CN101864612B - Preparation method of cationic dyeable halogen-free flame retardant polyester fiber - Google Patents
Preparation method of cationic dyeable halogen-free flame retardant polyester fiber Download PDFInfo
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- CN101864612B CN101864612B CN2010102072294A CN201010207229A CN101864612B CN 101864612 B CN101864612 B CN 101864612B CN 2010102072294 A CN2010102072294 A CN 2010102072294A CN 201010207229 A CN201010207229 A CN 201010207229A CN 101864612 B CN101864612 B CN 101864612B
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Abstract
The invention relates to a preparation method of the cationic dyeable halogen-free flame retardant polyester fiber, which comprises the following process steps: 1. adding monosodium isophthalic sulfonate, 2-propyloic hypophosphorous acid and de-ionized water into a reaction container, filtering out reaction products after the reaction is completed, and carrying out baking to obtain cationic dyeable flame retardant compounds; 2. adding terephthalic acid, products in the first step and glycol into an esterification kettle, then, adding antimony ethylene glycalate, conducting the materials into a polycondensation kettle, and carrying out reaction and material outlet to obtain cationic dyeable flame retardant polyester slices; and 3. drying the cationic dyeable flame retardant polyester slices prepared in the second step through a vacuum drum drying machine, carrying out spinning on the dried slices on a spinning machine according to a conventional polyester spinning process to obtain the cationic dyeable halogen-free flame retardant polyester fiber. The invention realizes the flame retardant performance and the cationic dyeable performance of the polyester through one-step addition, avoids the complicated process and the occurrence of various kinds of secondary reaction caused by a traditional method of adding flame retardant agents and cationic dyeable auxiliary agents in two steps, and has more stable and obvious flame retardant and cationic dyeable effect.
Description
(1) technical field
The present invention relates to the preparation method of the halogen-free flame retardant polyester fiber that a cationoid can dye.This polyester fiber has the cation dye chromophil characteristic, can be applicable to aviation, railway and various industries such as other traffic and transportation system and fire-fighting.
(2) background technology
Polyester fiber has a lot of premium properties, and high like fracture strength and elastic modelling quantity, resilience is moderate, and HEAT SETTING property is excellent, and heat-resisting good with light resistance, fabric has quick-drying washable characteristic etc., takes widely and the industry purposes so have.But the terylene structure is tight, and degree of crystallinity is high, and inner big molecule does not have the hydrophily gene, thus the dyeing difficulty, and polyester fiber can burn, and these have all limited the actual production and the application of polyester fiber to a certain extent.So developing a kind of fire-retardant polyester fibre of cationic-dyeable is necessary.
In the special public clear 34-10497 communique of Japan, the sulfonic M-phthalic acid composition of containing metal that has proposed 2～3 moles of % of a kind of use with polyethylene terephthalate copolymer and must cation dyeable polyester.But by this patent documentation gained polyester fiber, can only under high temperature, high pressure, implement dyeing, with shufflings such as natural fabric system, polyurethane fiber, mixed knitting after, can not dye.
Application number is flame retardant polyester polymer and the manufacturing approach thereof that 200410084108.X provides a kind of available cationic dyeing.The DMIP that its utilization contains metal sulfonate NaOH as the catalyst condition under; Make that with glycol reaction the degree of ester exchange reaction is more than 95% respectively; Thereby the synthetic M-phthalic acid dihydroxy ethyl ester that contains metal sulfonate (in this building-up process, have a large amount of methyl alcohol and produce, the methanol treatment device arranged) so equipment is also supporting.Add TPA (terephthalic acid (TPA)) and continue esterification, be transferred to polycondensation vessel after the completion, add catalyst antimony trioxide, ethoxy phosphoric acid fire retardant and manganese acetate and make the cationic-dyeable flame retardant polyester.This method through the substep add the cationic-dyeable agent, fire retardant obtains polyester and has cationic-dyeable and fire resistance; But its complex manufacturing; Add NaOH, manganese acetate etc. in process of production as catalyst; Because additive types is many, in course of reaction, can produce various side reactions, finally influence the performance of product; And when polycondensation, add ethoxy phosphoric acid can with the sulfonate generation sulfurous acid that reacts, finally cause the cationic-dyeable performance to descend even disappear.
