CN102767081B - Method for preparing hydrophilic finishing agent of polyester fabric through waste polyester - Google Patents
Method for preparing hydrophilic finishing agent of polyester fabric through waste polyester Download PDFInfo
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- CN102767081B CN102767081B CN201210287346.5A CN201210287346A CN102767081B CN 102767081 B CN102767081 B CN 102767081B CN 201210287346 A CN201210287346 A CN 201210287346A CN 102767081 B CN102767081 B CN 102767081B
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- polyester
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to a method for preparing a hydrophilic finishing agent of polyester fabric through waste polyester, and belongs to the technical field of the polyester chemical industry. The method includes subjecting the waste polyester and ethylene glycol to alcoholysis to obtain ethylene glycol terephthalate, and then adding isophthalic acid-5-sulfonate or a derivative, polyethylene glycol, acetate of alkali metal and a complex heat stabilizer for a polymerization reaction so as to obtain the agent. The preparing method is simple; the obtained hydrophilic finishing agent has a good color and water solubility and can be dissolved in water easily without an emulsifier; and simultaneously, the waste polyester can be recycled.
Description
Technical field
The present invention relates to the useless polyester of a kind of use for the method for polyester textile hydrophilic finishing agent, belong to terylene chemical technology field.
Background technology
Polyester (terylene) fabric has powerful large, and the advantages such as wear resistance, stiffness, good stability of the dimension, are widely used at garment industry.But polyester fiber regain only 0.4%, so the hygroscopicity of polyester textile is poor, easily produces static and contamination, polyester textile is poor for the snugness of fit of garment material.Hydrophily and the snugness of fit of polyester textile are closely related, improve the hydrophily of fabric and just can improve the snugness of fit of polyester textile.It is the effective ways that improve its snugness of fit that polyester textile is carried out to hydrophilic finish.
Chinese patent CN200810024025 " moisture absorption perspiration-discharging dressing agent and production technology thereof and application " provides a kind of and has carried out modification, makes it to have formula, production technology and the application of the moisture absorption perspiration-discharging dressing agent of good moisture absorbing and sweat releasing property for polyester fiber, and described moisture absorption perspiration-discharging dressing agent is the molecular weight that generates of polyethylene glycol, ethylene glycol, polyethers and dimethyl terephthalate (DMT) reaction at the polyester/polyether segmented copolymer of 30000～50000 high molecular.Chinese patent CN200810244319 " for modifier of polyester fiber and its preparation method and application " disclose a kind of for polyester fiber is carried out modification modifier, and its preparation method and application, described modifier is by polyethylene glycol, ethylene glycol, polyethers, dimethyl terephthalate (DMT), two ends organic silicon modified by polyether and catalyst acetic acid slaine, adopts molecular weight that two step method continuous production processes produces at polyester and polyether/organosilicon terpolymer of 1000～50000 high molecular.Chinese patent CN201010532418 " preparation method of polyester, polyether modified silicone oil ternary copolymer textile finishing agent " provides the preparation method of a kind of polyester, polyether modified silicone oil ternary copolymer textile finishing agent.In practice, find the poorly water-soluble of this kind fabric finishing agent, in water, dissolve or difficulties in dispersion, need emulsifying agent could dissolve or emulsification.
Chinese patent CN200710026196 " take reclaim polyester waste material prepare the method for multifunctional polyester finishing agent for terylene as raw material " provides a kind of and take that to reclaim polyester waste material be raw material, makes the block copolymer terylene multifunctional polyester finishing agent with similar polyester molecule segment by hydrolysis, polymerization, sulfonation.According to this patent, reclaim after polyester waste material melting and dimethyl terephthalate (DMT), polyethylene glycol, polyether reactant, then with sulfuric acid sulfonation, make to introduce in strand sulfonic acid group, carry out again polymerisation and prepare multifunctional polyester finishing agent, the introducing of sulfonic acid group improves the water-soluble of product, and product easily dissolves or disperses in water.The method is directly used sulfuric acid sulfonation, complex process.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, propose the useless polyester of a kind of use for the method for polyester textile hydrophilic finishing agent, technique is simple, and gained polyester textile hydrophilic finishing agent color and luster is good, and good water solubility does not need emulsifying agent just can be easy to be dissolved in water.Adopt useless polyester can realize the recycle of useless polyester simultaneously.
