TW200914515A - Flame-retardant cationic dye-dyeable copolyester polymer, manufacturing method thereof and flame-retardant cationic dye-dyeable copolyester fibers - Google Patents

Abstract

Disclosed herein are a flame-retardant cationic dye-dyeable copolyester polymer, a manufacturing method thereof, and a fiber using the same copolyester polymer. Specifically, the present invention provides a flame-retardant cationic dye-dyeable copolyester polymer comprising 0.5 to 3 mol% of a metal sulfonate-containing compound based on the total carboxylic groups of the polymer and 500 to 50000 ppm of a phosphorus-based flame retardant in terms of phosphorus atoms based on the total weight of the polymer, preparation thereof, and a fiber using the same copolyester polymer. Therefore, the present invention enables inexpensive production of a copolyester polymer and a fiber thereof having excellent cationic dyeability and flame retardancy via a three-tubular TPA polymerization process.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymerized vinegar polymer which can be dyed by a flame-retardant cationic dye, and a process for producing the same, which is a copolymerized vinegar fiber which can be dyed by a cationic cationic dye. More specifically, the present invention relates to a flame retardant cationic dye-dyeable copolyester polymer which exhibits excellent cationic dyeability and high barrier properties, which are prepared by a TPA polymerization method; a method for producing the same; and a cationic dye A dyeable copolyester fiber which has excellent false twist processability. [Prior Art] A conventional method for preparing a flame-retardant cationic dye, a color-soluble copolymer, and a fiber thereof using a metal rhein compound, and a disadvantage of the conventional method High manufacturing costs. Furthermore: 1糸 is represented by the following compounds: 9,10_二气如亚-10-2,3-爹 爹 propyl propyl 10-distributed phenanthrene The derivative has a low phosphorus content, so it must be added, /, with only a large amount of flame retardant added to achieve flammability. As a result, the high resistance d of the phosphorus-based flame retardant causes a severe temperature, and the polymer is often melted during the manufacturing period of the false twist yarn, and the processability is deteriorated. u This has led to a strong need for this method, which can provide excellent dyeability and resistance at low cost and low cost: "Copolymer with improved false twist processability Cool fiber., and 9,10-_ hydrogen_9_noise-1 〇_2 3- _ μ shangan derivative, - propyl propyl ketone, - oxygen 200914515 ο

One (CHiX — CH — C00R

CH plant COOR5

Wherein R4 and R5 are independently a monovalent ester to form a functional group, and p is 1 to an integer. Reference 1 · 曰本未审查专利专利编号2005_273043 Reference 2: 曰本未审查专利专利编号2004-丨〇751 6 Reference 3: 未本未审查专利专利编号号 2〇〇6_169687 The present invention has been made in view of the above problems, and an object of the present invention is to provide a flame retardant cationic dye-dyeable copolyester polymer which has an excellent combination of positive and negative. The % ion dyeability and flame retardancy at atmospheric pressure is another object of the present invention to provide a dyeable copolyester polymer, which is cost-effective. A flame retardant cationic dye is produced which has improved processability and another object of the invention of the winter is a colored copolyester fiber having a superior composition and a woven or needle fabric. The flame-retardant cationic dye can be dyed and processed, and the above-mentioned polycondensation is used according to the invention. The above-mentioned is a flame-retardant cationic aggression, and the purpose is to provide a flame-retardant cationic dye, , the polyester polymer to achieve, the color of the copolymerized polymer comprises: 200914515 based on the total carboxyl group of the polymer, 05 to 3 people in the eight-way inch 0 of the metal containing % salt Compound, formula 1:

S03M where the alkali metal, · and cooch2ch2oh 5〇0〇〇ppm

In the case of a phosphorus atom based on the total weight of the polymer, a phosphorus-based flame retardant of 5 Å to 2, Formula 2: II υ R1 - 0-f - CH2 - CH ϋ - ο - R3