Both at home and abroad in the report of the flame retardant polyester of cationic-dyeable, all exist with application number be the same problem of 200410084108.X, complex manufacturing; And because fire retardant and cationic-dyeable additive all are to be divided into esterification with two stages of polycondensation add, all kinds of corresponding catalyst of needs interpolation cause intermediate by-products to increase; So reaction is unstable; Need to add various stabilizing agents and composite catalyst, finally cause cost to increase, and along with the aggravation of side reaction; Some accessory substances are added, and properties of product can't well be improved.
(3) summary of the invention
The objective of the invention is to overcome traditional complicated technology, add all kinds of catalyst, ethoxy fire retardant and cationic-dyeable auxiliary agent at high temperature react performances such as influencing stock-dye; Provide a kind of technology simple; The additive addition is few; And the reactant that utilizes the carboxyethyl fire retardant to make with the reaction of cationic-dyeable auxiliary agent has fire-retardant and can dye characteristic, and is very little to other performance impact of polyester fiber, the preparation method of the halogen-free flame retardant polyester fiber of the cationic-dyeable that cost is low.
The objective of the invention is to realize like this: a kind of preparation method of halogen-free flame retardant polyester fiber of cationic-dyeable; Be to generate flame retardant cationic dyeable type auxiliary agent by 2-carboxyethyl hypophosphorous acid (CEPPA) and sodiosulfoisophthalic acid reaction; And then same terephthalic acid (TPA) (PTA), ethylene glycol (EG) react and make, and concrete steps are following:
Synthesizing of step 1, cationic-dyeable and fire-retardant complexing agent
Is 1: 1.5～2.5: 10～30 with sodiosulfoisophthalic acid, 2-carboxyethyl hypophosphorous acid (CEPPA) in molar ratio with deionized water; Add in the reaction vessel; Water-bath is heated to 50～80 ℃, reacts 1～5 hour, after question response finishes; Filter out reaction product, oven dry obtains the fire-retardant compound of cationic-dyeable under 110～150 ℃ of temperature.
Synthesizing of the halogen-free antiflaming polyester section of step 2, cationic-dyeable
With terephthalic acid (TPA) (PTA), step 1 product and ethylene glycol (EG) is 1: 0.02～0.08: 1.15～1.25 in molar ratio, joins in the esterifying kettle, and esterifying kettle stirs and is warmed up to 230～250 ℃; Control esterifying kettle internal pressure reaches 200～400kPa; Reacted 1～2 hour, and esterification yield was reached finish esterification, pressure relief more than 90～99%; The catalyst glycol antimony that adds terephthalic acid (TPA) (PTA) quality 0.01～0.1% then; Mix to stir after 10～20 minutes, import in the polycondensation vessel, start vavuum pump make system pressure remain on-50～-105kPa; Reaction temperature is controlled at 260～280 ℃, reacts discharging in 1～4 hour and obtains the section of cationic-dyeable flame retardant polyester.
The preparation of the halogen-free flame retardant polyester fiber of step 3, cationic-dyeable
The cationic-dyeable flame retardant polyester section of step 2 preparation is dry through the vacuum drum drying machine, 130～150 ℃ of baking temperatures, temperature retention time is 4～12 hours; Dried section is carried out spinning according to the polyester spinning technique of routine on spinning machine, obtain the halogen-free flame retardant polyester fiber of cationic-dyeable.