Technical scheme of the present invention is as follows: a kind of preparation method of polyester textile hydrophilic finishing agent, comprise alcoholysis, the copolymerization two-step reaction of useless polyester, and concrete steps are as follows:
(1) alcoholysis of useless polyester: ethylene glycol, useless polyester are joined in reactor, and wherein the weight ratio of ethylene glycol and useless polyester is 0.3～1.0:1; Under pressure 0.1～0.3MPa, 210～240 ℃ of conditions of temperature, alcoholysis reaction is 2～4 hours; Reduce again pressure and stir 1～1.5 hour to normal pressure, 230～240 ℃ of conditions of temperature, filter the alcoholysis product ethylene glycol terephthalate that obtains useless polyester.
(2) copolyreaction: step (1) alcoholysis product is moved into polymerization reaction kettle, add M-phthalic acid-5-sulfonate or derivatives thereof, or the ethylene glycol solution that M-phthalic acid-5-sulfonate or derivatives thereof is made into mass fraction 20～40% is added; The alkali metal acetate that adds again useless weight polyester 0.05～0.2%, stir 40min～60min, then the polyethylene glycol that the mean molecule quantity that adds useless weight polyester 80～180% is 600～6000, finally add composite thermal stabilizer, stir 25min～35min, precondensation 30～60min under 240～270 ℃ of conditions of low vacuum, temperature of 4000～600Pa, then polyase 13 0～120min obtains hydrophilic finishing agent under 600～100Pa high vacuum, 270～280 ℃ of conditions of temperature.
The weight ratio of the described ethylene glycol of above-mentioned steps (1) and useless polyester is preferably 0.4～0.7:1.
The addition conversion of above-mentioned M-phthalic acid-5-sulfonate or derivatives thereof is the 5-sodium sulfo isophthalate of equivalent (SSIPA) calculating, and addition is 10～20% of useless weight polyester.Wherein M-phthalic acid-5-sulfonate is selected from 5-sodium sulfo isophthalate (SSIPA) or M-phthalic acid-5-Sulfonic Lithium, M-phthalic acid-5-sulfonate derivatives is selected from a kind of in Sodium Dimethyl Isophthalate-5-sulfonate, dimethyl isophthalate-5-Sulfonic Lithium, 5-sodium sulfo isophthalate glycol ester (SIPE) or M-phthalic acid-5-Sulfonic Lithium glycol ester, preferably 5-sodium sulfo isophthalate glycol ester.
Above-mentioned alkali metal acetate is selected from a kind of in sodium acetate, potassium acetate or lithium acetate, preferably sodium acetate.
The mean molecule quantity of above-mentioned polyethylene glycol preferably 1000～4000.
Above-mentioned composite thermal stabilizer is that stabilizing agent forms by the antioxidant with sterically hindered phenol and phosphorus, and the addition that is stabilizing agent with antioxidant and the phosphorus of sterically hindered phenol is respectively 0.04～0.08% and 0.02～0.06% of useless weight polyester.Described with sterically hindered phenol antioxidant be selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), 2,2-thiobis (4-methyl-6-tert-butyl phenol) (antioxidant 2246) or [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] octadecanol (antioxidant 1076).Described phosphorus is that stabilizing agent is selected from a kind of in phosphoric acid, phosphorous acid, phosphate or phosphite ester.
Useless polyester of the present invention comprises polyester give up piece, polyester waste silks, waste polyester bottle etc.For preventing from introducing impurity, useless polyester preferably has greatly the useless piece of the polyethylene terephthalate (PET) of light, has greatly the PET of light without silk noil, waste polyester bottle sheet.The useless piece of polyester is ground into the particle that particle diameter is less than 5mm before application, and polyester waste silks length is cut into and is less than 10cm, and waste polyester bottle is ground into the fragment that diameter is less than 20mm.
In the alcoholysis process of the useless polyester of step of the present invention (1), ethylene glycol addition is very few, and ethylene glycol is few to the immersion volume of useless polyester, and the alcoholysis time of useless polyester is long; Ethylene glycol addition is excessive, can cause the excess waste of ethylene glycol, and in later process, unnecessary ethylene glycol also will be discharged simultaneously, need to consume a large amount of heats.Therefore the weight ratio of ethylene glycol and useless polyester is elected 0.3～1.0:1 as, is preferably 0.4～0.7:1.
If the addition of M-phthalic acid-5-sulfonate or derivatives thereof of the present invention is too small, polyester water-soluble influenced; Addition is excessive, and the cost of product increases, and product water dissolubility is excessively good simultaneously, affects the wash durability of polyester textile product.Therefore the conversion of the addition of M-phthalic acid-5-sulfonate or derivatives thereof of the present invention is calculated as 10～20% of the weight polyester that gives up for the 5-sodium sulfo isophthalate of equivalent (SSIPA).