Ft2 wherein R1, R2 and r3 are each independently a gas, a stupid or a calcination group. According to another aspect of the present invention, there is provided a method of producing a flame retardant cationic dye dyeable copolymerized vinegar polymer by a polymerization method using terephthalic acid (TPA) as a starting material, wherein The polymer comprises a compound of the formula 2 having a genus of 2 sulfonate based on the total rebellion of the polymer of '0.5 to 3 mol%' and 500 to 50000 ppm based on the phosphorus atom based on the total weight of the polymer. A phosphorus-based flame retardant represented by Formula 2. According to still another aspect of the present invention, there is provided a flame-retardant cationic material-dyeable copolymerized vinegar fiber which is prepared by using the above-mentioned copolymerized vinegar polymer, and a woven or knitted fabric. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The above and other features of the present invention will be described in detail with reference to the accompanying drawings. invention. The invention will be described in more detail below with reference to Fig. 1 . Briefly, the TPA polymerization process for preparing the polymer of the present invention will be described as follows: (a) A slurry of TPA and ethylene glycol (EG) as a reactant is prepared in the preparation reactor 1, and then stored. In the slurry reservoir 2. (b) The slurry of the storage tank 2 is supplied to the first esterification reactor (hereinafter referred to as "^, DE-1") 3 for esterification 'where the base polymer is always retained. (c) The second transport line filter (tank filter) 4 transfers the esterified aroma from the DE-1 reactor 3 to the second esterification reactor (hereinafter referred to as "DE-2," ) 5. (d) The transferred oligomer is further reacted in the DE 2 reactor 5, and then the metal sulfonate-containing compound of the formula and the dish-based flame retardant of the formula 2 are added thereto. 0) transferring the obtained flame-retardant polymerase from the DE 2 reaction amount of 5 to the polycondensation reactor (hereinafter referred to as PC reactor) 7 via the second transfer line filter (basket filter) 6, and The reaction produces a flame-retardant polyester. (f) The polymer prepared in the PC reactor 7 is discharged from the granulator 8 and then cut into small pieces. In order to exhibit cationic dye dyeability in the present invention, use The m-dicarboxylic acid of the metal of the formula (1) to the bismuth salt is acetoacetic acid (hereinafter referred to as "Des"). When using a conventional commercially available metal sulfonate-containing stearic acid When brewing without the use of isophthalic acid double-methane (DES), it may still be partially unreacted in the τρΑ polymerization process, thus causing an increased filling pressure and impairing processability during the spinning process. Preventing side reactions such as gel formation due to thermal decomposition of DES, and adding the metal sulfonate-containing compound of Formula 1 to DE-2 reactor 5. The formula 'sole can be added separately or with Formula 2 Phosphorus-based flame retardants are simultaneously added. It is preferred to separately add the compounds of Formula 1 & 2. Specifically, After dissolving in ethylene glycol (EG), a phosphorus-based flame retardant is first added, and then a metal-containing phthalate is added after vinegarization between the phosphorus-based flame retardant and EG. Based on the total carboxyl group, the metal sulfonate-containing compound preferably has a 〇·5 to 3 mol% range. When the metal phthalate-containing compound has a g 畺 lower than 〇·5 mol At the time of %, it is difficult to achieve cationic dye dyeability. On the other hand, when the content of the metal sulfonate-containing compound is higher than 3, the degree of polymerization of the filling may be difficult due to the rapid increase of the melt viscosity. In the present invention, the phosphorus-based flame retardant of Formula 2 is used to impart flame retardancy. The formula of the present invention is used to impart flame retardancy. The flame retardant of 2 has a high phosphorus content for being responsible for flame retardancy, such as a flame retardant (9,10-dihydro-9-oxo-10-2,3-dicarbonylpropyl-) Compared with the 10-phosphonium phenanthrene _10_oxide derivative), the flame retardant of the formula 2 can exert the desired flame retardancy 'even if added in small amounts And effective: lowering the melting point of the prepared polymer. The phosphorus-based flame retardant is preferably in the range of 5 〇〇 to (10) ❹卯, in the case of phosphorus atoms responsible for flame retardancy, The total weight of the material is based on the benchmark. When the phosphorus content is less than 500 Ppm, it is difficult to achieve flame retardancy. On the other hand, when the phosphorus content is higher than 50 ppm, 200914515 may have disadvantages such as lowering the melting point of the polymer and increasing the manufacturing cost, rather than improving Flame-retardant. The phosphorus-based flame retardant of Formula 2 may be added in the form of a powder, a solution thereof in (10), or a acetated product of EG, and a phosphorus-based flame retardant may be added after the towel is dissolved. The addition of a powdery flame retardant reduces the reaction rate of the oligomer, which may result in deterioration of the polymerization processability. The addition of the acetated product can disadvantageously result in the production of a large amount of by-product, diethylene glycol (DEg). Further, it is preferred to add the phosphorus-based flame retardant of the formula 2 to the reactor 5. When the flame retardant is introduced into the polymer preparation reactor i' slurry tank 2 or just reactor 3, it will lead to long-term retention of the phosphorus-based flame retardant in the reactor, resulting in the continued increase of by-products (4). Therefore, the uniformity of the polymer is impaired. When the flame retardant is introduced into the PC reactor 7, the time after the condensation is reversed is delayed, making it difficult to control the reaction cycle. The poly(p-ethylidene dicarboxylate) (pET) according to the present invention was polymerized using butyl (yield: 1丨6%), and its yield was theoretically higher than that of DMp (yield: 99%). As the polycondensation catalyst, an antimony compound which is widely used in the production of polyester is used, and is excellent in cost effectiveness and physical properties. Diethylene glycol (DEG) is produced as a by-product from the acid component of TPA during the TPA polymerization process. In the present