At first through sodiosulfoisophthalic acid and 2-carboxyethyl hypophosphorous acid, synthetic flame retardant cationic dyeable type auxiliary agent can react with polyester under the effect of catalyst glycol antimony, need not to add in addition the catalyst of other type in the present invention.Avoid two steps of tradition to add fire retardant and cationic-dyeable auxiliary agent, needed to add various different catalysts, effectively suppressed the generation of all kinds of side reactions.And the carboxyl class phosphoric acid fire retardant that uses can not react with sulfonate, and the sulfonic acid group of cationic-dyeable does not reduce, and does not influence the stainability ability.Compare with 200410084108.X, not only production cost is significantly reduced, and properties of product have obtained improving greatly.
The present invention is through research of long-term molecular structure and test, found a kind of can with the fire retardant 2-carboxyethyl hypophosphorous acid of sodiosulfoisophthalic acid generation chemical reaction, synthesized a kind of novel flame retardant cationic dyeable auxiliary agent.A kind ofly like this have fire-retardant and the auxiliary agent cationic-dyeable performance concurrently; With respect to independent fire retardant and the cationic-dyeable auxiliary agent that adds; Can add the fire-retardant and cation dyeable of accomplishing polyester through a step; Avoid two steps of tradition to add the complicated technology that fire retardants and cationic-dyeable auxiliary agent bring and the generation of all kinds of side reactions, have stable more, fire-retardant and cationic-dyeable effect significantly.
The halogen-free antiflaming polyester of the cationic-dyeable that the present invention obtains, the more conventional PET polyester slice of inherent viscosity and fusing point is close, has better spinnability, can not influence other performance of fiber.Utilize the halogen-free flame retardant polyester fiber of conventional spining technology spinning cationic-dyeable, the antioxygen index of fiber has reached 38～40, has the good flame performance, and cation stain can obtain gay colours.
Technology of the present invention is simple, and the additive addition is few, and very little to other performance impact of polyester fiber, cost is low, meets the requirement of actual production and application.
(4) specific embodiment
Embodiment 1:
Synthesizing of step 1, cationic-dyeable and fire-retardant complexing agent
Is 1: 1.5: 10 with sodiosulfoisophthalic acid, 2-carboxyethyl hypophosphorous acid (CEPPA) in molar ratio with deionized water; Add in the glass reaction container; Water-bath is heated to 50 ℃, reacts 1 hour, after question response finishes; Filter out reaction product, oven dry obtains the fire-retardant compound of cationic-dyeable under 110～150 ℃ of temperature.
Synthesizing of the halogen-free antiflaming polyester section of step 2, cationic-dyeable
With terephthalic acid (TPA) (PTA), step 1 product and ethylene glycol (EG) is 1: 0.02: 1.15 in molar ratio, joins in the esterifying kettle, and esterifying kettle stirs and is warmed up to 230 ℃; Control esterifying kettle internal pressure reaches 200kPa, reacts 1 hour, esterification yield is reached finish esterification more than 90%; Pressure relief adds the catalyst glycol antimony of terephthalic acid (TPA) (PTA) quality 0.01% then, mixes and stirs after 10 minutes; Import in the polycondensation vessel; Start vavuum pump system pressure is remained on-50kPa, reaction temperature is controlled at 260 ℃, reacts discharging in 1 hour and obtains the section of cationic-dyeable flame retardant polyester.
The preparation of the halogen-free flame retardant polyester fiber of step 3, cationic-dyeable
The cationic-dyeable flame retardant polyester section of step 2 preparation is dry through the vacuum drum drying machine, 130 ℃ of baking temperatures, temperature retention time is 4 hours; Dried section is carried out spinning according to the polyester spinning technique of routine on spinning machine, obtain the halogen-free flame retardant polyester fiber of cationic-dyeable.
Embodiment 2:
Synthesizing of step 1, cationic-dyeable and fire-retardant complexing agent
Is 1: 2: 20 with sodiosulfoisophthalic acid, 2-carboxyethyl hypophosphorous acid (CEPPA) in molar ratio with deionized water; Add in the glass reaction container; Water-bath is heated to 60 ℃, reacts 3 hours, after question response finishes; Filter out reaction product, oven dry obtains the fire-retardant compound of cationic-dyeable under 130 ℃ of temperature.