In copolyreaction of the present invention, molecular weight polyethylene glycol is too low, and the hydrophilic effect of product is poor, and molecular weight is too high, and the reactivity of polyethylene glycol reduces, and affects the water soluble characteristic of product.Polyethylene glycol consumption is few, affects the water-soluble of product; Consumption is excessive, and due to the poor heat stability of polyethylene glycol, product easily turns to be yellow, and the water resistance of product is poor simultaneously.Therefore polyethylene glycol mean molecule quantity of the present invention elects 600～6000 as, and preferably 1000～4000.Addition is elected 80～180% of useless weight polyester as.
Because M-phthalic acid-5-sulfonate or derivatives thereof is acid, it adds the dehydration of membership aggravation ethylene glycol self, and the present invention matches the dehydration that alkali metal acetate can suppress ethylene glycol itself in production well, reduces the content of diethylene glycol (DEG) in product.
In composite thermal stabilizer of the present invention, with the anti-oxidant action of sterically hindered phenol, be to reduce product oxidation Decomposition degree under hot conditions, phosphoric acid, phosphorous acid or its ester class are as heat stabilizer, and its effect is the degree that reduces product thermal degradation under hot conditions.Composite thermal stabilizer add the heat resistance that can improve product, be beneficial to and under hot conditions, produce and use.
Compared with prior art, hydrophilic finishing agent of the present invention has well water-soluble, does not need emulsifying agent just can be dissolved in hot water, and stable storing.Because polyethylene glycol adds after useless polyester alcoholysis reaction, shortened its time of staying at high temperature, reduce the possibility of its thermal decomposition, add the use of compound stabilizer, the stability of product is improved, product color is good.The present invention only need give up alcoholysis, the copolymerization two-step reaction of polyester, technique is simple, is easy to realize industrialized mass.And the present invention be take and given up polyester as raw material, turns waste into wealth, be conducive to the development of chemical fibre industry resource.
The specific embodiment
Below by embodiment, the invention will be further described.In embodiment, raw materials used and equipment is this area routine techniques.
Embodiment 1
Select that to have greatly the useless piece of the polyester of light be raw material, be ground into the particle that particle diameter is less than 5mm, be useless polyester granulate.The useless polyester granulate of 1000kg, 600kg ethylene glycol are put in the reactor of belt stirrer, at 230 ℃ of pressure 0.2MPa, temperature, alcoholysis reaction is 2 hours, after reactor stirring can be rotated with setting stick, starter motor stirs, reduce gradually pressure to normal pressure, be warmed up to 240 ℃, insulation reaction 1 hour, the alcoholysis product ethylene glycol terephthalate of the polyester that must give up.
After being filtered, above-mentioned product moves into polymerization reaction kettle, ethylene glycol solution (the SIPE weight content 40% in solution that adds 463kg 5-sodium sulfo isophthalate glycol ester (SIPE), hereinafter to be referred as SIPE40, amounting to into SSIPA is 139.5kg), sodium acetate 1.0kg, stir 60 minutes, then adding mean molecule quantity is 1450 polyethylene glycol (PEG1450) 1500kg, 0.5kg antioxidant 1010, 0.4kg trimethyl phosphate, stir 30 minutes, at low vacuum 2000～1000Pa, precondensation 45min at 260～270 ℃ of temperature, at high vacuum 400～150Pa, polymerization 60min discharging at 275～280 ℃ of temperature, after cooling, obtain oyster white waxy solid product.
Embodiment 2
The SIPE40 that adds as different from Example 1 555kg.
Embodiment 3
As embodiment 1, difference is that to add 1200kg mean molecule quantity be 1000 polyethylene glycol (PEG1000).
Embodiment 4
As embodiment 1, difference is that to add 1800kg mean molecule quantity be 2000 polyethylene glycol (PEG2000).
Embodiment 5
As embodiment 1, difference is the ethylene glycol solution that adds the SIPE of 900kg, SIPE weight content 20% in solution (being called for short SIPE20).
Comparative example 1
In copolyreaction, do not add as different from Example 1 the ethylene glycol solution of 5-sodium sulfo isophthalate glycol ester (SIPE).
Comparative example 2
That to add the SIPE40(of 185kg to amount to into SSIPA addition be 5.5% < 10% with embodiment 1 difference), product is oyster white waxy solid.
Comparative example 3
Adding as different from Example 1 the SIPE40(of 700kg to amount to into SSIPA addition is 21%).