invention, the DEG content of the polymer is preferably in the range of 15 to 45 % by weight based on the total weight of the polymer. In the polymerization method according to the present invention, DE (3 content cannot be lower than i 5 wt%. When t DEG content is higher than h5 wt%, the obtained flame retardant cationic dye dyeable copolyester fiber cannot be improved. Dyeing. However, although the DEG content exceeds 4.5 wt%, the spinnability and false twist properties of the polymer may be impaired due to very poor thermal stability, 200914515. Unreacted based on the total weight of the polymer. The content of the end of the TPA and the thermal decomposition is preferably in the range of 30 to 60 equivalent / ° town. When the content of the terminal carboxyl group is 30 equivalent / ton, the reaction temperature is lowered and the EG content is caused. As a result, the reaction time is increased, thus leading to unfavorable results such as degradation of the polymer and increase in by-product DEG. On the other hand, when the content of the terminal carboxyl group is higher than 60 equivalents / ridicule, the degradation of the polymer may This leads to gelation or other problems because most of the terminal carboxyl groups are produced by thermal decomposition. The content of unreacted TPA in the polymer is preferably less than 20 ppm because unreacted TPA neither melts when the content exceeds 20 ppm. It does not dissolve well in the solvent, which may impair the spinnability of the polymer. The inherent viscosity of the polymer prepared in the present invention is preferably in the range of 〇.5 to 0.7 dl/g. At 0.5 dl/g, it is difficult to process the polymer into the original yarn' and the polymer cannot be used to make the original yarn because of the very poor strength. When the intrinsic viscosity is higher than 0.7 dl/g, the melt viscosity of the polymer is clearly The increase, because of the ionic bond between the metal acid salt compounds to be added, which leads to the inapplicability of the conventional polyester polymerization equipment, and it is difficult to achieve uniform melting of the polymer during the spinning process. It is in the range of 21 5 to 240 ° C. When the tempering temperature is lower than 21 5 ° C, 'the spinning property may be damaged due to low heat resistance' and due to the polymer during the process: Wrapping and sticking, it is difficult to manufacture false crepe or impair workability. When polyethylene terephthalate (PET) is copolymerized by 200914515, the melting point increases. Therefore, it is difficult to obtain a melting point higher than 240 c. Polymer. On the other hand, when When the temperature is higher than 240 〇c, the unreacted copolymerized monomer may remain in the polymer, thus impairing the quality of the polymer and the fiber. EXAMPLES The present invention will now be described in more detail with reference to the following examples. The examples are for illustrative purposes only and are not intended to limit the scope and spirit of the invention. (Example 1 In a slurry preparation reactor 1, EG and TPA are mixed at a molar ratio (G value) of 1.25:1, To prepare a slurry, and to store the obtained slurry in the slurry storage tank 2. The slurry is continuously fed into the DE-1 reactor 3, wherein the _3 singly melts the base polymer to the benzene. Dihydroxyethyl formate and mix at 258 C. When the esterification of the polymer in the DE-1 reactor 3 reached 96%, the 1.5-esterified oligomer was transferred to the De_2 〇 reactor 5 via the basket filter 4. The oligomer transferred to the DE-2 reactor 5 was continuously stirred for 9 minutes. In the DE-2 reactor 5, 7200 ppm of 3-hydroxyphenylphosphinyl propionic acid (HPP) was added as a phosphorus-based flame retardant of Formula 2 in terms of phosphorus atoms based on the total polymer weight. A concentration of 50% by weight was dissolved in the EG. Then, the reaction is continued under mixing. After 90 minutes, based on the total carboxyl group, a sodium sulfoisophthalate (DES) having a degree of intrinsicity of 1.3 mol% was added as the metal sulfonate compound of the formula 1, and in the DE-2. Stir in the reactor 5. The unreacted EG contained in the phosphorus-based flame retardant and the metal sulfonate-containing compound is removed in a low vacuum state, and then transferred to the polycondensation reactor 7. In a polypolymer 12 200914515, a 1% antimony trioxide solution was added to the polymer of the condensation reactor 7 (trioxide concentration = 300 ppm based on the weight of the polymer), followed by 285.反应 React under high vacuum for 4 hours. The reaction product is discharged via a granulator 8. The physical properties of the obtained polymer are shown in Table 1 below. Example 2 The polymer of Example 1 was spun at 288 C using a conventional melt spinning apparatus at a rate of 2800 meters per minute. Using a disc-shaped false twister, the resulting partially oriented yarn (POY) 133 dtex/48 monofilament will be false-twisted at a draw ratio of i 66 (500 m/min yarn speed, and 20 (TC) Heater temperature)' to prepare a false twist yarn of 84 dtex/48 monofilament. A good false yarn was obtained, which showed no adhesion to the hot plate and no hairiness. The false twisted yarn was knitted by the right, then by the cationic dye (Kayacryl , Japan National Chemical Co., Ltd.)) Uniform dyeing. When evaluating flame retardancy, the yarn exhibited good flame retardancy, corresponding to a limiting oxygen index (LOI) of 32. Comparative Example 1 Same as the example A method of preparing a polymer, except that based on the total weight of the polymer, 200 ppm of 3-hydroxyphenylphosphinyl propionic acid (HPP) is added in terms of phosphorus atoms. Physical properties of the polymer. Comparative Example Polymers were prepared in the same manner as in Example 1, except that the total carboxyl group of the complex was used as a reference, and 丨0 mol% of bishydroxyethyl succinate was added ( DES). The prepared polymer is easily embrittled and therefore not cut into small pieces. The physical properties of the obtained polymer are shown in the following Table 1. 13 200914515 η Comparative Example 3 The polymer was prepared in the same manner as in Example 1 except that the following compounds were added as a phosphorus-based flame retardant- ~ Ask is to borrow 0 / 〇 compound (R4 and R5 = -CH2CH2 〇 h not material in the 65 weight ' and ρ = η 7 _ liquid, to produce 7200ppm dish atomic yttrium., < c - alcohol soluble 0. The physical properties of the polymer obtained from Table 1 below. The results shown in (9,10 --wind-9-° evil-10-2,3--Miscellaneous, rebel propyl-1〇_ Oxide derivatives) 0 醯 醯 菲 菲 -1 〇 〇.