Synthesizing of the halogen-free antiflaming polyester section of step 2, cationic-dyeable
With terephthalic acid (TPA) (PTA), step 1 product and ethylene glycol (EG) is 1: 0.04: 1.2 in molar ratio, joins in the esterifying kettle, and esterifying kettle stirs and is warmed up to 240 ℃; Control esterifying kettle internal pressure reaches 300kPa, reacts 1.5 hours, esterification yield is reached finish esterification more than 95%; Pressure relief adds the catalyst glycol antimony of terephthalic acid (TPA) (PTA) quality 0.05% then, mixes and stirs after 15 minutes; Import in the polycondensation vessel; Start vavuum pump system pressure is remained on-80kPa, reaction temperature is controlled at 270 ℃, reacts discharging in 2 hours and obtains the section of cationic-dyeable flame retardant polyester.
The preparation of the halogen-free flame retardant polyester fiber of step 3, cationic-dyeable
The cationic-dyeable flame retardant polyester section of step 2 preparation is dry through the vacuum drum drying machine, 140 ℃ of baking temperatures, temperature retention time is 6 hours; Dried section is carried out spinning according to the polyester spinning technique of routine on spinning machine, obtain the halogen-free flame retardant polyester fiber of cationic-dyeable.
Embodiment 3:
Synthesizing of step 1, cationic-dyeable and fire-retardant complexing agent
Is 1: 2.5: 30 with sodiosulfoisophthalic acid, 2-carboxyethyl hypophosphorous acid (CEPPA) in molar ratio with deionized water; Add in the glass reaction container; Water-bath is heated to 80 ℃, reacts 5 hours, after question response finishes; Filter out reaction product, oven dry obtains the fire-retardant compound of cationic-dyeable under 150 ℃ of temperature.
Synthesizing of the halogen-free antiflaming polyester section of step 2, cationic-dyeable
With terephthalic acid (TPA) (PTA), step 1 product and ethylene glycol (EG) is 1: 0.08: 1.25 in molar ratio, joins in the esterifying kettle, and esterifying kettle stirs and is warmed up to 250 ℃; Control esterifying kettle internal pressure reaches 400kPa, reacts 2 hours, esterification yield is reached finish esterification more than 99%; Pressure relief adds the catalyst glycol antimony of terephthalic acid (TPA) (PTA) quality 0.1% then, mixes and stirs after 20 minutes; Import in the polycondensation vessel; Start vavuum pump system pressure is remained on-105kPa, reaction temperature is controlled at 280 ℃, reacts discharging in 4 hours and obtains the section of cationic-dyeable flame retardant polyester.
The preparation of the halogen-free flame retardant polyester fiber of step 3, cationic-dyeable
The cationic-dyeable flame retardant polyester section of step 2 preparation is dry through the vacuum drum drying machine, 150 ℃ of baking temperatures, temperature retention time is 12 hours; Dried section is carried out spinning according to the polyester spinning technique of routine on spinning machine, obtain the halogen-free flame retardant polyester fiber of cationic-dyeable.