Comparative example 4
As embodiment 1, difference is to add the polyethylene glycol that the mean molecule quantity of 1500kg is 400.
Comparative example 5
Do not add as different from Example 1 antioxidant 1010 and trimethyl phosphate, product is micro-yellow waxy solid.
Comparative example 6
By 865kg terephthalic acid (TPA), 100kg ethylene glycol, the ethylene glycol solution of the 5-sodium sulfo isophthalate glycol ester (SIPE) of 463kg (SIPE weight content 40% in solution), 1500kg mean molecule quantity is 1450 polyethylene glycol, 0.5kg antioxidant 1010, 0.4kg trimethyl phosphate, 1.0kg sodium acetate all adds making beating still, after making beating evenly, enter esterifying kettle, normal pressure esterification at 250 ℃, esterification finishes rear immigration polymeric kettle, low vacuum at 2000～1000Pa, precondensation at 260～270 ℃ of temperature, at high vacuum 400～150Pa, polymerization 60min discharging at 275～280 ℃ of temperature, after cooling, obtain yellow wax-like solid product.
Get respectively above-described embodiment and comparative example product 10g adds in 90g water, stir and be heated to 70～80 ℃ and be incubated 20 minutes, observe product and dissolve situation, the results are shown in Table 1.
Respectively above-described embodiment and the complete molten product of comparative example are made into 3% the aqueous solution, adopt conventional finishing technique: dipping (finishing agent 30g/L, pH value--6,25 ℃ of temperature; bath raio 1: 30) → bis-soak two roll (pick-up rate 80%) → preliminary drying (80 ℃; 3min) → bake (180 ℃, 4sec) → take out cloth specimen → washing → oven dry, weave cotton cloth and carry out hydrophilic finiss and measure its measure wicking height wash/cotton plain weaving machine; Fabric is measured to its measure wicking height again by after GB/T8629-2001 standard wash 20 times.The results are shown in Table 1.
The performance of table 1 hydrophilic finishing agent product and fabric
Note 1: according to the measure wicking height of FZ/T01071-2008 standard testing 20min.
From table 1, adopt preparation method of the present invention, the polyester textile hydrophilic finishing agent making not only color and luster is good, non-yellowing, soluble in water, simultaneously water-fastness, possess excellent hygroscopicity.From comparative example 1-3, on basis of the present invention, 5-sodium sulfo isophthalate glycol ester (SIPE) do not add or addition very few, the water-soluble reduction of gained hydrophilic finishing agent; Amount to into SSIPA addition when too much, the washable weak effect of product.In comparative example 4, molecular weight polyethylene glycol is too low, the hydrophilic and washable weak effect of product.From comparative example 5, on basis of the present invention, do not add heat stabilizer, the micro-Huang of products obtained therefrom color and luster.As comparative example 6, when all polymerization reactants all participate in esterification, the color and luster of products obtained therefrom also turns to be yellow.
Claims (9)
1. a preparation method for polyester textile hydrophilic finishing agent, is characterized in that, comprises the steps:
(1) alcoholysis of useless polyester: ethylene glycol, useless polyester are joined in reactor, and wherein the weight ratio of ethylene glycol and useless polyester is 0.3～1.0:1; Under pressure 0.1～0.3MPa, 210～240 ℃ of conditions of temperature, alcoholysis reaction is 2～4 hours, then reduces pressure and stir 1～1.5 hour to normal pressure, 230～240 ℃ of conditions of temperature, filters the alcoholysis product ethylene glycol terephthalate that obtains useless polyester;
(2) copolyreaction: step (1) alcoholysis product is moved into polymerization reaction kettle, add M-phthalic acid-5-sulfonate or derivatives thereof, or the ethylene glycol solution that M-phthalic acid-5-sulfonate or derivatives thereof is made into mass fraction 20～40% is added; The alkali-metal acetate that adds again useless weight polyester 0.05～0.2%, stir 40min～60min, then the polyethylene glycol that the mean molecule quantity that adds useless weight polyester 80～180% is 600～6000, finally add composite thermal stabilizer, stir 25min～35min, precondensation 30～60min under 240～270 ℃ of conditions of low vacuum, temperature of 4000～600Pa; Under 600～100Pa high vacuum, 270～280 ℃ of conditions of temperature, polyase 13 0～120min obtains hydrophilic finishing agent again;
The 5-sodium sulfo isophthalate that the addition conversion of above-mentioned M-phthalic acid-5-sulfonate or derivatives thereof is equivalent calculates, and addition is 10～20% of useless weight polyester;
Above-mentioned composite thermal stabilizer is that stabilizing agent forms by the antioxidant with sterically hindered phenol and phosphorus, and the addition that is stabilizing agent with antioxidant and the phosphorus of sterically hindered phenol is respectively 0.04～0.08% and 0.02～0.06% of useless weight polyester;
Described M-phthalic acid-5-sulfonate is selected from 5-sodium sulfo isophthalate or M-phthalic acid-5-Sulfonic Lithium; M-phthalic acid-5-sulfonate derivatives is selected from a kind of in Sodium Dimethyl Isophthalate-5-sulfonate, dimethyl isophthalate-5-Sulfonic Lithium, 5-sodium sulfo isophthalate glycol ester or M-phthalic acid-5-Sulfonic Lithium glycol ester.
