according to claim 1, is characterized in that, the inherent viscosity of described organosilicon polyester composite is 0.5-1.2dl/g.
15. preparation methods according to claim 1, is characterized in that, the inherent viscosity of described organosilicon polyester composite is 0.6-0.7dl/g.
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| CN106592004B (en) * | 2016-11-22 | 2018-09-21 | 厦门翔鹭化纤股份有限公司 | A kind of preparation method of hot-melt polyester fiber |
| WO2019086982A1 (en) | 2017-11-06 | 2019-05-09 | King Abdullah University Of Science And Technology | Method and device for making copolymer-wrapped nanotube fibers |
| CN108035044A (en) * | 2017-12-28 | 2018-05-15 | 宁波三同编织有限公司 | A kind of organosilicon-polyimide modified High-temperature-respolyester polyester fiber shell fabric and preparation method thereof |
| CN108660537B (en) * | 2018-05-21 | 2020-05-19 | 东华大学 | Preparation method of heat-sensitive copolyester fiber |
| CN108624982B (en) * | 2018-05-21 | 2020-05-12 | 东华大学 | Preparation method of cation modified PTT copolyester fiber |
| CN109134831A (en) * | 2018-07-28 | 2019-01-04 | 广东舜天新材料有限公司 | A kind of copolyesters preparation method of high yield |
| CN115612080A (en) * | 2021-07-14 | 2023-01-17 | 华润化学材料科技股份有限公司 | Silicon-containing polyester and preparation method thereof |
| CN115785419B (en) * | 2023-01-31 | 2023-05-02 | 富海(东营)新材料科技有限公司 | Modified PETG copolyester, preparation method thereof and preparation method of foamed particles thereof |
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