CN101864612A - 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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- CN101864612A CN101864612A CN 201010207229 CN201010207229A CN101864612A CN 101864612 A CN101864612 A CN 101864612A CN 201010207229 CN201010207229 CN 201010207229 CN 201010207229 A CN201010207229 A CN 201010207229A CN 101864612 A CN101864612 A CN 101864612A
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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 as fracture strength and elastic modelling quantity height, resilience is moderate, the HEAT SETTING excellence, 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, the degree of crystallinity height, 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 Japanese Patent Publication 34-10497 communique, 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 provides a kind of flame retardant polyester polymer and manufacture method thereof of available cationic dyeing for 200410084108.X.The dimethyl isophthalate 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 methyl alcohol processor arranged) so equipment is also supporting.Add TPA (terephthalic acid (TPA)) and continue esterification, be transferred to polycondensation vessel after finishing, add catalyst antimony trioxide, ethoxy phosphoric acid fire retardant and manganese acetate and make the cationic-dyeable flame retardant polyester.This method by 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 and two stages of polycondensation add, need to add all kinds of corresponding catalyst, 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, other performance impact to polyester fiber is very little, the preparation method of the halogen-free flame retardant polyester fiber of the cationic-dyeable that cost is low.
The object of the present invention is achieved 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 as follows:
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 ℃, reacted 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) are 1: 0.02～0.08: 1.15～1.25 in molar ratio, join in the esterifying kettle, esterifying kettle stirs and is warmed up to 230～250 ℃, control esterifying kettle internal pressure reaches 200～400kPa, reacted 1～2 hour, esterification yield is reached finish esterification more than 90～99%, pressure relief, the catalyst glycol antimony that adds terephthalic acid (TPA) (PTA) quality 0.01～0.1% then, mix and 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 of step 2 preparation is cut into slices through vacuum drum drying machine drying, 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.
The present invention is at first by sodiosulfoisophthalic acid and 2-carboxyethyl hypophosphorous acid, and 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.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 energy.Compare with 200410084108.X, not only production cost is significantly reduced, and properties of product have obtained improving greatly.
The present invention is by 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 the fire-retardant and 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 finishing polyester by 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, significant fire-retardant and cationic-dyeable effect.
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, the requirement of realistic 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 ℃, reacted 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) are 1: 0.02: 1.15 in molar ratio, join in the esterifying kettle, esterifying kettle stirs and is warmed up to 230 ℃, control esterifying kettle internal pressure reaches 200kPa, reacted 1 hour, esterification yield is reached finish esterification more than 90%, pressure relief, the catalyst glycol antimony that adds terephthalic acid (TPA) (PTA) quality 0.01% then, mix and stir 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 of step 2 preparation is cut into slices through vacuum drum drying machine drying, 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 ℃, reacted 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) are 1: 0.04: 1.2 in molar ratio, join in the esterifying kettle, esterifying kettle stirs and is warmed up to 240 ℃, control esterifying kettle internal pressure reaches 300kPa, reacted 1.5 hours, esterification yield is reached finish esterification more than 95%, pressure relief, the catalyst glycol antimony that adds terephthalic acid (TPA) (PTA) quality 0.05% then, mix and stir 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 of step 2 preparation is cut into slices through vacuum drum drying machine drying, 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 ℃, reacted 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) are 1: 0.08: 1.25 in molar ratio, join in the esterifying kettle, esterifying kettle stirs and is warmed up to 250 ℃, control esterifying kettle internal pressure reaches 400kPa, reacted 2 hours, esterification yield is reached finish esterification more than 99%, pressure relief, the catalyst glycol antimony that adds terephthalic acid (TPA) (PTA) quality 0.1% then, mix and stir 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 of step 2 preparation is cut into slices through vacuum drum drying machine drying, 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 described 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 ℃, reacted 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 are 1: 0.02～0.08: 1.15～1.25 in molar ratio, join in the esterifying kettle, esterifying kettle stirs and is warmed up to 230～250 ℃, control esterifying kettle internal pressure reaches 200～400kPa, reacted 1～2 hour, esterification yield is reached finish esterification more than 90～99%, pressure relief, the catalyst glycol antimony that adds terephthalic acid (TPA) quality 0.01～0.1% then mixes and stirs after 10～20 minutes, imports 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 of step 2 preparation is cut into slices through vacuum drum drying machine drying, 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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| CN102704032A (en) * | 2012-06-19 | 2012-10-03 | 扬州思窈化纤有限公司 | Production process of cationic regenerative colored polyester staple fiber |
| CN103603070A (en) * | 2013-10-21 | 2014-02-26 | 桐乡市中辰化纤有限公司 | Preparation method of high-comfort triangular hollow microporous fiber |
| 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 |
| CN114000226A (en) * | 2021-12-31 | 2022-02-01 | 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 |
| CN115821418A (en) * | 2022-10-18 | 2023-03-21 | 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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| CN115821418A (en) * | 2022-10-18 | 2023-03-21 | 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 |
| 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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