2. the preparation method of polyester textile hydrophilic finishing agent as claimed in claim 1, is characterized in that, described M-phthalic acid-5-sulfonate derivatives is 5-sodium sulfo isophthalate glycol ester.
3. the preparation method of polyester textile hydrophilic finishing agent as claimed in claim 1, it is characterized in that, the described antioxidant with sterically hindered phenol is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2'-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butyl phenol) or [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] octadecanol ester; Described phosphorus is that stabilizing agent is selected from a kind of in phosphoric acid, phosphorous acid, phosphate or phosphite ester.
4. the preparation method of polyester textile hydrophilic finishing agent as claimed in claim 1, is characterized in that, described alkali-metal acetate is selected from sodium acetate, potassium acetate or lithium acetate.
5. the preparation method of polyester textile hydrophilic finishing agent as claimed in claim 4, is characterized in that, described alkali-metal acetate is sodium acetate.
6. the preparation method of polyester textile hydrophilic finishing agent as claimed in claim 1, is characterized in that, in described step (1), the weight ratio of ethylene glycol and useless polyester is 0.4～0.7:1.
7. the preparation method of polyester textile hydrophilic finishing agent as claimed in claim 1, is characterized in that, described polyethylene glycol mean molecule quantity is 1000～4000.
8. the preparation method of the polyester textile hydrophilic finishing agent as described in claim 1-7 any one, is characterized in that, described useless polyester is selected from polyester useless piece, polyester waste silks or waste polyester bottle; The useless piece of polyester is ground into the particle that particle diameter is less than 5mm, and polyester waste silks is cut into length and is less than 10cm, and waste polyester bottle is ground into the fragment that diameter is less than 20mm.
9. the preparation method of polyester textile hydrophilic finishing agent as claimed in claim 8, is characterized in that, described useless polyester is selected from greatly the polyethylene terephthalate of light give up piece, oil-free polyester waste silk or waste polyester bottle sheet.
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| CN201210287346.5A CN102767081B (en) | 2012-08-13 | 2012-08-13 | Method for preparing hydrophilic finishing agent of polyester fabric through waste polyester |
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| CN201210287346.5A CN102767081B (en) | 2012-08-13 | 2012-08-13 | Method for preparing hydrophilic finishing agent of polyester fabric through waste polyester |
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| CN102767081B true CN102767081B (en) | 2014-02-26 |
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| CN103114440B (en) * | 2013-03-14 | 2014-09-03 | 浙江金三发非织造布有限公司 | Production technology of full terylene non-woven fabric with hydrophilic function |
| CN113174035B (en) * | 2021-05-08 | 2022-12-02 | 湖北山特莱新材料有限公司 | Multifunctional water-soluble polyester slurry |
| CN115584019A (en) * | 2022-09-27 | 2023-01-10 | 福建赛隆科技有限公司 | CDP, ECDP and method for preparing CDP, ECDP by regenerating DMT |
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| CN101372810B (en) * | 2007-08-20 | 2011-11-09 | 无锡宜澄化学有限公司 | Method for preparing polyester integrated finishing agent for terylene from raw material reclaimed from polyester waste material |
| CN102617990A (en) * | 2011-01-31 | 2012-08-01 | 北京博维特投资有限公司 | Preparation method of co-mixed polyester for preparing hygroscopic polyester fibers |
| CN102391487B (en) * | 2011-09-19 | 2012-10-10 | 吴江市港洋化纤有限公司 | Preparation method for anti-pilling, anti-aging and normal-pressure cation dyeable polyester chips |
| CN102617839B (en) * | 2012-04-11 | 2013-11-06 | 山东巨业精细化工有限公司 | Method for preparing water-soluble polyesters for composite fibers by waste polyesters |
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