P-(CH2)c-CH-C00R4 I I 0 CH-C00R5 to 5 wherein R4 and R5 are independently a monovalent ester to form a functional integer. The soil, and P, a comparative example 4, were spun and false-twisted in the same manner as in Example 2. The polymer exhibited a mass of good preparation. During the process period, the entanglement of the sorcerer's squad is 4, but it will adhere to the heating plate during the false 枉 and 枉. The occurrence of the drop ~ ~ Umbrella low heat treatment temperature will cause the hairy rabbit to be born, due to the false yarn in the disc-shaped false twister. ',,, it is difficult to get a good false twist yarn 14 200914515 Table melting temperature (°c) Example polymer IV (dl/g) 〇£0 (% by weight)

220.8 7200 253.2 7200 214.5 Phosphorus content (ppm) 200 7200 Metal sulfonate content (mole 0 / 〇) 1.3 1.3 10.0 1.3 ◎ The polymer of Comparative Example 2 showed no stunning peak on DSC. The polymerization prepared in the present invention The physical properties of the material were analyzed as follows: 1 • Degree of esterification of terephthalic acid: The concentration of the carboxylic acid of the esterified oligomer was measured by titration. 2_Intrinsic viscosity (IV): The polymer was dissolved in a 6:4 (w/w) solution of phenol and u,2,2-tetrachloroethane. The iv was measured in a constant temperature bath at 30 ° C using an Ubbei〇hde viscometer. 3. Melting temperature and glass transition temperature: A differential scanning calorimeter (DSC7, PerkinElmer) was used at a heating rate of 1 Torr/min. ' 4. Disc flame retardant and DES content analysis.