Claims (1)
1. the preparation method of the halogen-free flame retardant polyester fiber of a cationic-dyeable is characterized in that said method comprises following processing step:
Synthesizing of step 1, cationic-dyeable and fire-retardant complexing agent
With sodiosulfoisophthalic acid, 2-carboxyethyl hypophosphorous acid and deionized water is 1: 1.5～2.5: 10～30 in molar ratio; Add in the reaction vessel, water-bath is heated to 50～80 ℃, reacts 1～5 hour; After question response finishes; Filter out reaction product, oven dry obtains the fire-retardant compound of cationic-dyeable under 110～150 ℃ of temperature
Synthesizing of the halogen-free antiflaming polyester section of step 2, cationic-dyeable
With terephthalic acid (TPA), step 1 product and ethylene glycol is 1: 0.02～0.08: 1.15～1.25 in molar ratio, joins in the esterifying kettle, and esterifying kettle stirs and is warmed up to 230～250 ℃; Control esterifying kettle internal pressure reaches 200～400kPa, reacts 1～2 hour, makes esterification yield reach 90～99% and finishes esterification; Pressure relief adds the catalyst glycol antimony of terephthalic acid (TPA) quality 0.01～0.1% then, mixes and stirs after 10～20 minutes; Import in the polycondensation vessel, start vavuum pump make system pressure remain on-50～-105kPa, reaction temperature is controlled at 260～280 ℃; React discharging in 1～4 hour and obtain the halogen-free antiflaming polyester section of cationic-dyeable
The preparation of the halogen-free flame retardant polyester fiber of step 3, cationic-dyeable
The halogen-free antiflaming polyester section of the cationic-dyeable of step 2 preparation is dry through the vacuum drum drying machine, 130～150 ℃ of baking temperatures, temperature retention time is 4～12 hours; Dried section is carried out spinning according to the polyester spinning technique of routine on spinning machine, obtain the halogen-free flame retardant polyester fiber of cationic-dyeable.
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| CN2010102072294A CN101864612B (en) | 2010-06-21 | 2010-06-21 | Preparation method of cationic dyeable halogen-free flame retardant polyester fiber |
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| CN102704032B (en) * | 2012-06-19 | 2013-09-25 | 扬州思窈化纤有限公司 | Production process of cationic regenerative colored polyester staple fiber |
| CN103603070B (en) * | 2013-10-21 | 2016-08-24 | 桐乡市中辰化纤有限公司 | The preparation method of the high micro-porous fibre of comfortable triangular hollow |
| CN104086756A (en) * | 2014-07-28 | 2014-10-08 | 营口康辉石化有限公司 | Production method of optical transparent film-level polyester |
| CN114000226B (en) * | 2021-12-31 | 2022-03-15 | 江苏新视界先进功能纤维创新中心有限公司 | Preparation method of cationic dyeable flame-retardant high-strength polyester fiber |
| CN115821418B (en) * | 2022-10-18 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye-dyeable polyester fiber based on autocatalysis |
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| US6218008B1 (en) * | 2000-07-21 | 2001-04-17 | Hyosung Corporation | Easy dyeable polyester fiber |
| CN1370857A (en) * | 2001-02-27 | 2002-09-25 | 天津石油化工公司化纤厂 | Production process of fire-retardant Dacron short-staple easy to be dyed with cationic dye |
| CN1696173A (en) * | 2004-05-10 | 2005-11-16 | （株）晓星 | Flame retardant polyesterpolymer able to dye by using cation pigment,its mfg.method and copolymer fiber using the same |
| CN1763275A (en) * | 2004-10-21 | 2006-04-26 | 天津石油化工公司化纤厂 | Method for manufacturing fire retardant-antistatic polyester fiber |
| CN101200820A (en) * | 2006-12-13 | 2008-06-18 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4536529B2 (en) * | 2005-01-20 | 2010-09-01 | 三菱レイヨン株式会社 | Method for producing cationic dyeable polyester thick yarn |
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|---|---|---|---|---|
| US6218008B1 (en) * | 2000-07-21 | 2001-04-17 | Hyosung Corporation | Easy dyeable polyester fiber |
| CN1370857A (en) * | 2001-02-27 | 2002-09-25 | 天津石油化工公司化纤厂 | Production process of fire-retardant Dacron short-staple easy to be dyed with cationic dye |
| CN1696173A (en) * | 2004-05-10 | 2005-11-16 | （株）晓星 | Flame retardant polyesterpolymer able to dye by using cation pigment,its mfg.method and copolymer fiber using the same |
| CN1763275A (en) * | 2004-10-21 | 2006-04-26 | 天津石油化工公司化纤厂 | Method for manufacturing fire retardant-antistatic polyester fiber |
| CN101200820A (en) * | 2006-12-13 | 2008-06-18 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
Non-Patent Citations (1)
| Title |
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| JP特开2006-200064A 2006.08.03 |
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