Preparation method of cationic dyeable halogen-free flame retardant polyester fiber

(A) technical field

The present invention relates to a class of cationic dyeable the halogen-free flame-retardant polyester fiber preparation. The polyester fiber has a cationic dye chromatophile characteristic, can be used in aviation, railway and other transportation system and fire-fighting, and other industries.

(B) background art

Polyester fiber has many excellent performance, such as rupture strength and high elastic modulus, moderate resilience, excellent hot shaping, heat-resistant and good light fastness, fabric has the advantages of easy washing and drying characteristics, it is a wide range of use and industrial use. However, polyester is of a compact structure, high crystallinity, internal macromolecule non-hydrophilic gene, the difficulty of dyeing, and polyester fiber can be combustion, these are limited to a certain extent of the polyester fiber in the actual production and application. Therefore, development of a cationic dyeable the flame-retardant polyester fiber is very necessary.

In Japan especially male illustrious 34-10497 in its Bulletin, put forward a use 2-3 metal the mol % of the sulfonic acid group of isophthalic acid component of the polyester by copolymerization cationic dyeable polyester. From the Patent literature, however, the resulting polyester fiber, can only be in the high-temperature, the dyeing under high pressure, in the Department of natural fiber, polyurethane fiber, mixage, the interlacing, dyeing can not be carried out.

Application number 200410084108. X provides a dyeing with cationic dyes the flame-retardant polyester polymer and method for producing the same. Utilization of the same containing metal sulfonate isophthalic acid dimethyl ester as NaOH under the conditions of the catalyst, is respectively connected with the ethylene glycol reaction so that the extent of transesterification reaction is 95% or more, thus synthetic containing metal sulfonate two hydroxy ethyl ester phenyldiformate the ground (in this synthesis process there will be a large amount of methanol to produce, so the apparatus also provided with a methanol processor). Plus TPA (terephthalic acid) continue to esterification, condensation cauldron after the completion of the transfer, add catalyst antimony trioxide, hydroxyethyl phosphate flame retardant and ethanoic acid manganese make cationic dyeable flame-retardant polyester. The method, through step-by-step by adding cationic can be agent, fire retardant get the polyester having cationic dyeable and flame retardant property, however, its production process is complicated, in the production process by adding NaOH, acetic acid manganese as a catalyst, more types of the additive, is to be produced in the reaction process various side reaction, ultimate impact the performance of the product; and in the condensation polymerization of hydroxyethyl phosphate is added to react with the sulfonate to produce sulfurous acid, eventually lead to cationic dyeability can drop even disappear.

Cationic dyeable at home and abroad in their coverage of the flame-retardant polyester, the application number exists 200410084108. X the same problem, the production process is complicated, and because the fire retardant and cationic dyeable additive are esterification and polycondensation is divided into two stages to add, the need to add various types of the corresponding catalysts, lead to intermediate by-product will increase, so the reaction is not stable, the need to add various stabilizer composite catalyst and, eventually lead to increased cost, and furthermore, with the increase of side reaction, some by-product gado, the performance of products will not get very good improvement.

(C) the content of the invention

The aim of the invention is to overcome the traditional complex process, adding various catalyst, hydroxyethyl fire retardant and cationic dyeable compounding chemicals react at high temperature impact performance such as dyeing fibers, provides a simple process, there is little adding amount of the additive, and utilize carboxyethylation flame-retardant medicinal preparation with made of cationic dyeable assistant reaction with the reactant of the flame-retardant and dyeable properties, other properties of the polyester fiber is a small, low cost cationic dyeable the halogen-free flame-retardant polyester fiber preparation.

The purpose of this invention is realized as follows: a cationic dyeable the halogen-free flame-retardant polyester fiber preparation method, is composed of a 2-carbencillin ethyl hypophosphorous acid (CEPPA) and isophthalic acid sulfonic acid sodium react to produce flame-retardant cation can be dye type additive, and then with terephthalic acid (PTA), prepared by reacting ethylene glycol (EG), specific steps are as follows:

Step one, of cationic dyeable and flame retardant compound synthesis

The isophthalic acid sulfonic acid sodium salt, 2-carbencillin ethyl acid according to the molar ratio with deionized water (CEPPA) the 1 [...] 1.5-2.5 the [...] 10-30, added in a reaction vessel, the water bath is heated to the 50-80 [...] , reaction 1-5 hours, after the end of reaction, the reaction product is filtered, in 110-150 the obtained temperature [...] oven dried under cationic dyeable flame-retardant composite.

Step two, of cationic dyeable of the synthesis of halogen-free flame-retardant polyester chip

The terephthalic acid (PTA), step one product and ethylene glycol (EG) ratio of the 1 [...] 0.02-0.08 the [...] 1.15-1.25, in is added to the esterification reactors, stirred and heated up to esterifying the 230-250 [...] , control esterification reactors internal pressure reaches the 200-400kPa, reaction 1-2 hour, the esterification rate reach 90-99% above esterification end of the, discharge pressure, and then adding the quality of terephthalic acid (PTA) 0.01-0.1% of the glycol antimony catalyst, mixing and stirring 10-20 minutes later, into the condensation polymerization kettle, start the vacuum pump in -50--105kPa maintain the system pressure, in the temperature control of reaction the 260-280 [...] , reaction 1-4 hours discharging gets the cationic dyeable fire-retardant polyester slice.

Step three, of cationic dyeable the halogen-free flame-retardant polyester fiber preparation

Step b preparation of cationic dyeable fire-retardant polyester slice by vacuum rotary drum drier, drying temperature the 130-150 [...] , the holding time is 4-12 hours; slice after drying in accordance with the conventional polyester spinning process for spinning the spinning machine, to obtain cationic dyeable the halogen-free flame-retardant polyester fiber.

The present invention first through the m-phthalic acid sodium sulfonate and 2-carbencillin ethyl hypophosphous acid, synthetic flame retardant cation can be dye type adjuvant, glycol antimony as a catalyst can be under the effect of reaction with the polyester, without adding other types of catalyst. Avoid the traditional two-step adding fire retardant and cationic dyeable assistant, need to add various different catalyst, various types of effectively inhibiting the occurrence of side reactions. And the use of the carboxyl groups of the phosphoric acid fire retardant, will not react with the sulfonate, sulfonic group of cationic dyeable not reduce, to dyeability is not affected. And 200410084108. X compared with, not only the production cost is greatly reduced, and the product performance is greatly improved.

This invention, through the molecular structure of the long-term research and testing, to find one of the isophthalic acid and sodium sulfonate chemical reaction of the fire retardant 2-propyloic hypophosphous acid, synthesized a new kind of flame retardant of cationic dyeable adjuvant. Such a with fire-resistant and cationic dyeability can be additive, relative to the independent of the fire retardant and cationic dyeable adjuvant, can add calais completed through the one-step flame-retardant and cationic dyeability of the polyester, prevent the traditional two-step adding fire retardant and cationic dyeable aid of various and complicated process for the occurrence of side reactions, with more stable, the role of cationic dyeable and flame-resistant.

The obtained cationic dyeable the halogen-free flame-retardant polyester, viscosity and melting point than the conventional PET similar polyester chip, has good spinnability, will not affect other properties of the fiber. Spun using conventional spinning techniques of cationic dyeable the halogen-free flame-retardant polyester fiber, the index reaches oxidation of fiber 38-40, has very good flame retardant properties, cationic dyed bright colors can be obtained.

The process of the invention is simple, there is little adding amount of additive, the effect on other properties of the polyester fiber is very small, low cost, in accordance with the requirements of the practical production and application.