• • Performed by 400 MHz NMR 5. DEG contains the polymer dissolved in ethanolamine and analyzed by gas chromatography. Head 15 200914515 6. Flame retardancy: After the false crepe, refining, reduction and dyeing, according to KSM 3032, it is evaluated as the limiting oxygen index (l〇i). As can be seen from the above description, according to the present invention, the fiber has excellent cationic dyeability under atmospheric migration, and § is excellent in two-tone color when mixed with flame-retardant poly(tetra) yarn. Effect and high resistance. A, ππ ^ . . . , , and again, the manufacturing method of the present invention can inexpensively produce a flame retardant cationic 1 α Α d ', color 々/, e ester polymer and fibers thereof, jg: The manufacturing period of the yarn indicates that the low frequency polymer melts. . . . Although the preferred embodiment of the present invention has been disclosed for the purpose of illustration, those skilled in the art will be able to devise various modifications, additions and substitutions. Attached to the scope of the patent application is the van and the gods. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a three-tube type T reactor for preparing a polymer of the present invention. Λ [Main component symbol description] 1 Preparation reactor 2 Slurry storage tank 3 First esterification reactor 4 First transfer line filter 5 Second esterification reactor 6 Second transfer line filter 7 Polycondensation reactor 8 Granulator 16

Claims (1)

200914515 X. Patent application scope: 1 · A flame retardant cationic dye dyeable copolyester polymer comprising: 0 to 5 to 3 moles based on the total carboxyl groups of the polymer. /. a metal sulfonate-containing compound of the formula: Formula 1: S03M H0CH2CH20C0 COOCH0CH2OH wherein the lanthanide alkali metal; and the phosphorus-based flame retardant represented by Formula 2 in an amount of 500 to 5 ppm based on the total weight of the phosphorus atom of the polymer, Formula 2: 0 0 , II | | R — 0—P—CH 2 —CH — — C — 0 — R 3 R 2 wherein R 1 , R 2 and R 3 are each independently hydrogen, phenyl or C! to c 7 alkyl. 2. The polymer of claim 1 wherein the polymer has an intrinsic viscosity of from 0.5 to 7.7 dl/g and a temperature of 215 of 240 ° C. 3. The polymer of claim 1 wherein the amount of terephthalic acid (TPA) unreacted in the polymer is less than 20 ppm. 4. The polymer of claim 1 wherein the content of terminal tethers in the polymer is in the range of from 3 to 60 equivalents. 5. The polymer of claim 1 wherein the amount of diethylene glycol (DEG) in the polymer is in the range of from 1.5 to 4% by weight based on the weight of the polymer. 17 200914515 6_ - A method for producing a flame retardant cationic dye dyeable copolyester polymer 'which uses a three-tube TPA polymerization method' wherein the polymer comprises: a total carboxyl group of the precursor as a reference, 〇 5 to 3 a metal sulfonate-containing compound of the formula ,, formula 1: H0CH2CH20C0 So3m C00CH?CH?0H wherein the μ-based alkali metal; and 500 to 50000 ppm of the phosphorus-based flame retardant represented by Formula 2 based on the total weight of the polymer-based phosphorus atom, Formula 2: R'-〇-Bu CH (3⁄4一J_〇_r3 wherein Rl, R2 and R3 are each independently hydrogen, phenyl or Ci to C7 alkyl. ^, the method of claim 6 of the patent scope, wherein the three-tube type τρΑ is gathered The method comprises the step of adding a metal sulfonate-containing compound of <1 and a flame retardant of the formula 2 to the second (f) t reaction H(DE_2). The method of claim 1, wherein the formula Metal: Before the introduction of the compound, the filled flame retardant of the formula 2 is added. The copolymerized polymer which can be dyed with the two special ion dyes is prepared by the polymer of the first item.哉 or knitted fabrics, which are prepared according to item 9 of the patent application, IS fiber.